GB1602902A

GB1602902A – Radiationsensitive copying composition
– Google Patents

GB1602902A – Radiationsensitive copying composition
– Google Patents
Radiationsensitive copying composition

Download PDF
Info

Publication number
GB1602902A

GB1602902A
GB16074/78A
GB1607478A
GB1602902A
GB 1602902 A
GB1602902 A
GB 1602902A
GB 16074/78 A
GB16074/78 A
GB 16074/78A
GB 1607478 A
GB1607478 A
GB 1607478A
GB 1602902 A
GB1602902 A
GB 1602902A
Authority
GB
United Kingdom
Prior art keywords
composition
groups
alkyl
radiation
substituted
Prior art date
1977-04-25
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB16074/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Hoechst AG

Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1977-04-25
Filing date
1978-04-24
Publication date
1981-11-18

1978-04-24
Application filed by Hoechst AG
filed
Critical
Hoechst AG

1981-11-18
Publication of GB1602902A
publication
Critical
patent/GB1602902A/en

Status
Expired
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

Classifications

G—PHYSICS

G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY

G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR

G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

G03F7/004—Photosensitive materials

G03F7/022—Quinonediazides

G—PHYSICS

G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY

G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR

G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

G03F7/004—Photosensitive materials

G—PHYSICS

G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY

G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR

G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

G03F7/004—Photosensitive materials

G03F7/016—Diazonium salts or compounds

G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders

G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds

G—PHYSICS

G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY

G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR

G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

G03F7/004—Photosensitive materials

G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof

Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface – process, composition, or product: radiation sensitive composition or product or process of making binder containing

Y10S430/1055—Radiation sensitive composition or product or process of making

Y10S430/114—Initiator containing

Y10S430/115—Cationic or anionic

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof

Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface – process, composition, or product: radiation sensitive composition or product or process of making binder containing

Y10S430/1055—Radiation sensitive composition or product or process of making

Y10S430/114—Initiator containing

Y10S430/12—Nitrogen compound containing

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof

Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface – process, composition, or product: radiation sensitive composition or product or process of making binder containing

Y10S430/1055—Radiation sensitive composition or product or process of making

Y10S430/114—Initiator containing

Y10S430/126—Halogen compound containing

Description

PATENT SPECIFICATION ( 11) 1602902
C ( 21) Application No 16074/78 ( 22) Filed 24 April 1978 0 ( 31) Convention Application No2 718 254 ( 19) C ( 32) Filed 25 April 1977 in e 2 ( 33) Fed Rep of Germany (DE) C ( 44) Complete Specification published 18 Nov 1981 ( 51) INT CL 3 C 08 G 4/00; GO 3 C 1/52, 1/72 ( 52) Index at acceptance C 3 R 19 DA 3 19 DAX 19 DB 4 19 P 5 P SM C 3 Y B 390 B 393 G 2 C 1 BIH 1 D 3 D 1 G 1 1 G 2 1 G 3 1 G 5 1 H C 4 A C 4 C 2 B 2 C 4 C 6 CXA ( 54) RADIATION-SENSITIVE COPYING COMPOSITION ( 71) We, HOECHST AKTIENGESELLSCHAFT, a Body Corporate organised according to the laws of the Federal Republic of Germany, of 30 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is performed to be particularly described in and by the 5 following statement:-
The present invention relates to radiation-sensitive compositions, as well as articles, employing such compositions, forming copying materials.
Positive-working light-sensitive copying materials, i e materials the copying layers of which become soluble in the exposed areas, are known Positiveworking 10 copying compositions based on o-quinone diazides have gained general acceptance.
Frequently, the light-sensitivity of these copying materials is not satisfactory.
The light-sensitivity may be increased by using catalytically-acting light-sensitive systems, because in this case the quantum yield becomes greater than 1, The 15 principle of initiating secondary reactions by means of photolytically produced acids and thus causing the exposed areas to become solufble fhas been recently proposed for positive-working systems In these materials, photochemically produced strong acids are used for splitting low or high molecular weight acetals and O N-acetals (i e, and acetal having one ether and one amino linkage) 20 containing aromatic compounds as hydroxyl or amine constituents (U S Patent No 3,779,778) or for splitting orthoesters and amide acetals (German Offenlegungschrift No 2,610,842) and British Specification No 1,548,757.
Furthermore, a combination of photochemical acid formers with certain polyaldehydes and polyketones has also been disclosed as a positiveworking 25 copying composition which yields visible images upon exposure (U S Patents Nos.
3,915,704, 3,915,706, 3,917,483 and 3,932,514).
These compositions are, however, not without disadvantages The polyaldehydes and polyketones which to a large extent determine the quality of the recording materials containing them are not capable of readily being provided with 30 material properties by which they might be adapted to practical requirements.
Despite their catalytical operation, the light-sensitivity of the copying compositions containing the above-mentioned acetals and O N-acetals is in practice not satisfactory Moreover, many of the above-mentioned acetals, O Nacetals and 0-esters are not readily available 35 The present invention provides a composition comprising a polymer having recurring units having acetal or ketal groups in the chain, each a-carbon atom of the alcohol constituent of the acetal or ketal being aliphatic or cycloaliphatic, the solubilitv of the polymer being increased by the action of an acid, and a compound which forms an acid under the influence of actinic radiation 40 The invention also provides a copying material comprising the composition of the invention in the form of a layer, either unsupported or supported on a permanant or temporary support.
In this specification, the term “actinic radiation” includes any radiation whose energy at least corresponds to that of short-wave visible light Longwave ultraviolet 45 radiation is particularly suitable, as are electron and laser beams.
2 1,602,902 2 The solubility of the polymer that is increased by acid action is advantageously that of the polymer in a developer liquid Suitable liquid developers are especially aqueous solutions, preferably weakly alkaline solutions, but organic solvents, which may, if desired, be mixed with water or with aqueous solutions, may also be used 5 The term “alcohol constituent” includes, especially, that part of the recurrent unit of the polymer which is derived from an alcohol, preferably a polyhydric alcohol The term shall, however, also cover that part of a hydroxyl alkyl carbonyl compound or a unit derived therefrom which carries one or more alcoholic OH groups, as will be explained in the following in greater detail 10 “Alcoholic OH groups” in the sense used in the present application are those groups of which not more than one is attached to a saturated aliphatic carbon atom It is essential for the carbon atoms in the a-position, each of which is connected to one oxygen atom only of the acetal or ketal group, to be saturated aliphatic or cycloaliphatic carbon atoms 15 Among the polymeric compounds containing recurrent acetal and/or ketal groupings, those are preferred which are obtainable by, and especially those obtained by, reaction of aldehydes and/or ketones (or their synthetic equivalents) with dihydric alcohols, with polyaddition and/or polycondensation, polymeric compounds containing units of the general formula I being particularly preferred: 20 A(-C-O R 3 C-O Rg-) I R, R, in this formula n is an integer from I to 40, preferably between I and 20, R 1 and R 4 are H, alkyl groups, preferably such with I to 12 carbon atoms, or aryl groups and 25 R 3 and RB are alkylene groups with at least 2, preferably 2 to 18, and most advantageously 4 to 18 carbon atoms and R 2 and R, are alkyl groups, preferably such with 1 to 12 carbon atoms, or aryl groups, and two of the groups R 1, R 2 and R 3 and two of the groups R 4, R, and R, may be connected with each other to form a substituted or unsubstituted ring, 30 or alternatively R 3 and RB are alkylene groups with at least 2, preferably from 2 to 18, and most advantageously 4 to 18 carbon atoms and R 2 and R 5 are alkoxy groups which are combined with R 3 and R 6 to form a substituted or unsubstituted, preferably 5 to 7-membered ring, and R 3 may be 35 combined with R 4 and, when is greater than 1, R, may be combined with R 6 of the neighbouring unit to form substituted or unsubstituted rings.
In the alkylenoxy groups R 3 and R-, the oxygen atom is on the right hand side of the group as shown in Formula I.
Aryl groups are mono or multinuclear aromatic or heteroaromatic groups, 40 normally with 6 to 20 carbon atoms, which may be substituted by alkyl, halogen, cyano, sulfonyl, acyl or carbalkoxy groups Mononuclear aromatic groups, especially phenyl groups, are preferred.
Alkyl groups are branched or unbranched, saturated or unsaturated, cyclic or open chains which may be substituted by, optionally substituted aryl, halogen, 45 cyano, ester, aryloxy or alkoxy groups and may contain ether or keto groups.
Preferred alkylene groups are saturated or unsaturated, branched or unbranched, aliphatic and cycloaliphatic groups, which may be substituted by ester groups, alkoxy groups or aryloxy groups or may contain keto groups Furthermore, individual members of the carbon chain may be replaced by hetero atoms, 50 preferably oxygen In each case, the terminal members of all alkylene groups should be saturated aliphatic or cycloaliphatic carbon atoms.
A special group among the polymeric compounds containing units corresponding to formula I are the polycondensation products containing recurrent units of the general formula II which are obtainable, or are obtained by, 55 reacting aldehydes R 1 CHO or acetals RCH(OR,)2 with diols HOR 3 OH:
1,602,902 ( CH-OR 3-O-m; 11 wherein m is an integer from 2 to 80, preferably between 3 and 40, R is an alkyl group, preferably one with I to 12 carbon atoms, or an aryl group, 5 R 3 is an alkylene group having at least two carbon atoms, preferably one with 4 to 18 carbon atoms, the oxygen atoms of the group O-R 3-O being linked to different carbon atoms of the alkylene group, and R 7 is an alkyl group, preferably one with I to 6 carbon atoms, especially a methyl or ethyl group 10 Otherwise, the aryl, alkyl and alkylene groups have the meanings defined above.
If different aldehydes or acetals and/or diols are used, different units corresponding to formula II are obtained in a statistical arrangement The statistical arrangement depends on the number of acetal-forming constituents and 15 their relative amounts In view of the easier availability of the aldehydes, as compared with acetals, aldehydes are preferred as the components forming polyacetals A general account of the methods of preparing acetals is given, for example, in “Methoden der organischen Chemie” (Methods of Organic Chemistry) by Houben-Weyl, Vol IV/3 20 The following compounds are mentioned as examples of suitable aldehydes, or of aldehydes from which the acetals used as initial substances are derived:
acetaldehyde, chloral, ethoxy acetaldehyde, benzyloxy acetaldehyde, phenyl acetaldehyde and diphenyl acetaldehyde, phenoxy acetaldehyde, propionaldehyde, 2-phenyl and 3-phenyl-propionaldehyde, isobutoxy and benzyloxy pivalic 25 aldehyde, 3-ethoxypropanal, 3-cyano-propanal, n-butanol, iso-butanal, 3chlorobutanal, 3-methoxy-butanal, 2 2-dimethyl-4-cyano-butanal, n-pentanal, 2 and 3methyl-pentanal, 2-bromo-3-methyl-butanal, 2-bromo-3-methyl-butanal, nhexanal, 2 and 3-ethyl-butanal, 4-methyl-pentanal, cyclopentane carbaldehyde, nheptanal, cyclohexane carbaldehyde, 1 2 3 6-tetrahydrobenzaldehyde, 3ethyl 30 pentanal, 3 and 4-methyl-hexanal, n-octanal, 2 and 4-ethyl-hexanal, 3 5 5trimethyl-hexanal, 4-methyl-heptanal, 3-ethyl-n-heptanal, decanal, the monohydroformylation product of dicyclopentadiene, dodecanal, crotonic aldehyde, benzaldehyde, 2-, 3 and 4-bromo-benzaldehyde, 2-, 3 and 4-chloro-benzaldehyde, 2 4-dichloro and 3 4-dichloro-benzaldehyde, 4-methoxybenzaldehyde, 35 2.3-dimethoxy and 2 4-dimethoxybenzaldehyde, 2-, 3 and 4-fluorobenzaldehyde, 2-, 3 and 4-methyl-benzaldehyde, 4-isopropyl-benzaldehyde, 3 and 4tetrafluoroethoxy-benzaldehyde, 1 and 2-naphthaldehyde, furfural and thiophene-2aldehyde.
Suitable dihydric aliphatic alcohols are, for example: Pentane-l 5-diol, n 40 hexane-1 6-diol, 2-ethyl-hexane-1 6-diol, 2 3-dimethyl-hexane-1 6-diol, heptane1.7-diol, cyclohexane-1 4-diol, nonane-1 7-diol, nonane-l 9-diol, 3 6dimethylnonane-I 9-diol, decane-I 10-diol, dodecane-l 12-diol, 1 4-bis(hydroxymethyl)cyclohexane, 2-ethyl 1 4-bis-(hydroxymethyl)-cyclohexane, 2-methyl-cyclohexane 1 4-diethanol, 2-methyl-cyclohexane 1 4-dipropanol, thiodipropylene 45 glycol, 3-methyl-pentane 1 5-diol, dibutylene-glycol, hydroxypivalic acidneopentylglycol ester, 4 8-bis-(hydroxymethyl)-tricyclodecane, n-butene-( 2)1 4-diol, n-but-2-yne-1 4-diol, n-hex-3-yne-2 5-diol, 1 4-bis-( 2-hydroxyethoxy)butyne-( 2), pxylyleneglycol, 2 5 dimethyl-hex-3-yne-2 5-diol, bis-( 2-hydroxyethyl)sulfide, 2 2 4 4-tetramethylcyclobutane-l 3-diol, di-, tri-, tetra-, penta and hexaethylene 50 glycol, di and tripropyleneglycol and polyethylenedglycols with an average molecular weight of 200, 300, 400 and 600.
A further special group of polymeric compounds containing units corresponding to the general formula I are the polycondensation products with recurrent units corresponding to the general formula I Ia, which are obtainable or 55 obtained by reaction of ketals R,(R 2)C(OR 7)2 with diols HOR 3 OH.
Rl C-OR 30-+ m; I Ia 4 1,602,902 4 where m, R, R 3 and R 7 have the meanings given under Formula II, and R 2 is an alkyl group, preferably with 1 to 12 carbon atoms, or an aryl group.
Moreover, R, and R 2 may be part of a common ring which may be substituted.
Aryl, alkyl and alkylene groups are those defined in connection with formula I If different ketals and/or diols are used, different units corresponding to formula I Ia 5 are obtained in a statistical arrangement The statistical arrangement depends on the number of ketal-forming constituents and their relative amounts The ketals used as initial compounds may be prepared analogously to the acetals defined by formula II Suitable diols are those listed in connection with formula II, for example 10
The ketals may be derived from the following ketones, for example: phenyl acetone, 1 3 diphenyl acetone, 2 2 diphenyl acetone, chloro and bromoacetone, benzyl acetone, butan 2 one, benzyl-propyl ketone, ethyl benzene ketone, benzyl methyl ketone, 5 methyl hexan 2 one, 2 methyl pentan 2 one, 2 methyl pentan 3 one, hexan 2 one, hexan 3 one, pentan 15 3 one, 2 methyl butan 3 one, 2 2 dimethyl butan 3 one, 5 methyl heptan 3 one, octan 3 one, octan 4 one, octan 2 one, nonan 2 one, nonan 3 one, nonan 5 one, heptan 2 one, heptan 3 one, heptan 4 one, undecan 5 one, undecan 6 one, dodecan 2 one, dodecan 3 one, dinonyl-ketone, undecan 4 one, undecan 2 one, tri 20 decan 2 one, tridecan 3 one, dodecan 5 one, dioctyl-ketone, 2methyl octan 3 one, cyclopropyl methyl ketone, decan 2 one, decan 3 one, decan 4 one, methyl a naphthyl ketone, didecyl ketone, diheptyl ketone, dihexyl ketone, 3 fluoro 4 methoxy acetophenone, acetophenone, 4 chloro acetophenone, 2 5 dichloroacetophenone, 4 bromo aceto 25 phenone, 2 4 dimethyl acetophenone, 2-, 3 and 4 fluoroacetophenone, desoxy benzoin, 2-, 3 and 4 methoxy acetophenone, 2-, 3 and 4 methyl acetophenone, propio phenone, 2 bromo propiophenone, 4 fluoro propiophenone, 4 methoxy propiophenone, butyrophenone, 4 chloro butyrophenone, valerophenone, benzophenone, 4 chloro benzophenone, 4 4 ‘ di 30 chloro benzophenone, 2 5 dimethyl benzophenone, 3 4 dimethyl benzophenone, 2 and 4 fluoro benzophenone, 4 methoxy benzophenone, cyclohexanone, 2 phenyl cyclohexanone, 2-, 3 and 4 methyl-cyclohexanone, 2 6 dimethyl cyclohexanone, 4-t-butyl cyclohexanone and 2-chloro-cyclohexanone 35 Special polymeric compounds with units corresponding to the general formula I are the polyaddition and condensation products containing recurrent units of the general formula III:
R, Rg -C H -K O R 30 l m III C OR 30 R m _ CH obtainable, or obtained by reaction of diols HOR 3 OH with enol ethers of the 40 following formula:
R 70 R / C=C R, N R 2/ R 9 wherein m, R 3 and R 7 have the meanings given under Formula II, and R 2 is H, an alkyl group, preferably one with 1 to 12 carbon atoms, or an aryl 45 group, R 8 and R 9 are alkyl or aryl groups, preferably, they should not have more than 11 carbon atoms together.
Furthermore, R 2 and R 8, or R 2 and Rg, or R 8 and R,9 may belong to a common ring which may be substituted The aryl, alkyl and alkylene groups are those 50 1,602,902 5 defined in connexion with formula I If different enol ethers and/or diols are used, different units of formula III are obtained in a statistical arrangement.
The enol ethers in which R 2 stands for H correspond to aldehydes containing at least one hydrogen atom attached to a saturated carbon atom in aposition to the carbonyl group, and the enol ethers in which R 2 is not H correspond to ketones 5 containing at least one hydrogen atom attached to a saturated carbon atom in a aposition to the carbonyl group Since, as already stated, enol ethers may be used as starting materials instead of the corresponding carbonyl compounds, they are also referred to as their synthetic equivalents Further synthetic equivalents are, for example, the alkynes, for example acetylene instead of acetaldehyde 10 Suitable enol ethers are the enol ethers corresponding to the aldehydes and ketones listed above, with the above reservation Their preparation is described, for example, in Houben-Weyl, Vol VI/3 and in “Leibigs Annalen der Chemnie”, 601, 81 ( 1956).
Suitable diols are, for example, those mentioned in connection with formulae 15 II and I Ia.
A further group of polymeric compounds containing recurrent acetal or ketal groups are the addition products obtained or obtainable by adding diols to dienol ethers.
Preferably, the diols mentioned in connection with formula II are used 20 Suitable dienol ethers are, e g, the divinyl ethers obtained by adding diols to acetylene: such compounds are described, for example, in “Liebigs Annalen der Chemie”, 601, 81 ( 1956) The following compounds are mentioned as examples of preferred divinyl ethers:
ethylenglycol, butane-l 4-diol and hexane-1 6-diol-divinyl ether, and the divinyl 25 ethers of polyalkylene glycols: diethyleneglycol divinyl ether is particularly preferred.
A further group of polymeric compounds containing units corresponding to the general formula I are the reaction products containing recurrent units corresponding to the general formula III which are obtainable by or produced by 30 the polyaddition of hydroxyalkyl-enol ethers These starting substances contain the carbonyl equivalent and the alcoholic constituent in the same molecule In this case, it is also possible for R 3 to be combined with R 8 or R 9 to form a possibly substituted ring.
If different hydroxy alkyl enol ethers are used, a polyaddition reaction 35 produces statistical sequences of different units corresponding to formula III.
Suitable hydroxyalkyl enol ethers are described, e g in “Liebigs Annalen der Chemie” 601, 81 ( 1956); they are prepared by adding diols to alkines, preferably acetylen Suitable representatives of such compounds are, e g: diethyleneglycol monovinyl ether and triethyleneglycol monovinyl ether 40 The above-Iescribed hydroxy alkyl vinyl ethers are also obtained, in the form of intermediate products that cannot be isolated, by the addition of I mol of 1,2 or 1,3-diol to alkylene dienol ethers, followed by intra-molecular reacetalization.
during which the 1 3-dioxolanes or 1 3-dioxanes corresponding to the diols are split off Under the acidic conditions prevailing, polyaddition of the hydroxyalkyl-enol 45 ethers to form polyacetals then occurs At the same time, the resulting 1 3dioxolane or 1 3-dioxane is isolated, besides a little diol.
A further group of polymeric compounds containing recurrent units corresponding to the general formula I are reaction products containing units of the general formula IV These compounds are obtainable or produced by 50 polycondensation of dialdehydes or diketones or their synthetic equivalents with tetrahydric alcohols.
0 R 1 R 1 O c Kc> R 3 I o R in this formula k is an integer from I to 40, preferably between 2 and 20 55 R 1 and R 1 ‘ are H, aryl groups or alkyl groups, preferably such with 1 to 12 carbon atoms which may be connected with each other to form a substituted or unsubstituted ring, R 2 is an alkylene group, preferably with I to 16 carbon atoms, or an arylene group, and R 3 is a 4-valent aliphatic group the free valences of which are attached to 5 different carbon atoms at such distances that 5 or 6-membered rings are formed with the acetal group.
The aryl, alkyl and alkylene groups are those listed in connection with formula I.
Suitable dialdehydes or diketones, or dialdehydes or diketones from which the 10 synthetic equivalents are derived are, for example: malonic dialdehyde, cyclohexa1.4-dione or adipic dialdehyde.
Suitable tetrahydric alcohols are, for example, 2 2 5 5-tetramethylolcyclopentanone and 2 2 6 6-tetramethyl-cyclohexanone.
The above-described preferred polymers may be easily, quickly and very 15 cheaply obtained by polycondensation of easily accessible aldehydes and diols The aldehydes may be replaced by the corresponding acetals or enol ethers, or by ketones or their ketals or the corresponding enol ethers.
This means that polyacetals or polyketals of practically any type can be prepared by polyaddition or polycondensation of aldehydes and ketones or their 20 synthetic equivalents, with diols Moreover, it is possible to vary the degree of polymerization within wide limits, for example, by further reacetalization at elevated temperatures, e g, analogously to the processes disclosed in German Offenlegungsschrift No 25 19 575.
Furthermore, it is possible to increase the molecular weight of the polyacetals 25 or polyketals in known manner by reaction of the terminal OH groups with polyfunctional compounds capable of reaction with OH groups, e g, with diisocyanates or diepoxides.
The molecular structure of the polyacetals and polyketals may be further modified by replacing a small portion of the diols employed by triols or tetraols 30 Thus, by causing a certain degree of branching of the polymeric molecules, the difference in solubility between the exposed and unexposed areas may be increased in a desirable manner Of course, the solubility of the branched polymers must be sufficient to enable the preparation of coating solutions in suitable solvents.
Suitable triols are, e g, glycerol, 1 2 6-hexanetriol, trimethylol propane, 1 4 7-tri 35 hydroxy-heptane and the reaction products thereof with ethylene oxide.
The above-mentioned aldehydes and ketones and the aldehydes and ketones from which their synthetic equivalents are derived, and the multivalent alcohols should not contain substituents which may cause difficulties during polyaddition or polycondensation 40 Besides a statistical structure, caused by copolyaddition and/or polycondensation of the above-mentioned aldehydes or ketones or their synthetic equivalents and diols, it is also possible for the polymeric compounds with recurrent units corresponding to the general formula I to have a planned structure 45 This may also be achieved in various ways Beside “symmetrical” variantsobtained, for example, by the above-described polycondensation of dialdehydes or diketones, or their synthetic equivalents, with tetrahydric alcohols “asymmetrical” variants are also possible Thus, polymeric compounds with recurrent units corresponding to the general formula I may be prepared, for 50 example, by the polyaddition of divinyl ethers which may be obtained, e g, by the addition of 1 mole of a diol to 2 moles of acetylene with diols.
It is apparent that, by their structure, the polymeric compounds containing recurrent units of the general formula I, can always be derived from an aldehyde or ketone, or the multiples or equivalentss thereof and a diol or a corresponding 55 multiple of a diol.
The statement that the polymeric compounds containing recurrent units corresponding to the general formula I result from a reaction of aldehydes and/or ketones, or their synthetic equivalents, with diols, under polyaddition and/or polycondensation, is to be understood in this wider sense 60 The methods of preparation described in detail in this specification are particularly easily performed processes for the preparation of polymeric compounds having recurrent units corresponding to formula I A survey of further processes is contained, e g in Houben-Weyl, Vol 14/2.
For the manufacture of the positive-working copying compositions according 65 1,602,902 to the invention, the described polyacetals and/or polyketals are mixed with substances which are capable of forming acids under photochemical action and/or by the action of high energy radiation, especially electron beams.
Advantageously, the copying compositions further include a polymeric, preferably water-insoluble binder which is soluble in organic solvents Since 5 aqueous alkaline solutions may be used with advantage as liquid developers for the copying compositions according to the invention and because developers of this type generally are more advantageous than developers based on organic solvents, such binders are preferred which are soluble or at least swellable in aqueous alkaline solutions 10 The phenol resins, especially the novolaks, found suitable for many positive copying compositions, have also proved very suitable and advantageous for the copying compositions according to the invention These binders, especially the more highly condensed resins containing substituted phenols, e g, cresols, as the formaldehyde-condensation partner, contribute to a pronounced differentiation 15 between the exposed and unexposed areas of the layer during development The novolaks may be modified in known manner, by a reaction of part of their hydroxy groups, e g, with chloroacetic acid, isocyanates, epoxides or carboxylic acid anhydrides Other alkali-soluble resins, such for example, as copolymers of maleic acid anhydride and styrene, or of vinyl actate and crotonic acid, or of methyl 20 methacrylate and methacrylic acid may also be used as binders The type and quantity of the alkali-soluble resin may vary according to the purpose for which the composition is intended; proportionss between 30 and 90 per cent by weight, preferably between 55 and 85 per cent by weight, of the solids content are preferred Additionally, numerous other resins may be incorporated, vinyl 25 polymers, such as polyvinyl acetates, polyacrylates, polyvinyl ethers and polyvinyl pyrrolidones, which in turn may be modified by comonomers, being preferred The most favorable proportion of such resins depends on the practical requirements of each case and on the influence upon the developing conditions; normally, it does not exceed 20 per cent by weight of the alkali-soluble resin For special 30 requirementss with respect to flexibility, adhesion, gloss other substances, such as polyglycols, cellulose derivatives, such as ethyl cellulose, wetting agents, dyestuffs and finely divided pigments, may be added to the light-sensitive composition in small quantities.
A vast number of kown compounds and mixtures, such as diazonium salts, 35 phosphonium salts, sulfonium salts and iodonium salts or halogen compounds, quinone diazide sulfochlorides and organometal/organohalogen combinations, may be used as radiation-sensitive constituents forming or splitting off acids during irradiation.
Suitable diazonium salts are the compounds with a useful absorption range 40 between 300 and 600 nm, which are known to be suitable for diazotype purposes A number of suitable diazonium compounds known to possess a satisfactory shelf-life are mentioned in the examples, compounds containing no basic substituents being preferred.
As a rule, the above-mentioned diazonium, phosphonium, sulfonium and 45 iodonium compounds are used in the form of salts soluble in organic solvents, normally as the separation products with complex acids, such as hydrofluoboric acid, hexafluorophosphoric acid, hexafluoantimonic acid or hexafluoroarsenic acid.
Alternatively, derivatives of positive-working o-quinone diazides may be used 50 In most cases, the acidity of the indene carboxylic acids produced by exposing the o-naphthoquinone diazides scarcely suffices for a satisfactory imagewise differentiation From this group of compounds, the naphthoquinone-1 2diazide-4sulfochloride is preferred, because, during its exposure, three acid functions are formed which give rise to a relatively high degree of intensification during splitting 55 off the polyacetals and polyketals.
In principle, all organic halogen compounds that are free radical-forming photoinitiators, for example, such containing more than one halogen atom attached to a carbon atom or an aromatic ring, may be used ass halogencontaining radiation-sensitive compounds capable of forming a hydrohalic acid Examples of 60 suchs compounds are disclosed in US Patents Nos 3,515,552, 3,536,489 and 3,779,778 and in German Offenlegungsschrift No 2,243,621 The effect of these halogen-containing compounds in the positive-working layers of the invention may be spectrally influenced and increased by the addition of known sensitizers.
Furthermore certain substituted trichloro methylpyrones, such as those 65 I 1,602,902 described in German Offenlegungsschrift No 2,610,842, may be used The new 2aryl-4 6-bis-trichloromethyl-5-triazines disclosed in our co-pending Application No 16075/78 (Serial No 1,602,903) were found to be particularly advantageous.
Examples of suitable initiators are:
4-(di-n-propyl-amino)-benzene-diazonium-tetrafluoroborate, 5 4-p-tolylmercapto-2,5-diethoxy-benzene-diazonium-hexafluophosphate, 4-p-tolylmercapto-2,5-diethoxy-benzene-diazonium-tetrafluoborate, diphenylamine-4-diazonium sulfate, 4-methyl-6-trichloromethyl-2-pyrone, 4-( 3,4,5-trimethoxy-styryl)-6-trichloromethyl-2-pyrone, 10 4-( 4-methoxy-styryl)-6-( 3,3,3-trichloro-propenyl)-2-pyrone,2-trichloromethyl-benzimidazole, 2-tribromomethyl-quinoline, 2,4-dimethyl 1 -tribromoacetyl-benzene, 3-nitro1-tribromo-acetyl-benzene, 15 4-dibromoacetyl-benzoic acid, 1,4-bis-dibromomethyl-benzene, tris-dibromomethyl-5-triazine, and 4,6-bis-trichloromethyl-5-triazines carrying one of the following substituents:
2-( 6-methoxy-naphth-2-yl)-, 20 2-(naphth-1-yl)-, 2-(naphth-2-yl), 2-( 4-ethoxyethyl-naphth 1 -yl)-, 2-(benzopyran-3-yl)2-( 4-methoxy-anthrac 1-yl)-, and 25 2-(phenanther-9-yl).
Other suitable initiators are mentioned in the examples.
The quantity of the initiator may widely vary depending on its chemical nature and the composition of the layer Favorable results are obtained with quantities ranging from 0 1 to 10 per cent by weight, based on the total weight of the solids, 30 quantities in the range from 0 2 to 5 per cent by weight being preferred Especially in the case of layers of more than 10,um thickness, it is recommended to add only a relatively small quantity of the acids-donor to the layer.
Soluble or finely distributed dispersible dyestuffs may be added to the lightsensitive composition, as also may UV-absorbing agents, if required for the 35 intended use of the material The most favorable proportions of the various components contained in the layer may be determined by simple routine experiment Examples of suitable solvents for the compositions according to the invention are ketones, such as methyl ethyl ketone, chlorinated hydrocarbons, such as trichloro-ethylene and 1,1,1-trichloroethane, alcohols, such as npropanol, 40 ethers, such as tetrahydrofuran, alcohol ethers, such as ethylene glycol monomethyl ethyl ether, and esters, such as butyl acetate Mixtures of these solvents may also be used, and other solvents, such as acetonitrile, dioxan, or dimethyl formamide may be added for special purposes In principle, all solvents are suitable which do not undergo an irreversible reaction with the components of 45 the layer.
When selecting the solvent, however, the intended coating method, the thickness of the layer, and the drying apparatus to be used should be considered.
Thin layers of up to 5 um prepared in small quantities for testing purposes are preferably applied by whirler-coating In this manner, layers of a thickness of more 50 than 60 umrn may be produced by a single application or by means of a doctor knife from solutions having a solids content of up to 40 per cent If both surfaces are to be coated, a dip coating process is preferred, advantageously using a low boiling point solvent so that the coating dries quickly Webs are coated by roller application, by means of slot dies or by spraying; sheet materials such as zinc or 55 multi-metal plates, may be coated with the aid of a curtain coater.
As compared with other known positive-working layers, especially such containing o-naphthoquinone diazides, greater advantages are achieved in the production of relatively thick layers, because the light-sensitivity of the lightsensitive compositions according to the invention is less dependent on the 60 thickness of the layers Exposure and processing of layers having a thickness of up to 100 pum and more is possible.
In the case of relatively thick layers of more than 10 pm thickness, the preferred supporting materials are plastic films which serve as temporary supports for transfer layers For this purpose, and for color proofing films, polyester films, 1,602,902 e.g, polyethylene terephthalate films, are preferred Polyolefin films, e g, polypropylene films, may also be used, however In the case of layers below a thickness of about 10 jum, metals are normally used as supports For the preparation of offset printing plates, mechanically or electrochemically roughened and possibly anodized aluminium plates may be used, which may additionally be 5 pretreated by a chemical process, for example, with polyvinyl phosphonic acid, silicates or phosphates Multi-metal plates containing copper and chromium or brass and chromium as the uppermost layers are also suitable For use as relief printing plates, the layers according to the present invention may be applied to zinc or magnesium plates, to commercially available micro-crystalline alloys thereof 10 suitable for powderless etching, or to etchable plastic materials, such as polyoxymethylene Due to their good adhesion and etching resistance on copper or nickel surfaces, the layers according to the invention are suitable for use, as intaglio and screen printing forms The copying compositions according to’ the is invention may also be used as photoresists for chemical milling 15 Finally, the coatings may be applied either directly or by transferring them from temporary supports to circuit board materials consisting of insulating plates with a copper layer on one or both surfaces thereof, or to glass or ceramics materials which may be pretreated with an adhesion-promoter, or to wafers of silicon which, in micro-electronics, were found to be suitable for imaging by 20 electron beams Moreover, it is possible to coat wood, textiles, and the surfaces of many materials, which advantageously are imaged by projection, provided the materials are resistant to the attack of alkaline developers.
Conventional apparatus and conditions may be used for drying the coated layers, temperatures around 1000 C and even brief heating to 120 WC being 25 withstood by the layers without detracting from their radiationsensitivity.
The light sources normally used for copying, viz tubular lamps, pulsed xenon sources, metal-halide-doped high pressure mercury vapor lamps, and carbon arc lamps, may also be used for exposing the material according to the present invention In addition thereto, the light-sensitive polyacetal and/or polyketal layers 30 may be exposed in conventional projection and enlargement apparatus to the light of metallic-filament lamps or by contact exposure under normal incandescent bulbs Further, coherent laser beams may be used for short exposure For the purposes of the present invention, short-wave lasers of adequate energy, for example green argon lasers, krypton-ion lasers, dyestuff lasers, and helium 35 cadmium lasers emitting between 300 and 600 nm were found to be suitable.
The laser beam is directed by a given, programmed line and/or screen movement.
As a further possibility, the material according to the invention may be irradiated with electron beams The copying compositions according to the 40 invention, like numerous other organic materials, may be thoroughly decomposed and cross-linked by electron beams, so that a negative image is formed after the unexposed areas have been removed by a solvent or by exposure without an original and development In the case of an electron beam of lower intensity and/or higher operating speed, however, the electron beam causes differentiation toward a 45 higher solubility, i e the irradiated areas of the layer may be removed by a developer It was found that the layers according to the present invention are considerably more sensitive to electron beams than are normal naphthoquinone diazide layers, and that a wide range of electron beams of relatively low energy efficiency may be used, as illustrated in the examples The most favorable 50 conditions may be easily ascertained by preliminary tests.
After image-wise exposure or irradiation the layers according to the invention may be removed virtually by the same developers as used for commercial naphthoquinone diazide layers and resist layers, or the copying conditions of the new layers may be advantageously adapted to known auxiliaries, such as developer 55 solutions and programmed spray developing devices The aqueouss developer solutions used may contain, for example, alkali phosphates, alkali silicates, or alkali hydroxides, and also wetting agents, and minor proportions of organic solvents In certain cases, mixtures of solvents and water may be used for development The most suitable developer may be determined by running tests with the layer in 60 question If necessary, the developing process may be assisted by mechanical means.
In order to increase their mechanical strength during the printing process and their resistance to wash-out solutions, correcting agents and UVhardenable printing inks, the developed plates may be briefly heated to relatively high 65 1,602,902 temperatures, as is known for diazo layers and described, for example, in British Patent No 1,154,749.
The present invention also provides a process for the production of relief images wherein a radiation-sensitive recording material comprising a) a compound which yields an acid under the influence of actinic radiation 5 and b) an organic polymeric compound which contains recurrent acetal or ketal groupings, the a-carbon atom of the alcohol constituent of which is aliphatic, in its main chain, and whose solubility is a developer liquid is increased by the action of an acid 10 is image-wise exposed to actinic radiation to such an extent that the solubility of the layer in a liquid developer is increased, and the irradiated portions of the layers are then removed by means of a developer.
If electron beams are used for performing the process of the invention it is also possible to use, besides the known photolytic acid-donors sensitive to light within 15 the visible and near UV range of the spectrum, acid donors which have their absorption ranges within the relatively short wave range of the electromagnetic spectrum and thus are less sensitive to daylight This has the advantage that the recording material according to the invention need not be handled in the absence of light and that a better storability of the materials may be achieved 20 Examples of such initiators are, e g: tribromomethyl-phenylsulfone, 2,2 ‘,4,4 ‘,6,6 ‘-hexabromodiphenylamine, pentabromoethane, 2,3,4,5-tetrachloroaniline, pentaerythritol-tetra-bromide, clophene-resin W, i e a chlorinated terphenyl resin, or chlorinated paraffins.
In the following, examples of polymers and copying compositions according to 25 the invention are described First the preparation of examples of the new polyacetals and polyketals will be described They are numbered Compounds 1 to 106 and will be referred to by these numbers in the remaining examples.
In the examples, the relation between parts by weight and parts by volume corresponds to that between grams and milliliters Percentages and proportions are 30 by weight unless otherwise stated.
General Instruction A for the preparation of Compounds Nos I to 46 illustrated in Table I In a solvent which is inert under the reaction conditions and forms an azeotrope with water, e g, benzene, toluene, xylene, chloroform or methylene 35 chloride, aldehyde and diol in a molar ratio of about 1:1 are heated to the boiling point, with reflux, in the presence of 1 to 2 per cent by weight of an acid catalyst, e.g, an acid ion exchanger, until no further reaction water is separated After neutralization, for example with sodium carbonate, the reaction mixture is filtered and freed from solvent The highly viscous oil remaining after removal of the 40 volatile constituents under high vacuum at 100 to 1500 C shows virtually no hydroxyl or carbonyl bands in the IR spectrum In the NMR spectrum, the characteristic signals for acetal protons stated in Table 1 are found.
The above-listed compounds are also obtained if the reaction water is directly distilled off In this case, it is possible to work without a solvent (see General 45 Instruction B) or to use a high-boiling point inert solvent, e g, odichlorobenzene.
Alternatively, it is possible to remove the reaction water under reduced pressure (see General Instruction C), if no solvent and a low reaction temperature are used.
1,602,902 1,602,902 TABLE 1
Compounds corresponding to General Formula II NMR acetal Com protons Yield pound a (ppm) (% of No R R 3 (CDCI 3) theory) Isopropyl n-Hexyl n-Hexyl Isopropyl Isopropyl Isopropyl n-Propyl 1-Ethyl-propyl 1-Ethyl-pentyl Phenyl Cyclohexyl Ethyl n-Butyl Isopropyl 3-Cyclohexene-1-yl 1-Ethyl-propyl Isopropyl Phenyl Phenyl Ethyl Ethyl n-Undecyl Ethyl Ethyl -(CH 2) 2-O-(CH 2)2-(CH 2) 2 (OCH 2 CH 2) 2-(CH 2) 2-(OCH 2 CH 2) 3-(CH 2) 2-(OCH 2 CH 2)2-(GH 2) 2-(OCH 2 CH 2)3p-Xylylene -(CH 2)2-(OCH 2 CH 2)2-(CH 2) 2-(OCH 2 CH 2)2-(CH 2) 2-(OCH 2 CH 2) 2-(CH 2)2-(OCH 2 CH 2) 2-(CH 2)2-(OCH 2 CH 2)2-(CH 2) 2-(OCH 2 CH)2-(CH 2)2-(OCH 2 CH 2)2-(CH) s-(CH 2)2-(OCH 2 CH 2)2p-Xylylene -(CH) 2-S-(CH 2) 2p-Xylylene -(CH 2) s1,4-Cyclohexylene 1-Ethyl-heptylene -(CH 2) 2-(OCH 2 CH 2) 21,4-Dimethyl-cyclohexan7,8-ylen -(CH 2)2-O-CH 2-C-CCH 2-O-(CH 2)2-(CH 2) 2-(OCH 2 CH 2) 24.15 4.56 4.54 4.18 4.17 4.35 4.60 4.41 4.48 5.62 4.22 4.50 4.57 4.07 4.35 4.55 4.15 5.71 5.45 4.48 4.37 4.57 4.34 4.56 2,4-Dichlorophenyl 6.11 1,602,902 TABLE 1 (Continued) Compounds corresponding to General Formula II NMR acetal Com protons Yield pound 8 (ppm) (% of No R, R 3 (CDC13) theory) Ethyl n-Pentyl n-Nonyl Ethyl Ethyl 2-Phenyl-ethyl 2-Phenyl-ethyl Ethyl Ethyl Ethyl Tricyclol 4.3 1 0 Idecyl (CH) 2 CH-CH 2-OCH 2-C(CH 3)24-Chloro-phenyl 3-Chlorophenyl 3-Chlorophenyl 4-Is opropyl-phenyl 1-Propenyl Ethyl Tricyclol 4.3 1 O O decyl Ethyl Isopropyl -(CH 2)2-(OCH 2 CH 2) 2-(CH 2)2-(OCH 2 CH 2)2-(CH 2) 3-(o CH 2 CH 2 CH 2)2p-Xylylene p-Xylylene -(CH 2) 2-(OCH 2 CH 2)2-(CH 2)2-(OCH 2 CH 2)4-(CH 2)2-(OCH 2 CH 2)6-(CH 2)2-(OCH 2 CH 2) 3-(CH 2)2-(OCH 2 CH 2)2-(CH 2) 2-(OCH 2 CH)2-(CH 2)2-(OCH 2 CH 2)2-(CH 2)s-(CH 2) 2-(OCH 2 CH 2) 2-(CH 2) s-(CH 2) -(CH 2) s-(CH 2) s-(CH)6-(CH 2)2-(OCH 2 CH 2) ) 4,8-Dimethyl-tricyclo-l 4 3 1 0-decan-11 12-ylene.
General Instruction B for the preparation of Compounds Nos 47 to 63 listed in Table 2 Acetal or ketal and diol, in a molar ratio of about 1:1, are heated in the presence of I to 2 per cent by weight of an acid catalyst, e g, mesitylene sulfonic acid, until the low boiling point alcohol formed during the reaction is completely 4.37 4.60 4.57 4.50 4.65 4.70 4.60 4.51 4.50 4.51 4.33 4.35 5.74 5.48 5.61 5.45 4.65 4.48 4.21 4.39 4.35 distilled off After adding an inert solvent and sodium carbonate in solid form, the reaction mixture is filtered and freed from solvent The highly viscous oil remaining after the removal of the volatile constituents under high vacuum at 100 to 150 C shows no hydroxyl bands in the IR spectrum.
The compounds may also be obtained by removing the low boiling point alcohol at low temperature under reduced pressure (see General Instruction C) or at a relatively high temperature in the presence of a high boiling point inert solvent, such as o-dichlorobenzene.
TABLE 2
Compounds corresponding to General Formula Ila Com Yield pound (% of No R 1 R 2 R 3 theory) Phenyl Trichloromethyl 1-Ethyl-p entyl 4-Me thoxy-pheny 1 Phenyl Phenyl HHHHMethyl Phenyl -(CH 2) Methyl Methyl n-Nonyl Methyl Ethyl Ethyl Mlethyl Isopropyl Phenyl n-Nonyl p-Tolyl Ethyl n-Nonyl a-Naphthyl Ethyl Ethyl n-Pentyl Methyl n-Dodecyl Methyl -(CH 2) 5-(CH 2) 2-(OCH 2 CH 2)2-(CH 2) 5-(CH 2) s-(CH)2-(OCH 2 CH 2)2-(CH 2) s -(CH 2) 2-(OCH 2 CH 2) 2-(CH 2) 2-(OCH 2 CH 2)2-(CH 2)2-(OCH 2 CH 2)2-(CH 2) 5 -(CH 2)s ) -(CH 2)2-(OCH 2 CH 2)3-(CH 2) s-(CH 2)2-(OCH 2 CH 2)spo Xylylene ) 1 4-Dimethyl-cyclohexan-7,8-ylene.
General Instruction C for the preparation of Compounds Nos 64 to 83 listed in Table 3 Vinyl ether and diol, in a molar ratio of about 1:1, are stirred for about 2 to 3 hours at room temperature or slightly elevated temperature in the presence of I to 2 per cent by weight of an acid catalyst, for example, potassium hydrogensulfate.
The low boiling point alcohol set free during the reaction is completely removed by means of a water jet vacuum After adding an inert solvent and solid sodium 54 79 1,602,902 carbonate the reaction mixture is filtered and freed from solvent The highly viscous oil remaining after removal of low boiling point constituents at 100 to C in a high vacuum shows virtually no hydroxyl bands and no bands within the double bond region in the IR spectrum In the NMR spectrum, the vinylic proton has disappeared.
The above-mentioned compounds are also obtained if the low boiling point alcohol is directly distilled off, without the use of a solvent (see General Instruction B) or in the presence of high boiling point inert solvents, such as odichlorobenzene.
TABLE 3
Compounds corresponding to General Formula III Com Yie Id pound (% of No R 2 R 8 R R 3 theory) n-Propyl n-Propyl n-Propyl n-Propyl n-Propyl n-Propyl Methyl HEthyl Ethyl Ethyl Ethyl Ethyl Ethyl Phenyl Methyl -(CH 2)4-(CH 2)4-(CH 2)4-(CH 2)4-(CH 2)4-(CH 2)4-(CH 2)4-(CH 2) 3 CH(CH 3)-, -(CH 2)2 CH(CH 3)CH 2-(CH 2) 3-CH(CH 3) 2 -tert -Butyl-butylene HHHHHHHPhenyl HHHHHHMethyl Methyl H HHPhenyl -(CH 2)2-(OCH 2 CH 2)2p-Xylylene -(CH 2) 1,44 Dimethyl-cyclohexan-7,8 -y lene ) -(CH 2)2-(OCH 2 CH 2)2-(CH 2) 2-(CH 2 CH 2) 2-(CH 2)2-(OCH 2 CH 2)2p-Xylylene 1,4-Dimethyl-cyclohexan-7,8-ylene ) -(CH 2), -(CH 2)2-O-(CH 2)2-(CH 2)2-(OCH 2 CH 2)2p-Xylylene -(CH 2)2-(OCH 2 CH 2)2 1,4-Dimethyl-cyclohexan-7,8-ylene -(CH)2-)(OH 2 CH 2)2 -(CH 2)2-(OCH 2 CH 2)2 ) 4,8-D imethyl-tricyclo 44 3 1 O l-decan-11 12-ylene.
72 1,602,902 1,602,902 15 Compounds Nos 84 to 93 For the preparation of Compounds Nos 84 to 93 listed in Table 4, one of the General Instructions A to C is applied The compounds are condensates The groups converted by Formula I and produced from carbonyl constituents or their equivalents and diol constituents are present in a statistical arrangement 5 The following compounds were reacted with each other:
Compound No 84: benzaldehyde and 2-ethyl-butyraldehyde with pentane-I 5diol Compound No 85: isobutyraldehyde with pentane-l 5-diol and diethyleneglycol Compound No 86: 2-ethyl-butyraldehyde and benzaldehyde with triethylene 10 glycol and pentane-l 5-diol Compound No 87: benzaldehyde and 2-ethyl-butyraldehyde with triethyleneglycol Compound No 88: benzaldehyde-diethylacetal and 2-ethyl-hexanal-diethylacetal with pentane-l 5-diol 15 Compound No 89: cyclohexanone-diethylketone and anisaldehydediethylacetal with triethyleneglycol Compound No 90: 2-methoxy-cyclohexene with triethyleneglycol and pentane1.5-diol Compound No 91: 2-methoxy-cyclohexene and 4-metfioxy-hept-3-ene with p 20 xylyleneglycol Compound No 92: benzaldehyde-diethylacetal and 2-methoxy-cyclohexene with triethyleneglycol Compound No 93: enanthic aldehyde and benzaldehydediethylacetal with triethyleneglycol 25 TABLE 4
Compounds corresponding to General Formula I C ompound Yield No R, R 2 R 3 R 4 Rs R 6 (% of theory) 84 Phlenyl 11 (C 1 f 2)s-O 1-Ethyl-propyl 11 (CH 2)3-O 68 t I Isopropyl -(CH 2)5-O H Isopropyl -(CH 2 CH 2 O)2 70 86 11 1-Ethyl-propyl -(C 112)s-O Phenyl H (CH 2 CH 2 O)3 53 87 Phenyl 1-1 -(C Fi 2 CH 2 O)3 H 1-Ethyl-propyl -(CH 2 CH 2 O)3 48 88 Phenyl H (CH 2)s-O 1 -Ethyl-pentyl H (CH 2),-O 73 89 -(C 12)s (C It 2 CH 2 O)3 p-Methoxy-phenyl H (CH 2 CH 2 O)3 81 -(CH 2) (CH 2 CH 2 O),3 -(CH 2)5 (CH 2)5-O 84 91 -(CH 2)s p-Xylyleneoxy n-Propyl n-Propyl p-Xylyleneoxy 51 92 -(CH 2)s / (CH 2 CH 2 O)3 H Phenyl -(CH 2 CH 2 O)3 80 93 t I I Phenyl -(CH 2 CH 2 O)3 n-Hexyl H (CH 2 CH 2 O)3 48 General Instruction D for the preparation of Compounds Nos 94 to 102 listed in Table 5 With cooling, an equivalent molar quantity of a divinyl ether is cautiously added, drop by drop, and in the presence of 1 to 2 per cent by weight of an acid catalyst, e g, sulfuric acid or p-toluenesulfonic acid, to a solution of the diol in an inert solvent, such as methylene chloride After three hours’ stirring at room temperature, the reaction mixture is neutralized by adding solid sodium carbonate and is then filtered and freed from solvent The highly viscous oil remaining after removal of the volatile constituents in a high vacuum at 100 to 150 C shows practically no hydroxyl bands and no bands in the double bond region in the IR spectrum An NMR spectrum does not show any vinylic proton The acetal proton signals characteristic for polyacetals are stated in Table 5.
C) O -o Ol 1 TABLE 5 -I Compounds corresponding to Formula I NMR Compound acetal Yield Nb R=R 4 R 2 =Rs R 3 R 6 protons (% of theory) 94 CH 3 H (CH 2)2-O-(CH 2)2 (CI 12)2-O-(CH 2)2 4 79 60 CH 3 H (CH 2)2-O-(CH 2)2 (CH 2)4 4 78 49 96 CH 3 H (CH 2)2-O-(CH 2)2 (CH 2)s 4 74 61 97 CH 3 H (CH 2)2-O-(CH 2)2 (CH 2)2 (OCH 2 CH 2)2 4-7 9 71 98 CH 3 H p-Xylylene -(CH 2)2-O-(CH 2)2 4 86 68 99 CH 3 H 1,4-Cyclohexylene -(CH 2)2-O-(CH 2)2 4 85 80 CH 3 H (CH 2)2-O-(CH 2)2 1,4-Dimethyl-cyclohexan-7,8-ylene 4 73 62 101 CH 3 H (CH 2)2-O-(CH 2)2 +) 4 70 99 102 CH 3 H (CH 2)4 (CH 2)2-(OCH 2 CH 2)2 4 75 62 +) 4,8 Dimethyl-tricyclo 44 3 1 O l-decan-11 12-ylene.
Compound No 103 While cooling with ice, 15 8 g of diethyleneglycol divinyl ether are cautiously added, drop by drop, to a solution of 7 6 g of propane-1 3-diol in 10 ml of methylenechloride to which 2 drops of concentrated sulfuric acid have been added.
After stirring the mixture for two hours at room temperature, a further 40 ml of methylenechloride and 1 g of solid sodium carbonate are added After filtration and concentration of the organic phase, a crude product results which contains acetaldehyde-trimethylene acetal among its volatile constituents After removal of the low boiling point constituents in a high vacuum at 150 C, 80 g of a viscous oil remain The signals obtained in an NMR spectrum l’HNMR (CDCI 3, TMS): 8 = 4 82 ppm (quartet, 1 acetal proton) 8 = 3 ‘ 68 ppm (singlet, 12 methylene protons), and 8 = 1 34 ppm (doublet, 3 methyl protons)l correspond to the recurrent unit of the diethyleneglycol monovinyl ether polymer.
The same reaction product is obtained, for example, by reaction of diethyleneglycol divinyl ether with ethyleneglycol, 2 2-diethyl-propane-1 3-diol and 2-ethyl-2-butyl-propane 1 3-diol.
0 0 xtl.
O -3 18 1,602,902 18 Compounds Nos 104 to 106 For the preparation of Compounds Nos 104 to 106 General Instructions B or C are applied to the following bis-acetals or bis-ketals and tetra(hydroxyalkyl) compounds:
Compound No 104: 2 2 5 5-tetramethylol-cyclopentanone and cyclohexane-1 4 5 dione-tetramethylketal Compound No 105: malonic dialdehyde-tetramethylacetal and 2 2 5 5-tetramethylol-cyclopentanone Compound No 106: adipic dialdehyde-tetraethylacetal and 2 2 5 5-tetramethylol-cyclopentanone 10 In all cases polymers are obtained which show a carbonyl band originating from the cyclopentanone constituent There are no further carbonyl or hydroxyl bands.
Example 1.
This example serves to show the suitability of very different polyacetal acid 15 donor combinations as components of positive-working copying compositions:
Brushed aluminium plates are whirler coated with a solution comprising 4.7 p b w of a cresol-formaldehyde novolak (melting point 105-120 C, by the capillary method according to DIN 53181), 1 4 p b w of a polymeric acetal, 20 0.23 p b w of the acid donor, 0.02 p b w of Crystal Violet, and 93.65 p b w of methyl ethyl ketone, layers of 1 2 1 um thickness being obtained The plates are image-wise exposed for 7 5 seconds from a distance of 110 cm under a 5 k W metal halide lamp and then 25 developed with one of the following developer solutions A or B:
Developer Solution A 5.55 of sodium metasilicate 9 H 20 3.4 % of trisodium phosphate 12 H 2 O 0 4 % of anhydrous sodium dihydrogen phosphate 30 90.7 O of completely desalted water.
Developer Solution B 0.6 % of Na OH 0.5 % of Na 2 Si O 2 5 H 20 1 0 % of n-butanol 35 97.9 % completely desalted water.
The following Table 6 shows the combinations of acid donors, the developers used, and the developing times.
TABLE 6
Developing Time No Compound Acid Donor Developer (seconds) 1 5 2,5-diethoxy-4 -(p-tolyl-mercapto)-benzene diazonium hexafluophosphate A 20 2 5 as in 1, but in the form of the tetrafluoborate A 45 3 6 naphthoquinone( 1 l 2)-diazide-( 2)4-sulfonic acid chloride B 10 4 10 2-( 4-ethoxy-naphth-1 y l)-4 6-bis-trichloromethyl-5-triazine A 20 13 2 5-diethoxy-4-( 4-ethoxy-phenyl)-benzene diazonium hexafluophosphate A 20 6 23 2-( 3-methoxynaphth-2-yl)-4 6-bis-trichloromethyl-5-triazine B 75 7 96 4-( 2 4- dimethoxy-styry 1)-6-trichloromethyl-pyr-2-one A 30 8 99 afterchlorinated 4 ( 4 -methoxystyryl)-6-trichloromethyl-pyr-2-one A 10 9 100 afterchlorinated 4-( 3 4-methylenedioxy-styryl)-6-trichloromethylpyr-2 -one A 50 43 2-( 4 7-dimethoxy-naphth-1 -yl)-46-bis-trichlor-o-methyl-5-triazine A 20 In all cases, a positive image of the original is obtained, the highest practical light-sensitivities being found in Tests No 4 and No 10.
Example 2.
A composite plate comprising an insulating material (phenol resin laminate) and a 35,um thick copper foil which may be used for the manufacture of circuit boards is provided with a resist layer of the following composition:
39 p b w of the novolak used in Ex 1 are dissolved in 71 p b w of a solvent mixture of 82 p b w of ethylene glycol monoethylether, 9 p.b w of butyl acetate, and 9 p b w of xylene.
84.2 p b w of this solution are used to dissolve a\ bo C) C) hi 1,602,902 20 12.1 p b w of Compound No 43, 0.5 p b w of 2-( 4-methoxystyryl)-4 6-bis-trichloromethyll-5-triazine, 0.8 b p w of the dyestuff “C I Solvent Blue 16 “, and 2.4 p b w of a modified silicon glycol (commercially available coating auxiliary), and 5 58.5 p b w of this solution are again dissolved with 41.5 p b w of the above solvent mixture.
The composite plate is immersed in this solution and withdrawn at a speed of cm/min After the coating has been dried for 10 minutes at 100 C, a 5,m thick layer results The coated plate is image-wise exposed for 70 seconds through a line 10 original, using the metal halide lamp used in Example 1 as the light source, and is then developed by spraying with Developer B used in Example I By etching with an iron trichloride solution, the bared copper layer is removed without attacking the unexposed areas of the layer which are covered by the resist layer.
The example is repeated, but in this case a lead/tin layer is electrodeposited 15 after development on the bared copper layer in a suitable bath The resist layer is resistant to this process, too.
Example 3.
For the preparation of a positive-working photoresist of high layer thickness, 29 64 p b w of the novolak used in Ex 1, 20 8.89 p b w of Compound No 94, 0.12 p b w of 2-( 4-methoxynaphth- 11-yl)-4,6-bistrichloromethyl)-5triazine, and 2.08 p b w of the coating auxiliary used in Ex 2 are dissolved in 25 59.27 p b w of butan-2-one.
With the aid of a wire bar No 40, a nickel plate provided with a customary electroconductive release layer is coated with this solution The coating is dried for minutes at a temperature of 100 C The dried layer is image-wise exposed for 120 seconds from a distance of 110 cm to the light of a 5 k W metal halide lamp By 30 shaking the plate in the Developer A used in Example 1, the exposed portions of the layer are dissolved within 2 5 minutes An electrotype stencil of about 60 Am thickness is thus produced which is used to form the webs of a nickel screen in a commercial nickel sulfamate bath After the completion of the electrodeposition process, the meshes are opened, i e the stencil is removed by dissolving the resist 35 with acetone If a cylinder is treated in this manner, printing forms for rotary screen printing results.
Example 4.
Brushed aluminium plates are coated by immersing them in solutions of 10 64 p b w of the novolak used in Ex 1, 40 3.20 p b w of polyacetal or polyketal, 0.16 p b w of 2-( 4-( 2-ethoxy-ethoxy)-naphth- 11-yl)-4 6-bistrichloromethyl-5triazine, in 86.00 p b w of methyl ethyl ketone.
After removal from the bath and evaporation of the solvent, the plates are 45 21 1,602,902 21 dried for 20 seconds in a current of warm air and then exposed under a line original covered by a 1 mm thick glass plate The exposure apparatus comprises four fluorescent lamps of type TLAK 40 W/05 S, manufactured by Messrs Philips, which are arranged at a distance of 4 cm from each other The distance between the periphery of the tubular lamps and the surface of the plates was about 5 cm The 5 exposure times used for the various polyacetals and polyketals are listed in the following table:
Exposure Time Exposure Time Compound (seconds) Compound (seconds) 11 15 54 7 10 22 55 3 16 19 56 19 17 5 57 10 21 10 58 4624 5 59 7 15 105 60 5 27 10 61 3 28 13 62 5 29 9 63 5 30 7 64 4 20 31 11 65 5 32 17 66 3 33 14 67 4 34 25 68 3 35 40 69 7 25 37 21 70 4 18 71 75 41 4 72 4 42 13 73 9 44 10 74 12 30 40 75 8 46 93 76 8 47 23 77 3 48 26 78 3 49 25 79 10 35 1,602,902 Exposure Time (seconds) Compound Exposure Time (seconds) 101 102 103 104 106 In all cases, a positive image of the original is produced after development with the Developer A used in Example 1.
Example 5.
Example 4 is repeated, except that instead of the novolak used in Example 1 the same quantity by weight of a phenol formaldehyde novolak is used which has a melting range of between 110 and 120 WC according to DIN 53181:
Compound Exposure Time (seconds) In these cases, too, the copying compositions are positive-working.
Example 6.
An offset printing form is prepared as follows:
An electrolytically roughened and anodized aluminium foil is whirler coated ( 150 revolutions per minute) with the following coating solution:
Compound 94.6 p b w of methyl ethyl ketone, 4.0 p b w of the novolak used in Ex 1, 1.2 p b w of Compound No 8, 0.2 p b w of the acid donor No 4 used in Ex 1, and 0 01 p b w of Crystal Violet 5 The resulting layer has a dry weight of approximately 1 5 to 2 0 g/m 2 The dry light-sensitive material is exposed for 20 seconds under a positive combined line and screen original, using a 5 k W metal halide lamp at a distance of 110 cm After exposure, an image becomes visible which shows a strong bluish-green contrast.
Developer A of Example 1 is used for development The exposed areas of the layer 10 are dissolved away within 30 seconds and the blue-colored, unexposed areas remain as the printing stencil.
The offset printing plate prepared in this manner is inked with greasy ink in the normal manner and clamped on a printing machine If the plate is to be stored, it may be wiped over with conventional preserver After 110,000 prints, the printing 15 run was stopped, although no damage to the 150 dot screen could be observed The printing run can be considerably increased by after-heating the developed printing form at about 230 to 2400 C.
Example 7.
In this example, the high thermal stability of the copying compositions 20 according to the invention is shown by comparison with corresponding copying layers based on the monomeric bis-acetal compounds disclosed in US Patent No.
3,779,778 Sometimes, a lack of thermal stability becomes apparent as a reduction of the resistance to developers, i e by an insufficient differentiation between the exposed and unexposed areas of the layer during development More frequently, 25 however, poor thermal stability becomes apparent by a marked increase of the developing time required; in extreme cases, it is no longer possible to dissolve the exposed areas of the layer in the normally used developer A severe thermal stress is regarded as a quick test of the storability of the material at room temperature or at moderately elevated temperature 30 Aluminium plates with an electrolytically roughened and anodized surface are coated with an about 2 gtm thick layer of the following composition:
78.8 o% of the novolak used in Ex 1, 22.3 % of monomeric or polymeric acetal, 3 7 of the acid donor used in Ex 2, and 35 0.2 of Crystal Violet.
A 6 per cent solution in methyl ethyl ketone is supplied by whirler coating All the plates are heated for the same time at 1000 C in a drier, exposed under an original, and then developed The following Table 7 shows the changes in the time required for development of the plates, as a function of the duration of thermal 40 stress.
1,602,902 TABLE 7 a: Heating Period (minutes) Monomeric b: Development (seconds) or polymeric Developer No acetal of Ex1 a b a b a b a b 1 bisphenol-A-bis B 0 30 30 90 60 150 100 150 tetrahydropyranylether 2 di-( 4-hydroxy B 0 40 30 180 60 210 100 210 phenyl)-sulfonebis-tetrahydropyranyl-ether 3 Compound No 8 A 0 40 30 40 60 40 100 40 4 Compound No 99 A 0 15 30 15 60 15 100 15 If, in the tests No 1 and 2, the Developer B according to Example 1 is replaced by the less aggressive Developer A, the times required for development will again increase considerably.
Similar thermal stabilities are obtained if compounds Nos 19 or 9 are used instead of compounds Nos 8 or 88.
Example 8
Aluminium plates with an electrolytically roughened and anodized surface are whirler coated with a solution comprising:
4 7 p b w of the novolak used in Ex 1, 1.4 p b w of polymeric acetal, 0.23 p b w of an acid donor, 0.02 p b w of Crystal Violet, and 93.05 p b w of butan-2-one 0 t O 4 r,.
J O O 25 ss in a manner such that the dried layers have a thickness of about 1 7 um The layers are image-wise irradiated over all spectral lines, using a 25 W argon-ion laser whose beam is optically polyacetal/acid donor combinations is determined by modifying the recording speed of the laser If the Developer A of Example 1 is used, the exposed areas of the layer are dissolved away within 15 to 90 seconds The trace of the laser may be brought out even more clearly by inking the nonirradiated areas with greasy ink.
The following maximum recording speeds were observed:
Combination Recording Speed (m/sec) Compound No 9 and 2.5-diethoxy-4-p-tolylmercaptobenzene-diazonium hexafluophosphate 100 Compound No 19 and 2-( 4-ethoxynaphth 1 -yl)-4 6-bistrichloromethyl-5-triazine 75 Compound No 12 and 4-( 4-methoxystyryl)-6-trichloromethyl-pyr-2-one 45 Example 9.
This example shows the imaging by electron beams of the layers containing the new compounds capable of being split up by acids:
Layers of about 2 gm thickness of the following composition 74.0 %o of the novolak used in Ex 1, 22.0 o of polymeric acetal, 3.8 / of an initiator, and 0.20 o of a dyestuff applied to mechanically roughened aluminum are irradiated with 11 k V electrons, and irradiated areas are solubilized under the conditions stated in Table 8.
1.602902 s)r t’J TABLE 8
Irradiated Compound Energy Developer Developing Time No Initiator ( Joule/cm 2) acc to Ex 1 (seconds) 2-(p-Methoxystyryl)-4,6-bis-trichloromethyl-5-triazine 1-5 1012 A 45 2 5-Diethoxy-4-p-tolylmercapto-benzene diazonium 1-40 10-2 A 45 hexafluophosphate 12 2-( 4 ethoxynaphth-1-yl)-4,6-bis-trichloromethyl-5 1-15 10-2 B 10 triazine 18 4-( 2 4-Dimethoxy-styryl)-6-trichloromethyl-pyr-2-one 1-15 10-2 A 45 19 2 5-Diethoxy-4-p-tolylmercapto-benzene-diazonium 1-15 10-2 B 15 hexafluophosphate Similar results are obtained by using acid donors, such as pentabromoethane and tris-tribromomethyl-5-triazine, which absorb in the relatively short wave range of the spectrum, i e beyond the visible light range and outside of the main emission range of customary light sources, but are highly active under electron radiation.
This process has the advantage that the layers may be handled under normal daylight.
Example 10.
A 25,um thick, biaxially stretched and thermally fixed film of polyethylene terephthalate is immersed in an aqueous solution containing 10 % of trichloro acetic acid, 1 % of polyvinyl alcohol, and 0 1 % of a wetting agent, and the film is then dried for 2 minutes at 140 C.
For the preparation of a positive-working dry resist layer, the thus pretreated polyester film is coated with a solution of 28 6 p b w of the novolak used in Ex 1, 8.6 p b w of Compound No 2, 0.5 p b w of the acid donor used in Ex 3, 2.1 p b w of the coating auxiliary used in Ex 2, and 0.2 p b w of “C I Solvent Blue No 16 ” as a dyestuff, C) C) hi dissolved in a mixture of 46 parts by weight of methyl ethyl ketone and 14 parts by weight of dioxane After drying, the layer has a thickness of about 40 to 50,um In order to protect it against dust and scratching, the layer may be covered by a top coating of polyethylene.
After removal of the top coating, circuit boards may be prepared from this 5 positive-working dry resist by laminating it in a commercial laminating device to a cleaned, previously heated support consisting of an insulating material with copper layers of 35,um thickness applied to one or both of its surfaces After stripping the support film, possibly followed by drying, exposure under an original to a 5 k W metal-halide lamp ( 110 cm distance, about 100 seconds) and developing for about 2 10 to 4 minutes by spraying with the Developer A used in Example I to which a small quantity of n-butanol may be added an imaged resist layer of high quality is obtained It withstands not only the conditions prevailing during etching processes, using, e g Fe C 13, but is also resistant to electroplating processes used for the production of through-hole printed circuits, especially if layers of copper and 15 nickel are electrodeposited after one another.
Example 11.
For the preparation of a re-enlargement plate, 4.0 p b w of the novolak used in Ex 1, 1 2 p b w of Compound No 10, 20 0.2 p b w of 2-( 4-ethoxynaphth 1 -yl)-4 6-bis-trichloromethyl-5-triazine, and 0.01 p b w of Crystal Violet, are dissolved in 94.6 p b w of methyl ethyl ketone, and the solution is whirler coated onto a brushed aluminium plate 25 The resulting plate is exposed for 3 minutes under a positive transparency from a distance of 65 cm, using a projector sold by Messrs Leitz (type Prado, f= 85 mm, 1:2 5) equipped with a 150 watt lamp By immersion in the Developer A stated in Example 1, an enlarged copy of the black and white line image on the positive transparency is obtained within 60 seconds, and the copy thus produced may be 30 reproduced by printing in a small offset press.
Similar results are obtained if Compound No 10 is replaced by equal quantities of Compounds No 14, 19, 8, 38, 20, 94, or 99.

Claims (19)

WHAT WE CLAIM IS:-

1 A radiation-sensitive copying composition which comprises a compound 35 that forms an acid under the influence of actinic radiation, and a polymer having recurring units having acetal or ketal groups in the chain, each a-carbon atom of the alcohol constituent of the acetal or ketal being aliphatic or cycloaliphatic, the solubility of the polymer being increased by the action of an acid.

2 A composition as claimed in claim 1, wherein the chains of the polymer 40 contain, on average, at least three acetal or ketal groups.

3 A composition as claimed in claim I or claim 2, wherein the alcohol constituent of the acetal or ketal is in at least dihydric alcohol.

4 A composition as claimed in any one of claims I to 3, wherein no carbon atom of the alcohol constituent is bonded to more than one oxygen of the acetal or 45 ketal.

A composition as claimed in any one of claims 1 to 4, wherein the alcohol constituent contains between 2 and 18 carbon atoms.

6 A composition as claimed in claim 1 or claim 2, wherein the alcohol constituent is derived from the hydroxy alkyl group of a hydroxy alkyl enol ether 50

7 A composition as claimed in claim 1, wherein the polymer contains units of the formula I:
R, RI AC-O-R 3-C-0 R, n R, R, 1,602,902 28 1,602,902 28 wherein n is an integer between 1 and 40, R 1 and R 4 are H, alkyl or aryl groups, and either R 3 and R 6 are H, alkyl or aryl groups and R 2 and Rs are alkyl or aryl groups, two of the groups R, R 2 and R 3 and two of 5 the groups R 4, Rs and R 6 optionally being combined to form a substituted or unsubstituted ring, R 3 and R 8 are alkylene groups and R 2 and Rs are alkoxy groups which form a substituted or unsubstituted ring with R 3 or R 6, 10 R 3 combining with R 4 and, when N is greater than 1, R, combining with R 6 of a neighbouring unit to form substituted or unsubstituted rings.

8 A composition as claimed in claim 1, wherein the polymer contains recurrent units of the formula II:
R 1 (-C-OR 3-0-)m 15 R 2 II wherein m is an integer between 2 and 80, R 1 is H or an alkyl or aryl group R 2 is an alkyl or aryl group, or wherein R 1 and R 2 together form a substituted or unsubstituted ring and 20 R 3 is an alkylene group which may be combined with one of the groups R, and R 2 to form a substituted or unsubstituted ring.

9 A composition as claimed in claim 1, wherein the polymer contains recurrent units of the formula III:
R R, CHI O-R m 25 R 2 _ III wherein m is an integer between 2 and 80, R 2 is H, an alkyl or an aryl group, R 3 is an alkylene group and R 8 and Rg are H, alkyl or aryl groups which may be combined with each other 30 or each of which may be combined with one of the groups R 2 and R 3 to form a substituted or unsubstituted ring.
A composition as claimed in claim 1, wherein the polymer contains units of the formula IV:
0 R 1 R

1 0 I c C RC 35 wherein k is an integer between I and 40, R 1 and R 1 ‘ are H, alkyl or aryl groups which may be combined with each other to form a possibly substituted ring, R 2 is an alkylene or arylene group and 40 R 3 is a 4-valent aliphatic group the free valences of which are attached to different carbon atoms at such distances that 5 or 6-memibered rings result.

11 A composition as claimed in claim 1, wherein the polymer contains, in the same molecule, different units of one or more of the formulae I, II, III or IV.

12 A composition as claimed in any one of claims 1 to 11, which also contains a polymeric binder.

13 A composition as claimed in claim 1, substantially as described in any one of examples 1 to 11 herein 5

14 A process for the production of a relief image, wherein a radiationsensitive recording material comprising a support and a recording layer comprising a composition as claimed in any one of claims 1 to 13, is image-wise exposed to actinic radiation to such an extent that the solubility of the layer in a developer liquid is increased and the irradiated portions of the layer are then removed by 10 means of a developer.

A process as claimed in claim 14, wherein the radiation is ionizing radiation.

16 A process as claimed in claim 14, wherein the radiation is ultraviolet 1 S radiation 15

17 A process as claimed in claim 14, wherein the radiation is laser radiation.

18 A relief image, whenever produced by a process as claimed in any one of claims 14 to 17.

19 A radiation sensitive recording material comprising a support bearing a layer of a composition as claimed in any one of claims 1 to 13 20 ABEL & IMRAY, Chartered Patent Agents, Northumberland House, 303/306 High Holborn, London, WC 1 V 7 LH.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1981.
Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
1,602,902

GB16074/78A
1977-04-25
1978-04-24
Radiationsensitive copying composition

Expired

GB1602902A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

DE2718254A

DE2718254C3
(en)

1977-04-25
1977-04-25

Radiation-sensitive copying paste

Publications (1)

Publication Number
Publication Date

GB1602902A
true

GB1602902A
(en)

1981-11-18

Family
ID=6007159
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

GB16074/78A
Expired

GB1602902A
(en)

1977-04-25
1978-04-24
Radiationsensitive copying composition

Country Status (16)

Country
Link

US
(1)

US4247611A
(en)

JP
(1)

JPS53133429A
(en)

AU
(1)

AU525946B2
(en)

BE
(1)

BE866305A
(en)

BR
(1)

BR7802527A
(en)

CA
(1)

CA1128804A
(en)

CH
(1)

CH635448A5
(en)

DE
(1)

DE2718254C3
(en)

DK
(1)

DK176778A
(en)

FR
(1)

FR2389155A1
(en)

GB
(1)

GB1602902A
(en)

IE
(1)

IE46621B1
(en)

IT
(1)

IT1102623B
(en)

NL
(1)

NL7804303A
(en)

SE
(1)

SE444232B
(en)

ZA
(1)

ZA782331B
(en)

Families Citing this family (112)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

DE2829511A1
(en)

*

1978-07-05
1980-01-24
Hoechst Ag

RADIATION-SENSITIVE MIXTURE AND METHOD FOR PRODUCING RELIEF IMAGES

DE2928636A1
(en)

*

1979-07-16
1981-02-12
Hoechst Ag

RADIATION-SENSITIVE MIXTURE AND METHOD FOR PRODUCING RELIEF IMAGES

US4356252A
(en)

*

1979-12-26
1982-10-26
E. I. Du Pont De Nemours And Company
Photosensitive negative-working tonable element

US4294909A
(en)

1979-12-26
1981-10-13
E. I. Du Pont De Nemours And Company
Photosensitive negative-working toning process

DE3023201A1
(en)

*

1980-06-21
1982-01-07
Hoechst Ag, 6000 Frankfurt

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE

DE3038605A1
(en)

*

1980-10-13
1982-06-03
Hoechst Ag, 6000 Frankfurt

METHOD FOR PRODUCING RELIEF COPIES

DE3039926A1
(en)

*

1980-10-23
1982-05-27
Hoechst Ag, 6000 Frankfurt

LIGHT SENSITIVE MIXTURE, LIGHT SENSITIVE COPY MATERIAL MADE THEREOF, AND METHOD FOR PRODUCING A PRINT FORM FROM THE COPY MATERIAL

DE3107109A1
(en)

*

1981-02-26
1982-09-09
Hoechst Ag, 6000 Frankfurt

LIGHT SENSITIVE MIXTURE AND COPY MATERIAL MADE THEREOF

US4366224A
(en)

*

1981-08-06
1982-12-28
American Hoechst Corporation
Inorganic lithium developer composition

US4365019A
(en)

*

1981-08-06
1982-12-21
Eastman Kodak Company
Positive-working resist quinone diazide containing composition and imaging method having improved development rates

DE3144480A1
(en)

*

1981-11-09
1983-05-19
Hoechst Ag, 6230 Frankfurt

LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE COPY MATERIAL MADE THEREOF

DE3144499A1
(en)

*

1981-11-09
1983-05-19
Hoechst Ag, 6230 Frankfurt

LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE COPY MATERIAL MADE THEREOF

DE3151078A1
(en)

*

1981-12-23
1983-07-28
Hoechst Ag, 6230 Frankfurt

METHOD FOR PRODUCING RELIEF IMAGES

JPS58219547A
(en)

*

1982-06-16
1983-12-21
Hitachi Ltd
Positive type radiation-sensitive organic high polymer material

JPS58219736A
(en)

*

1982-06-16
1983-12-21
Hitachi Ltd
Manufacture of relief structure

US4491628A
(en)

*

1982-08-23
1985-01-01
International Business Machines Corporation
Positive- and negative-working resist compositions with acid generating photoinitiator and polymer with acid labile groups pendant from polymer backbone

DE3236560A1
(en)

1982-10-02
1984-04-05
Hoechst Ag, 6230 Frankfurt

LIGHT SENSITIVE LAYER TRANSFER MATERIAL AND METHOD FOR PRODUCING A PHOTORESIS TEMPLATE

DE3323343A1
(en)

*

1983-06-29
1985-01-10
Hoechst Ag, 6230 Frankfurt

LIGHT SENSITIVE MIXTURE AND COPY MATERIAL MADE THEREOF

JPS6010250A
(en)

*

1983-06-30
1985-01-19
Fujitsu Ltd
Formation of pattern

GB8333901D0
(en)

*

1983-12-20
1984-02-01
Minnesota Mining & Mfg
Radiationsensitive compositions

US4564575A
(en)

*

1984-01-30
1986-01-14
International Business Machines Corporation
Tailoring of novolak and diazoquinone positive resists by acylation of novolak

DE3406927A1
(en)

*

1984-02-25
1985-08-29
Hoechst Ag, 6230 Frankfurt

RADIATION-SENSITIVE MIXTURE BASED ON ACID-CLEARABLE COMPOUNDS

GB8413395D0
(en)

*

1984-05-25
1984-07-04
Ciba Geigy Ag
Production of images

EP0164083B1
(en)

*

1984-06-07
1991-05-02
Hoechst Aktiengesellschaft
Positively acting light-sensitive coating solution

US4708925A
(en)

*

1984-12-11
1987-11-24
Minnesota Mining And Manufacturing Company
Photosolubilizable compositions containing novolac phenolic resin

DE3445276A1
(en)

*

1984-12-12
1986-06-19
Hoechst Ag, 6230 Frankfurt

RADIATION-SENSITIVE MIXTURE, LIGHT-SENSITIVE RECORDING MATERIAL MADE THEREOF AND METHOD FOR PRODUCING A FLAT PRINTING FORM

US4634659A
(en)

*

1984-12-19
1987-01-06
Lehigh University
Processing-free planographic printing plate

US4737426A
(en)

*

1985-05-15
1988-04-12
Ciba-Geigy Corporation
Cyclic acetals or ketals of beta-keto esters or amides

US4663269A
(en)

*

1985-08-07
1987-05-05
Polytechnic Institute Of New York
Method of forming highly sensitive photoresist film in the absence of water

JPS62124557A
(en)

*

1985-11-25
1987-06-05
Konishiroku Photo Ind Co Ltd
Photosensitive composition and photosensitive lithographic plate material

CA1307695C
(en)

*

1986-01-13
1992-09-22
Wayne Edmund Feely
Photosensitive compounds and thermally stable and aqueous developablenegative images

CA1308596C
(en)

*

1986-01-13
1992-10-13
Rohm And Haas Company
Microplastic structures and method of manufacture

US4897336A
(en)

*

1986-04-11
1990-01-30
Chien James C W
Self-developing radiation sensitive resist with amorphous polymer having haloalkyl substitution derived from cycic ether

DE3621376A1
(en)

*

1986-06-26
1988-01-07
Hoechst Ag

RADIATION-SENSITIVE RECORDING MATERIAL

DE3628720A1
(en)

*

1986-08-23
1988-02-25
Hoechst Ag

PRESENSITIZED PRINTING PLATE AND METHOD FOR PRODUCING A PRINTING FOR THE WATERLESS FLAT PRINTING

DE3635303A1
(en)

1986-10-17
1988-04-28
Hoechst Ag

METHOD FOR REMOVING MODIFICATION OF CARRIER MATERIALS MADE OF ALUMINUM OR ITS ALLOYS, AND THEIR ALLOYS AND THEIR USE IN THE PRODUCTION OF OFFSET PRINTING PLATES

JPH0654382B2
(en)

*

1986-11-18
1994-07-20
富士写真フイルム株式会社

Photosensitive composition

JPS63265242A
(en)

*

1987-04-23
1988-11-01
Fuji Photo Film Co Ltd
Malticolor image forming method

DE3725741A1
(en)

*

1987-08-04
1989-02-16
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE

DE3725949A1
(en)

*

1987-08-05
1989-02-16
Hoechst Ag

LIGHT SENSITIVE MIXTURE, LIGHT SENSITIVE COPY MATERIAL MADE THEREOF AND METHOD FOR PRODUCING NEGATIVE RELIEF COPIES

DE3730783A1
(en)

*

1987-09-13
1989-03-23
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL THEREOF

DE3730787A1
(en)

*

1987-09-13
1989-03-23
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL MANUFACTURED THEREFROM

DE3821585A1
(en)

*

1987-09-13
1989-03-23
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL FOR HIGH-ENERGY RADIATION

DE3730785A1
(en)

*

1987-09-13
1989-03-23
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL THEREOF

DE3737734A1
(en)

*

1987-11-06
1989-05-18
Hoechst Ag

RADIATION-SENSITIVE MIXTURE

JP2623309B2
(en)

*

1988-02-22
1997-06-25
ユーシービー ソシエテ アノニム

How to get a resist pattern

DE3810631A1
(en)

*

1988-03-29
1989-10-12
Hoechst Ag

POSITIVELY WORKING LIGHT-SENSITIVE MIXTURE AND RECORDING MATERIAL MADE THEREOF WITH HIGH HEAT RESISTANCE

EP0347381B1
(en)

*

1988-06-13
1992-02-12
Ciba-Geigy Ag
Unsaturated beta-ketoesteracetals and their applications

DE3820699A1
(en)

*

1988-06-18
1989-12-21
Hoechst Ag

RADIATION-SENSITIVE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL MANUFACTURED THEREOF

DE3821584A1
(en)

*

1988-06-25
1989-12-28
Hoechst Ag

RADIATION-HARDENABLE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL FOR HIGH-ENERGY RADIATION

DE3827901A1
(en)

*

1988-08-17
1990-02-22
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL PRODUCED THEREOF

DE3907953A1
(en)

*

1989-03-11
1990-09-13
Hoechst Ag

RADIATIONMARKABLE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL MADE THEREFROM FOR HIGHERERGETIC RADIATION

DE3907954A1
(en)

*

1989-03-11
1990-09-13
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL PREPARED THEREOF FOR HIGH-SERGETIC RADIATION

DE69029104T2
(en)

1989-07-12
1997-03-20
Fuji Photo Film Co Ltd

Polysiloxanes and positive working resist

DE3930087A1
(en)

*

1989-09-09
1991-03-14
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL THEREOF

DE3930086A1
(en)

*

1989-09-09
1991-03-21
Hoechst Ag

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL THEREOF

DE3940965A1
(en)

*

1989-12-12
1991-06-13
Basf Ag

RADIATION-SENSITIVE MIXTURE AND METHOD FOR PRODUCING RELIEF STRUCTURES

DE4002397A1
(en)

*

1990-01-27
1991-08-01
Hoechst Ag
Positive photosensitive mixt. contg. hydroxy-aralkyl acrylate polymer – and sensitiser, useful in printing plate mfr. and as photoresist

DE4003025A1
(en)

*

1990-02-02
1991-08-08
Hoechst Ag

RADIATION-SENSITIVE MIXTURE, RADIATION-SENSITIVE RECORDING MATERIAL PRODUCED THEREOF AND METHOD FOR THE PRODUCTION OF RELIEF RECORDS

JPH0480758A
(en)

*

1990-07-23
1992-03-13
Fuji Photo Film Co Ltd
Photosensitive composition

EP0502819A1
(en)

*

1991-03-01
1992-09-09
Ciba-Geigy Ag
Acid hardenable copolymers

EP0501919A1
(en)

*

1991-03-01
1992-09-02
Ciba-Geigy Ag
Radiation-sensitive compositions based on polyphenols and acetals

DE4112969A1
(en)

*

1991-04-20
1992-10-22
Hoechst Ag

ACID-CLEARABLE RADIATION-SENSITIVE COMPOUNDS, THIS CONTAINING RADIATION-SENSITIVE MIXTURE AND THE RADIO-SENSITIVE RECORDING MATERIAL MADE THEREOF

DE4112970A1
(en)

*

1991-04-20
1992-10-22
Hoechst Ag

Acid-cleavable radiation-sensitive compounds, the radiation-sensitive mixture containing them and radiation radiation-sensitive material made from them

DE4112968A1
(en)

*

1991-04-20
1992-10-22
Hoechst Ag

ACID-FUSIBLE COMPOUNDS, THIS CONTAINING POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE, AND MADE FROM THIS RADIATION-SENSITIVE RECORDING MATERIAL

US5364738A
(en)

*

1991-10-07
1994-11-15
Fuji Photo Film Co., Ltd.
Light-sensitive composition

JP2944296B2
(en)

1992-04-06
1999-08-30
富士写真フイルム株式会社

Manufacturing method of photosensitive lithographic printing plate

US5353705A
(en)

*

1992-07-20
1994-10-11
Presstek, Inc.
Lithographic printing members having secondary ablation layers for use with laser-discharge imaging apparatus

US5339737B1
(en)

*

1992-07-20
1997-06-10
Presstek Inc
Lithographic printing plates for use with laser-discharge imaging apparatus

AU674518B2
(en)

*

1992-07-20
1997-01-02
Presstek, Inc.
Lithographic printing plates for use with laser-discharge imaging apparatus

US5379698A
(en)

*

1992-07-20
1995-01-10
Presstek, Inc.
Lithographic printing members for use with laser-discharge imaging

USRE35512F1
(en)

*

1992-07-20
1998-08-04
Presstek Inc
Lithographic printing members for use with laser-discharge imaging

US5351617A
(en)

*

1992-07-20
1994-10-04
Presstek, Inc.
Method for laser-discharge imaging a printing plate

DE4242050A1
(en)

*

1992-12-14
1994-06-16
Hoechst Ag

Polymers with N, N-disubstituted sulfonamide side groups and their use

DE4242051A1
(en)

*

1992-12-14
1994-06-16
Hoechst Ag

N, N-disubstituted sulfonamides and the radiation-sensitive mixture produced with them

JPH06230574A
(en)

*

1993-02-05
1994-08-19
Fuji Photo Film Co Ltd
Positive type photosensitive composition

US5372915A
(en)

*

1993-05-19
1994-12-13
Eastman Kodak Company
Method of making a lithographic printing plate containing a resole resin and a novolac resin in the radiation sensitive layer

JPH07140666A
(en)

*

1993-06-04
1995-06-02
Internatl Business Mach Corp
Micro-lithographic resist composition, acid instability compound, formation of micro-lithographic relief image and acid sensitive polymer composition

GB9326150D0
(en)

*

1993-12-22
1994-02-23
Alcan Int Ltd
Electrochemical roughening method

DE4414897A1
(en)

*

1994-04-28
1995-11-02
Hoechst Ag

Aromatic diazonium salts and their use in radiation-sensitive mixtures

DE4414896A1
(en)

*

1994-04-28
1995-11-02
Hoechst Ag

Positive working radiation sensitive mixture

US5466557A
(en)

*

1994-08-29
1995-11-14
Eastman Kodak Company
Radiation-sensitive composition containing a resole resin, a novolac resin, a latent bronsted acid, an infrared absorber and terephthalaldehyde and use thereof in lithographic printing plates

JPH0876380A
(en)

1994-09-06
1996-03-22
Fuji Photo Film Co Ltd
Positive printing plate composition

DE4444669A1
(en)

1994-12-15
1996-06-20
Hoechst Ag

Radiation sensitive mixture

JPH0954437A
(en)

1995-06-05
1997-02-25
Fuji Photo Film Co Ltd
Chemical amplification type positive resist composition

JP3506817B2
(en)

*

1995-07-26
2004-03-15
クラリアント インターナショナル リミテッド

Radiation sensitive composition

TW466256B
(en)

1995-11-24
2001-12-01
Ciba Sc Holding Ag
Borate photoinitiator compounds and compositions comprising the same

JP3591672B2
(en)

1996-02-05
2004-11-24
富士写真フイルム株式会社

Positive photosensitive composition

US6060222A
(en)

*

1996-11-19
2000-05-09
Kodak Polcyhrome Graphics Llc
1Postitve-working imaging composition and element and method of forming positive image with a laser

JP3858374B2
(en)

*

1997-09-18
2006-12-13
コニカミノルタホールディングス株式会社

Photosensitive composition and image forming material

US6174646B1
(en)

*

1997-10-21
2001-01-16
Konica Corporation
Image forming method

GB2335283B
(en)

1998-03-13
2002-05-08
Horsell Graphic Ind Ltd
Improvements in relation to pattern-forming methods

EP1031878A1
(en)

1999-02-23
2000-08-30
Shipley Company LLC
Novel polymers and photoresist compositions comprising same

JP3969909B2
(en)

1999-09-27
2007-09-05
富士フイルム株式会社

Positive photoresist composition

JP3963624B2
(en)

1999-12-22
2007-08-22
富士フイルム株式会社

Positive photoresist composition for deep ultraviolet exposure

AUPQ700100A0
(en)

*

2000-04-18
2000-05-11
Orbital Engine Company (Australia) Proprietary Limited
Engine speed control for internal combustion engines

AU8015701A
(en)

*

2000-08-29
2002-03-13
Jsr Corp
Composition having refractive index sensitively changeable by radiation and method for forming refractive index pattern

AU2258302A
(en)

*

2000-12-11
2002-06-24
Jsr Corp
Radiation-sensitive composition changing in refractive index and method of changing refractive index

US7071255B2
(en)

2001-02-19
2006-07-04
Jsr Corporation
Radiation-sensitive composition capable of having refractive index distribution

US7125647B2
(en)

2001-03-13
2006-10-24
Jsr Corporation
Radiation-sensitive composition changing in refractive index and utilization thereof

JP2003043682A
(en)

*

2001-08-01
2003-02-13
Jsr Corp
Radiation sensitive composition with variable dielectric constant and method for varying dielectric constant

EP1468036B1
(en)

*

2002-01-14
2008-10-08
The General Hospital Corporation
Biodegradable polyketal polymers and methods for their formation and use

US7255972B2
(en)

2002-10-23
2007-08-14
Az Electronic Materials Usa Corp.
Chemically amplified positive photosensitive resin composition

JP4163964B2
(en)

*

2003-01-07
2008-10-08
岡本化学工業株式会社

Image forming composition and photosensitive lithographic printing plate using the same

JP4440600B2
(en)

*

2003-10-31
2010-03-24
Ａｚエレクトロニックマテリアルズ株式会社

Chemically amplified photosensitive resin composition for thick and ultra-thick films

JP4396443B2
(en)

2004-08-18
2010-01-13
コニカミノルタエムジー株式会社

Method for producing and using photosensitive lithographic printing plate

US20070172758A1
(en)

*

2006-01-20
2007-07-26
Konica Minolta Medical & Graphic, Inc.
Planographic printing plate material and its manufacturing process

JP2010113142A
(en)

*

2008-11-06
2010-05-20
Sekisui Chem Co Ltd
Positive photosensitive composition and method for forming electrically conductive pattern

JP5419208B2
(en)

*

2009-05-11
2014-02-19
株式会社ダイセル

Alternating copolymer and process for producing the same

US8846981B2
(en)

2012-01-30
2014-09-30
Southern Lithoplate, Inc.
1,1-di[(alkylphenoxy)ethoxy]cyclohexanes

US8632943B2
(en)

2012-01-30
2014-01-21
Southern Lithoplate, Inc.
Near-infrared sensitive, positive-working, image forming composition and photographic element containing a 1,1-di[(alkylphenoxy)ethoxy]cyclohexane

US9063420B2
(en)

*

2013-07-16
2015-06-23
Rohm And Haas Electronic Materials Llc
Photoresist composition, coated substrate, and method of forming electronic device

Family Cites Families (15)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US2892712A
(en)

*

1954-04-23
1959-06-30
Du Pont
Process for preparing relief images

GB1180845A
(en)

*

1967-08-08
1970-02-11
Agfa Gevaert Nv
Light-Sensitive Polymers and their use in the preparation of Photographic Printing Plates

US3753718A
(en)

*

1972-02-04
1973-08-21
Scott Paper Co
Photosensitive medium comprising a cyclic acetal of furfural, a lower haloalkane, and silica

US3779778A
(en)

*

1972-02-09
1973-12-18
Minnesota Mining & Mfg
Photosolubilizable compositions and elements

DE2232365C2
(en)

*

1972-07-01
1982-06-09
Basf Ag, 6700 Ludwigshafen

Mixtures polymerizable by UV radiation

US4007209A
(en)

*

1972-07-01
1977-02-08
Badische Anilin- & Soda-Fabrik Aktiengesellschaft
Acetals which act as photoinitiators

US3915704A
(en)

*

1973-11-01
1975-10-28
Xerox Corp
Photoinduced, acid catalyzed degradation of degradable polymers

US3964907A
(en)

*

1973-11-12
1976-06-22
Xerox Corporation
Method for the preparation of relief printing masters

US3984253A
(en)

*

1974-04-22
1976-10-05
Eastman Kodak Company
Imaging processes and elements therefor

US3923514A
(en)

*

1974-06-27
1975-12-02
Xerox Corp
Method for the preparation of relief printing masters

US3963491A
(en)

*

1974-06-27
1976-06-15
Xerox Corporation
Imaging method

US3991033A
(en)

*

1975-01-30
1976-11-09
E. I. Du Pont De Nemours & Company
Photosensitive and degradable polyoxymethylene polymers and their application in imaging

CH621416A5
(en)

*

1975-03-27
1981-01-30
Hoechst Ag

US4086210A
(en)

*

1976-05-10
1978-04-25
Eastman Kodak Company
Radiation sensitive polymeric o-nitrophenyl acetals

US4108839A
(en)

*

1977-01-21
1978-08-22
E. I. Du Pont De Nemours And Company
Photosensitive polyaldehydes and use in photoimaging

1977

1977-04-25
DE
DE2718254A
patent/DE2718254C3/en
not_active
Expired

1978

1978-04-21
NL
NL7804303A
patent/NL7804303A/en
not_active
Application Discontinuation

1978-04-21
AU
AU35356/78A
patent/AU525946B2/en
not_active
Expired

1978-04-21
SE
SE7804587A
patent/SE444232B/en
not_active
IP Right Cessation

1978-04-21
CA
CA301,725A
patent/CA1128804A/en
not_active
Expired

1978-04-21
IE
IE787/78A
patent/IE46621B1/en
unknown

1978-04-21
IT
IT49011/78A
patent/IT1102623B/en
active

1978-04-24
BE
BE187054A
patent/BE866305A/en
not_active
IP Right Cessation

1978-04-24
GB
GB16074/78A
patent/GB1602902A/en
not_active
Expired

1978-04-24
FR
FR7812009A
patent/FR2389155A1/en
active
Granted

1978-04-24
JP
JP4919678A
patent/JPS53133429A/en
active
Granted

1978-04-24
ZA
ZA00782331A
patent/ZA782331B/en
unknown

1978-04-24
CH
CH441978A
patent/CH635448A5/en
not_active
IP Right Cessation

1978-04-24
DK
DK176778A
patent/DK176778A/en
not_active
Application Discontinuation

1978-04-24
BR
BR7802527A
patent/BR7802527A/en
unknown

1978-04-24
US
US05/899,271
patent/US4247611A/en
not_active
Expired – Lifetime

Also Published As

Publication number
Publication date

FR2389155B1
(en)

1982-02-26

BE866305A
(en)

1978-10-24

JPS6239420B2
(en)

1987-08-22

NL7804303A
(en)

1978-10-27

IE780787L
(en)

1978-10-25

CH635448A5
(en)

1983-03-31

BR7802527A
(en)

1978-12-12

AU3535678A
(en)

1979-10-25

IE46621B1
(en)

1983-08-10

AU525946B2
(en)

1982-12-09

SE7804587L
(en)

1978-10-26

IT7849011D0
(en)

1978-04-21

SE444232B
(en)

1986-03-24

CA1128804A
(en)

1982-08-03

DE2718254A1
(en)

1978-11-02

ZA782331B
(en)

1979-04-25

DK176778A
(en)

1978-10-26

FR2389155A1
(en)

1978-11-24

IT1102623B
(en)

1985-10-07

DE2718254B2
(en)

1979-08-02

JPS53133429A
(en)

1978-11-21

DE2718254C3
(en)

1980-04-10

US4247611A
(en)

1981-01-27

Similar Documents

Publication
Publication Date
Title

US4247611A
(en)

1981-01-27

Positive-working radiation-sensitive copying composition and method of using to form relief images

US4248957A
(en)

1981-02-03

Acid degradable radiation-sensitive mixture

US4250247A
(en)

1981-02-10

Acid degradable radiation-sensitive mixture

US4101323A
(en)

1978-07-18

Radiation-sensitive copying composition

EP0417556B1
(en)

1996-12-11

Positive-working radiation-sensitive mixture and recording material prepared therefrom

CA1103508A
(en)

1981-06-23

Radiation-sensitive copying composition

US4678737A
(en)

1987-07-07

Radiation-sensitive composition and recording material based on compounds which can be split by acid

JP2854112B2
(en)

1999-02-03

Positive processing radiation-sensitive mixtures and radiation-sensitive copying materials produced therefrom

US4311782A
(en)

1982-01-19

Radiation-sensitive mixture and process for the production of relief images

US5015554A
(en)

1991-05-14

Positive radiation-sensitive mixture

EP0444493B1
(en)

1996-11-20

Negative working radiation sensitive composition and radiation sensitive recording material produced therefrom

JPS61277679A
(en)

1986-12-08

Beta-ketoester or cyclic acetal or cyclic ketal of beta-amide, composition, image formation and product therefrom

EP0059250A1
(en)

1982-09-08

Light-sensitive composition and copying material prepared therefrom

US4840867A
(en)

1989-06-20

Positive-working radiation-sensitive recording material with radiation-sensitive 1,2-quinone diazide underlayer and thicker positive-working radiation-sensitive overlayer

US5354643A
(en)

1994-10-11

Oligomeric compounds with acid-labile protective groups useful in positive-working radiation-sensitive mixture

JPS63287950A
(en)

1988-11-25

Radiosensitive recording material

US4639406A
(en)

1987-01-27

Light-sensitive compound, light-sensitive mixture, and light-sensitive copying material prepared therefrom with 0-naphthoquinone diazide compound

KR100249066B1
(en)

2000-03-15

Acid-cleavable compounds, positive-work radiation-sensitive mixture containing these compounds, and radiation-sensitive material

JPH01106040A
(en)

1989-04-24

Positive type radiosensitive mixture and positive type radiosensitive recording material and manufacture of said recording material

DE3730787A1
(en)

1989-03-23

POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND RADIATION-SENSITIVE RECORDING MATERIAL MANUFACTURED THEREFROM

US3526503A
(en)

1970-09-01

Photoresist composition

US4983501A
(en)

1991-01-08

Positive-working radiation-sensitive composition and radiation-sensitive recording material prepared therewith

JP3040593B2
(en)

2000-05-15

Negative radiation-sensitive mixture and radiation-sensitive recording material produced using this mixture

EP0068346A1
(en)

1983-01-05

Photosensitive mixture on the basis of o-naphthoquinone diazides, and photosensitive copying material produced therefrom

JPH05221954A
(en)

1993-08-31

Radiosensitive compound that can be cleaved by acid, radiosensitive mixture containing the compound, and radiosensitive recording material prepared from the mixture

Legal Events

Date
Code
Title
Description

1982-02-10
PS
Patent sealed [section 19, patents act 1949]

1998-05-13
PE20
Patent expired after termination of 20 years

Effective date:
19980423

Download PDF in English