GB1584912A - Creation of Inventions and Patents with Artificial Intelligence

GB1584912A – Radiation-sensitive composition
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GB1584912A – Radiation-sensitive composition
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Radiation-sensitive composition

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Publication number
GB1584912A

GB1584912A
GB6018/78A
GB601878A
GB1584912A
GB 1584912 A
GB1584912 A
GB 1584912A
GB 6018/78 A
GB6018/78 A
GB 6018/78A
GB 601878 A
GB601878 A
GB 601878A
GB 1584912 A
GB1584912 A
GB 1584912A
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GB
United Kingdom
Prior art keywords
radiation
brominated
sensitive composition
stabilizer
sensitive
Prior art date
1977-02-18
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

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GB6018/78A
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Hitachi Ltd

Nippon Telegraph and Telephone Corp

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Hitachi Ltd
Nippon Telegraph and Telephone Corp
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.)
1977-02-18
Filing date
1978-02-15
Publication date
1981-02-18

1978-02-15
Application filed by Hitachi Ltd, Nippon Telegraph and Telephone Corp
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Hitachi Ltd

1981-02-18
Publication of GB1584912A
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patent/GB1584912A/en

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legal-status
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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

G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients

C08K5/00—Use of organic ingredients

C08K5/0008—Organic ingredients according to more than one of the “one dot” groups of C08K5/01 – C08K5/59

C08K5/005—Stabilisers against oxidation, heat, light, ozone

Description

PATENT SPECIFICATION ( 11) 1 584 912
( 21) Application No 6018/78 ( 22) Filed 15 Feb 1978 ( 19) : ( 31) Convention Application No 52/016232 ( 32) Filed 18 Feb 1977 in ( 33) Japan (JP)
( 44) Complete Specification Published 18 Feb 1981
1 In ( 51) INT CL 3 CO 8 L 63/08 _ ( 52) Index at Acceptance C 3 K 210 271 284 290 292 CZ C 3 W 213 C 304 ( 54) RADIATION-SENSITIVE COMPOSITION ( 71) We, HITACHI, LTD, a Japanese Company of 1-5-1 Marunouchi, Chiyodaku, Tokyo, Japan, and NIPPON TELEGRAPH AND TELEPHONE PUBLIC CORPORATION, a Japanese Company of 1-6 1-chome, Uchisaiwai-cho, Chiyoda-ku, Tokyo, Japan, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the 5 following statement:-
This invention relates to radiation-sensitive organic polymeric materials, particularly materials sensitive to radiation such as electron beams, ion beams, yrays, neutron beams and X-rays.
A particular problem with known materials of this kind is instability The term “instabil 10 ity” is intended to mean the characteristic which causes insolubility (spontaneous insolubilization) of unirradiated parts of the polymeric material.
As is well known, electron beam-sensitive organic polymers can be employed to replace the photosensitive resins and are being put into practical use, as for example, resist materials The resist materials are broadly classified into either photo resists exploiting photosen 15 sitivity or electron-beam resists exploiting electron-beam sensitivity Deep-UV resist, X-ray resist and electron-beam resist materials are noted as those in which precision working is possible.
It has been previously proposed to have as a material of this type a radiation-sensitive material which comprises a polymeric material having a plurality of epoxy groups and a 20 plurality of bromine atoms in at least one of the constituent monomers thereof (Japanese Patent Application No 51-16029, corresponding to U K Patent 1529123 This radiationsensitive material is made of at least one polymeric material selected from brominated and epoxidized polymers of butadiene, brominated and epoxidized copolymers of butadiene, 25 brominated and epoxidized polymers of isoprene, brominated and epoxidized copolymers of isoprene, brominated products of copolymers of butadiene with addition-polymerizable compounds containing an epoxy group, brominated products of copolymers of isoprene with 30 addition-polymerizable compounds containing an epoxy group, and epoxidized products of copolymers of either butadiene or isoprene with additionpolymerizable compounds containing a bromine atom.
The polymeric materials can be produced by subjecting a polymer or copolymer containing a plurality of carbon-to-carbon double bonds in one molecule, such as polybutadiene, 35 polyisoprene, a butadiene copolymer or an isoprene copolymer, to addition with bromine and simultaneous or subsequent epoxidation, or by subjecting to bromination a copolymer of a diene compound with an addition-polymerizable monomer containing an epoxy group.
As radiation sensitive materials, these polymeric materials have high sensitivity, high resolution and high contrast characteristics Owing to their high sensitivity, they are useful 40 as recording materials in the field of recording information.
The employment of a radiation-sensitive material as an electron beam resist will now be explained with reference to Figs 1-A to 1-C of the accompanying drawings.
As shown in Fig 1-A, a metallic evaporated film 2 is formed on a glass substrate 1, and a coating film 3 of radiation-sensitive material is formed thereon A part of the coating film 3 45 2 1,584,912 2 is irradiated by a suitable dose of an electron beam 4 whereafter the coating film is treated with a suitable organic solvent which acts as a liquid developer The part of the coating film which has not been subjected to the irradiation by the electron beam is dissolved and removed by the action of the solvent and only that part of the coating film which has been rendered insoluble by the irradiation by the electron beam remains undissolved by the 5 solvent, thus attaining the situation illustrated in Fig 1-B The structure is then further treated with chemicals which etch the metallic evaporated film 2, to obtain the structure shown in Fig 1-C, wherein the metallic evaporated film is left only in an area corresponding to the remaining part of the coating film 3 and the rest of the film has been dissolved away.
In this way, there can be obtained a glass plate in which the film remains only in the area 10 irradiated by the electron beam If the irradiation of the polymer coating film by the electron beam is in the form of a pattern, the parts of metallic evaporated film remaining after the step of etching the film will follow the form of the pattern Using electron-beam irradiation equipment and the electron-beam resist in this manner, even a complicated and very fine pattern can be worked extremely precisely, and a metallic evaporated film of any 15 desired design can thus be obtained Similarly when a sample and a mask are held in close contact and they are irradiated by electromagnetic waves of short wavelengths, e g X-rays, a complicated and very fine pattern can be worked extremely precisely and a metallic evaporated film of any desired design can be obtained.
It has been found, however, that when the polymeric material containing epoxy groups 20 and bromine atoms is allowed to stand after synthesis, prior to being used in the steps described above, a phenomenon is observed in which the width of a line irradiated by an electron beam becomes somewhat greater than the width of the beam of the irradiating light It has also been found that the resist solution also undergoes insolubilization little by little when allowed to stand, that the viscosity and sensitivity of the resist solution rises with 25 insolubilization, and that when insolubilization becomes more pronounced, a situation in which the entire solution solidifies can take place.
For example, when a structure as in Fig 1-B is obtained by irradiation of the appropriate part of the coating film 3 with the electron beam and sometime thereafter development with the organic solvent, the sensitivity may alter depending on the time interval between irradi 30 ation and development, and the degree of fog and therefore the width of a line may alter depending on the development period or fogging may appear in an unirradiated area.
Such fogging and related phenomena can cause instability in the devices in which the films are used, and become a very serious problem in the precision production of semiconductor devices, especially in the field of integrated circuits (IC’s), magnetic bubble domain 35 memories etc requiring high working precision in complicated microcircuits Prevention or mitigation of such fogging and related phenomena is thus very important.
The phenomenon by which the organic polymer coating film in the unirradiated area or the resist solution becomes insoluble as described above is usually called “spontaneous insolubilization” or “instability” Although the mechanism by which the phenomenon is 40 caused is not clear, it is thought that the most important cause is that the polymeric resist material is dissolved little by little and induces cross linkage in the undissolved resist material, whether it has been irradiated or not; where the phenomenon occurs in the non-irradiated part it causes fog; at the non-irradiated peripheries to irradiated parts it gives rise to line broadening 45 According to the present invention there is provided a radiationsensitive composition comprising a radiation-sensitive polymeric material in which each polymer molecule contains a plurality of epoxy groups and a plurality of bromine atoms, and at least one stabilizer selected from coupounds having stable free radicals, polymerization inhibitors, ketoneamine reaction products and phenols 50 By the invention it is possible to provide a radiation-sensitive composition in which “instability” is eliminated or substantially reduced.
As a result of experiments in which a variety of additives were introduced as stabilizers into radiation-sensitive polymers, it has been discovered that compounds having stable free radicals, polymerization inhibitors, ketone-amine reaction products or phenols all being 55 soluble in organic substances, having particularly good “instability” preventing or suppressing effects Accordingly, this invention proposes that these stabilizers are added to the polymeric material In this way, the “instability” can be easily prevented or mitigated, possibly without any substantial degradation of the sensitivities of the polymeric material to radiations such as electron beams, ion beams, y-rays, neutron beams and Xrays 60 The mechanism causing instability is not certain However, since instability prevention is produced by adding compounds having stable free radicals, polymerization inhibitors, ketone-amine reaction products or phenol derivatives, it is thought that the polymeric material, i e the resist material, dissolves little by little to generate radicals which cause instability It is thought that these active radicals are inactivated by the additives as men 65 1,584,912 3 1,584,912 3 tioned above, with the result that the cross linkage of the polymers caused by the active radicals will be reduced or stopped.
Suitable compounds having stable free radicals include 2,2-diphenyl-1picrylhydrazyl and a-y-bisdiphenylene-,8-phenylallyl Suitable polymerization inhibitors include:
hydroquinone monomethyl ether; 5 benzoquinone; methylquinone; 2,5-dimethylquinone; thymoquinone; trimethylquinone; 10 tetramethylquinone; chloranil; 1,4-naphthoquinone; phenanthraquinone; chrysenequinone; 15 2-methoxyquinone; 2-chlorobenzoquinone; dichlorobenzoquinone; methylnaphthoquinone; dichloronaphthoquinone; 20 anthraquinone; and 2-tert-butylanthraquinone Suitable ketone-amine reaction products, include, for example, polymerization products of 2,2,4-trimethyl-1,2-dihydroquinoline, and quinoline derivates of 6-ethoxy2, 2,4trimethyl-1,2-dihydroquinoline and 6-dodecyl-2,2,4-trimethyl-1,2dihydroquinoline Suit 25 able phenol derivatives include for example 4,4 ‘-dihydroxydiphenyl; dihydroxydiphenyl methane derivatives; and 1, 1-bis-( 4-hydroxyphenyl)-cyclohexane.
Suitable methods for adding the stabilizer to the high molecular weight compound include dissolving the stabilizer in an organic solvent before the high molecular weight compound is dissolved in the solvent Alternatively, the stabilizer may be dissolved simul 30 taneously with the high molecular weight compound or may be dissolved in a solution in which the high molecular weight compound is already dissolved With all these methods, substantially equal effects can be achieved It should be noted that the duration of the addition should be sufficient to dissolve the additive so that it does not exist in the solution in the solid state Even when the quantity of stabilizer added is slight, the effect is noticed 35 In general, as the quantity of stabilizer added is larger, the effect is more noticeable When the additive is added in large quantities, it is sometimes precipitated in the coating film formed later It is therefore necessary to restrict the quantity of stabilizer added so that no precipitation occurs Precipitation of the additive in the coating film causes pinholes in the film and lowers the accuracy of etching; therefore it must be avoided It has been found that 40 the preferably amount of stabilizer, based on the weight of the high molecular weight compound is 0 01 to 5 weight %.
The high molecular weight compound used may be one or more of brominated and epoxidized polymers of butadiene, brominated and epoxidized copolymers of butadiene, 45 brominated and epoxidized polymers of isoprene, brominated and epoxidized copolymers of isoprene, brominated products of copolymers of butadiene with additionpolymerizable compounds containing an epoxy group, brominated products of copolymers of isoprene with addition-polymerizable compounds containing an epoxy group, and epoxidized products of 50 copolymers of one of butadiene and isoprene with addition-polymerizable compounds containing a bromine atom.
The polymer of butadiene employed may be any of 1,2-polybutadiene, 1,4polybutadiene, polybutadienes having both the 1,2 and 1,4-structure and mixtures thereof.
The same applies to the polymers of isoprene Copolymers of butadiene which can be used 55 are known butadiene copolymers such as styrene-butadiene copolymers and butadieneisoprene copolymers Likewise, known isoprene copolymers can be used Examples of epoxy group containing addition-polymerizable monomers which may be used include glycidyl acrylate and glycidyl methacrylate.
The preferred range of epoxidation is 10 % to 70 % and the preferred range of bromina 60 tion is 7 % to 50 % The “degree of epoxidation” or “degree of bromination” means the ratio of the number of expoxidized or brominated monomer units in the polymer or copolymer to the total number of monomer units The calculation of the degree of epoxidation or bromination is done on the supposition that one monomer unit is epoxidized by one atom of oxygen or that one monomer unit is brominated by two atoms of bromine Since 65 4 1,584,912 4 either reaction, epoxidation or bromination, takes place on one monomer unit, the sum of the degree of epoxidation and the degree of bromination is always lower than or equal to %.
A preferred range for the molecular weight of the high molecular weight compound is from 500 to 10,000,000 A more preferable range is from 100,000 to 2,000, 000 These 5 values of the molecular weight are derived from viscosity measurements.
When radiation-sensitive compositions of this invention are employed as an electronbeam resist, a suitable liquid developer is any solvent capable of dissolving the composition and incapable of dissolving the radiation-cross-linked product of the high molecular weight compound Among such solvent, dioxane, butyl acetate and mixed solvents containing 10 dioxane or butyl acetate, for example butyl acetate-ethyl cellosolve or dioxane-ethyl Cellosolve are all excellent liquid developers ‘Cellosolve’ is a Registered Trade Marks.
When compositions of this invention are employed as, for example, electron-beam resists in the fabrication of photo-resist masks for manufacturing semiconductor devices, masks of extraordinarily high working precision are attainable When the surface of a coating film of 15 a composition of this invention is scanned by an-electron beam directly without any mask, a resist film of the desired shape having an extraordinarily high working precision is attainable This technique then can in practice replace conventional photolithography in the field of semiconductor technology Furthermore, compositions of this invention may be satisfactorily usable as recording material for recording a very fine pattern, for example high 20 density picture recording, electron-beam holography or X-ray holography.
Examples of the invention will now be given, as illustrative of it.
In all of the following examples, in order to gauge the extent of the “instability”, there is indicated either the electron-beam sensitivity after a solution of the radiation-sensitive composition has been left to stand for a certain time, or the solubility in a solvent after a 25 coating film has been left to stand for a certain time.
EXAMPLE 1
To 50 ml of monochlorobenzene was added 1 5 g of 1,2-polybutadiene (RB 820 manufactured by the Japan Synthetic Rubber Co and having a 1,2 structure content of about 82 %, a 1,4-structure content of about 18 % and a molecular weight of about 160,000), and 30 the mixture was heated to form a homogeneous solution There was added to the solution at room temperature a solution of peracetic acid in acetic acid in an amount sufficient to epoxidize all the double bonds of the 1,2-polybutadiene, and the mixture was agitated for 2 hours to effect epoxidation of the 1,2-polybutadiene.
The acetic acid solution of peracetic acid used for the epoxidation was prepared in the 35 following manner 0 20 ml of concentrated sulfuric acid, 22 ml of glacial acetic acid and 4 1 ml of 30 % aqueous hydrogen peroxide were mixed together, and the mixture was allowed to stand at room temperature overnight 3 0 g of sodium acetate trihydrate was added to and dissolved in the mixture The resulting precipitate of sodium sulfate was removed to obtain an acetic acid solution of peracetic acid which contained about 1 1 moles per liter of 40 peracetic acid After the said two hour period, the continuous agitation was maintained while a solution of 2 3 g of potassium bromide (containing bromine in an amount sufficient to add to 35 % of the original double bonds in the starting 1,2polybutadiene) in 7 ml of water was added to the reaction mixture By the reaction of the potassium bromide with the peracetic acid left in the reaction mixture, bromine was generated and the reaction mixture 45 became brown As the addition of the bromine to the double bonds of the 1, 2polybutadiene proceeded, the bromine was gradually consumed and the reaction mixture became colorless when all the bromine had been consumed.
The reaction mixture was washed twice with about 200 ml of water and 2 0 g of sodium bicarbonate was added to neutralize the remaining acetic acid-and any minute amount of 50 peracetic acid which might remain Then 25 ml of cyclohexane was added to the reaction mixture and the resulting mixture was centrifuged to recover a transparent supernatant 50 ml of cyclohexane was added to the supernatant to precipitate the resulting polymeric compound The polymeric compound was dissolved in 20 ml of monochlorobenzene to form a homogenous monochlorobenzene solution of brominated epoxidized 1,2 55 polybutadiene The epoxidization and bromination of the 1,2-polybutadiene was confirmed by infrared spectroscopy which showed absorption peaks at a wave number of 830 cm indicating an epoxy group and at 600 cm indicating a carbon-to-bromine bond The degree of epoxidation of the high molecular compound was found to be about 18 %, and the degree of bromination about 35 % 60 The monochlorobenzene solution of the brominated epoxidized 1,2polybutadiene was divided into two 1 weight-% of 2,2-diphenyl-1-picrylhydrazyl (based on the polymer weight) was added as a stabilizer to one of the divided parts and a homogenous mixed solution obtained After allowing the two solutions to stand at room temperature for 50 days, the electron-beam sensitivity characteristics of these resist materials were measured as 65 1,584,912 5 follows Each solution was spin-coated and dried on an oxidized silicon wafer to form a polymer film having a thickness of 0 3 to 0 6 gim The coated wafer was placed in an electron beam exposure apparatus and was irradiated in vacuo with an electron beam having an acceleration voltage of 15 KV, while the dose was varied Then, the coated wafer was taken out of the apparatus and dipped in a developer for 2 minutes to effect develop 5 ment, the developer consisting of n-butyl acetate and ethyl cellosolve in a volumetric ratio of 3: 2 Thereafter, the developer was removed by hot air drying, and the thickness of the polymer film insolubilized by exposure to the electron beam and left on the surface of the silicon wafer was measured by means of an interference microscope The thickness of the film left after the development was plotted with respect to the electron beam dose, to obtain 10 a graphical representation of the electron-beam sensitivity characteristic.
The electron-beam sensitivity characteristics thus obtained in Fig 2 of the accompanying drawing as curves 21 and 22 The curve 21 is the sensitivity curve of the radiation-sensitive material having no additive, while the curve 22 is that of the radiationsensitive composition containing the stabilizer For reference, the electron-beam sensitivity characteristic of the 15 brominated epoxidized 1,2-polybutadiene with no stabilizer added thereto as measured immediately after the synthesis is shown as a curve 23 in Fig 2.
It is apparent from Fig 2 that the radiation-sensitive material with no added stabilizer had the sensitivity made approximately three times higher at a crosslinked film thickness of 50 % when left to stand at the room temperature for 50 days after the synthesis It is also 20 understood that, as the gradient of the sensitivity curve decreases, a low contrast characteristic is exhibited.
On the other hand, the curves 22 and 23 agree perfectly, and the radiation-sensitive composition in which 1 weight-% of 2,2-diphenyl-1-picrylhydrazyl as based on the polymer is added as the stabilizer, does not show altered sensitivity, even when allowed to stand at 25 room temperature for 50 days It can also be seen that since the gradient of the sensitivity curve does not change over the 50 days, a remarkable stabilizing effect has been achieved.
EXAMPLE 2
A radiation-sensitive composition was prepared using the same brominated epoxidized 1,2-polybutadiene as in Example 1 and adding 0 1 weight-% of 2,2-diphenyl1 30 picrylhydrazyl After allowing this composition to stand at room temperature for 30 days, measurements were made by the same method as in Example 1 A sensitivity curve the same as curve 22 in Fig 2 was obtained This indicates that the composition is equally stabilized.
EXAMPLE 3 35
A radiation-sensitive composition was prepared using the same brominated epoxidized 1,2-polybutadiene as in Example 1 and adding 0 01 weight-% of 2,2diphenyl-1picrylhydrazyl After allowing this composition to stand at room temperature for 50 days, measurements were made by same method as in Example 1 A sensitivity characteristic as indicated in curve 24 in Fig 2 was obtained This composition is in fact effective provided 40 that it is used within a short period.
EXAMPLE 4
A radiation-sensitive composition was prepared using the same brominated epoxidized 1,2-polybutadiene as in Example 1 and adding 0 5 weight-% of a,ybisdiphenylene/3-phenylallyl After allowing this composition to stand at room temperature for 50 days, 45 measurements were made by the same method as in Example 1 A sensitivity curve the same as the curve 22 in Fig 2 was obtained.
EXAMPLE 5
A radiation-sensitive composition was prepared using a brominated epoxidized 1,2polybutadiene synthesized by the same method as in Example 1 and adding 1 weight-% of 50 hydroquinone monomethyl ether After this composition had been allowed to stand at room temperature for 30 days, it was applied to the surface of a chromium evaporated film on a glass substrate and then dried Even when allowed to stand at room temperature for 4 days, the coating film thus formed could easily be dissolved and removed by a liquid developer consisting of n-butyl acetate and ethyl cellosolve at a volumetric ratio of 1: 1, 55 and no insolubilized part remained In contrast, a comparative example in which hydroquinone monomethyl ether was not added could not be dissolved perfectly and removed by the aforementioned developer, and an evident insolubilized film was left.
Besides the foregoing examples, similar tests were conducted on benzoquinone, etc In all the cases, a stabilizing effect was noted It has been found that, as previously described any 60 compound having stable radicals or quinones, which can be dissolved in organic solvents, can be used as a stabilizer in this invention.
EXAMPLE 6
A radiation-sensitive composition was prepared using the same brominated epoxidized 1,2-polybutadiene as in Example 1 and adding 1 weight-% of a polymerization product of 65 1,584,912 2,2,4-trimethyl-1,2-dihydroquinoline (Antigen RD manufactured by Sumitomo Chemicals Co.) After this composition had been allowed to stand at room temperature for 30 days, measurements were made by the same method as in Example 1 A sensitivity curve the same as the curve 22 in Fig 2 was obtained.
EXAMPLE 7 5
A radiation-sensitive composition was prepared using the same brominated epoxidized 1,2-polybutadiene as in Example 1 and adding 0 5 weight-% of 6ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (Nokrak AW manufactured by Ouchi Shinko Co.) After allowing this composition to stand at room temperature for 35 days, measurements were made by the same method as in Example 1 The sensitivity curve was the same 10 as the curve 22 in Fig 2.
EXAMPLE 8
A radiation-sensitive composition was prepared using the same brominated epoxidized 1,2-polybutadiene as in Example 1 and adding 0 3 weight-% of a lowtemperature reaction product between diphenyl amine and acetone (Antigen AM manufactured by Sumitomo 15 Chemicals Co) After this composition has stood at room temperature for 50 days, measurements were made by the same method as in Example 1 The sensitivity curve was the same as the curve 22 in Fig 2.
EXAMPLE 9
A radiation-sensitive composition was prepared using the same brominated epoxidized 20 1,2-polybutadiene as in Example 1 and 0 5 weight-% of 1,1-bis-( 4hydroxyphenyl)cyclohexane being a phenol derivative (Antigen W manufactured by Sumitomo Chemicals Co.) was added After this composition had stood at room temperature for 50 days, measurements were made by the same method as in Example 1 The sensitivity curve was the same as the curve 22 in Fig2 25 EXAMPLE 10
1.9 g of 1,4-polyisoprene (Cariflex IR 309 manufactured by Shell Chemical Corp) was dissolved in 50 ml of monochlorobenzene to form a homogeneous solution A solution of 3.3 g of potassium bromide (containing bromine in an amount sufficient to add to 50 % of the double bonds of the 1,4-polyisoprene) in 10 ml of water was added to the above 30 solution The mixture was agitated sufficiently While agitation was occurring, 32 ml of an acetic solution of peracetic acid prepared in the manner described in Example 1 was added to the mixture The color of bromine formed by the reaction between peracetic and potassium bromide disappeared almost instantaneously as the addition of the bromine to the double bonds of the 1,4-polyisoprene occurred After completion of the addition of perace 35 tic acid, the reaction mixture was agitated for 2 hours to achieve epoxidation Subsequently, the reaction mixture was neutralized and refined by the same method as in example 1.
Finally, the polymer solution was dissolved in a solution consisting of 20 ml of monochlorobenzene and 20 ml of toluene, to obtain a solution of brominated epoxidized 1,4polyisoprene 40 The electron-beam sensitivity characteristic of the brominated epoxidized 1,4polyisoprene thus obtained was measured in the same manner as in Example 1 As the result, a crosslinked film began to remain at a dose of 2 5 x 10-8 C/cm 2, and the thickness of the crosslinked film became equal to that of a coating film at a dose of 4 x 10-7 C/cm 2 A radiation-sensitive composition was prepared by adding to the polymer solution, 1 45 weight-% of 6 ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (Nokrak AW manufactured by Ouchi Shinko Co) After this composition had been allowed to stand at the room temperature for 100 days, its electron-beam sensitivity was measured The same values were obtained as measured immediately after the synthesis, and this indicated that no instability had occurred 50 EXAMPLE 11
A process similar to Example 7 in which the quantity of 6ethoxy-2,2,4-trimethyl-l,2-dihydroquinoline was 5 weight-% was performed In this case, the same result as in Example 7 was obtained with no pinholes appearing in the film.
In the foregoing examples, brominated substances of epoxidized 1,2polybutadiene and 55 epoxidized 1,4-polyisoprene have been exemplified as the radiationsensitive materials It has been found that similar effects are achieved on other materials made of brominated substances such as a copolymer of epoxidized isoprene, a copolymer between an additionpolymerizable compound having a glycidyl group and butadiene, and a copolymer between an addition-polymerizable compound having a glycidyl group and isoprene 60

Claims (9)

WHAT WE CLAIM IS:-

1 A radiation-sensitive composition comprising a radiation-sensitive polymeric material in which each polymer molecule contains a plurality of epoxy groups and a plurality of bromine atoms, and at least one stabilizer selected from compounds having stable free radicals, polymerization inhibitors, ketone-amine reaction products and phenols 65 1,584,912

2 A radiation-sensitive composition according to claim 1, wherein said stabilizer or stabilizers are present in the amount 0 01 to 5 weight-% with respect to said radiationsensitive polymer.

3 A radiation-sensitive composition according to claim 1 or claim 2, wherein said stabilizer has stable free radicals and is 2,2-diphenyl-1-picrylhydrazyl and/or a,ya 5 bisdiphenylene-/3-phenylallyl.

4 A radiation-sensitive composition according to claim 1 or claim 2 wherein said stabilizer is polymerization inhibitor and is selected from hydroquinone monomethyl ether; benzoquinone; 10 methylquinone; 2,5-dimethylquinone; thymoquinone; trimethylquinone; tetramethylquinone; 15 chloranil; 1,4-naphthoquinone, phenanthraquinone; chrysenequinone; 2-methoxyquinone; 20 2-chlorobenzoquinone; dichlorobenzoquinone; methylnaphthoquinone; dichloronaphthoquinone; anthraquinone; and 25 2-tert-butylanthraquinone.

A radiation-sensitive composition according to claim 1 or claim 2 wherein said stabilizer is a ketoneamine reaction product and is selected from polymerization products of 2,2,4-trimethyl 1,2-dihydroquinoline; 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; and 30 6-dodecyl-2,2,4-trimethyl 1,2-dihydroquinoline.

6 A radiation-sensitive composition according to claim 1 or claim 2 wherein said stabilizer is a phenol and is selected from 4,4 ‘-dihydroxydiphenyl; dihydroxydiphenyl methane derivatives; and 35 1,1 -bis-( 4-hydroxyphenyl)-cyclohexane.

7 A radiation-sensitive composition according to any one of claims 1 to 6 wherein said radiation n-sensitive polymeric material comprises at least one of brominated and epoxidized polymers of butadiene, brominated and epoxidized copolymers of butadiene, 40 brominated and epoxidized polymers of isoprene, brominated and epoxidized copolymers of isoprene, brominated products of copolymers of butadiene with additionpolymerizable compounds containing an epoxy group, brominated products of copolymers of isoprene with addition-polymerizable com 45 pounds containing an epoxy group, and epoxidized products of copolymers of one of butadiene and isoprene with additionpolymerizable compounds containing a bromine atom.

8 A radiation-sensitive composition according to any one of claims 1 to 7, wherein the degree of epoxidation of the said radiation-sensitive polymeric material is in the range 50 10-70 % with respect to the total monomer units in the polymer or copolymer, and the degree of bromination of the said radiation-sensitive polymer material is in the range 7 to % with respect to the total monomer units in the polymer or copolymer.

9 A radiation-sensitive composition containing a stabilizer substantially as herein described in any of the Examples 55 MEWBURN ELLIS & CO, Chartered Patent Agents 70-72 Chancery Lane, London WC 2 A l AD Agents for the Applicants 60 Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited Croydon, Surrey 1981.
Published by The Patent Office, 25 Southampton Buildings London, WC 2 A l AY, from which copies may be obtained.

GB6018/78A
1977-02-18
1978-02-15
Radiation-sensitive composition

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GB1584912A
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1977-02-18
1977-02-18
Radiation sensitive organic high molecular material

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Radiation-sensitive composition

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FR
(1)

FR2381338A1
(en)

GB
(1)

GB1584912A
(en)

NL
(1)

NL178331C
(en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

GB1602724A
(en)

1977-04-26
1981-11-18
Standard Telephones Cables Ltd
Resist material for x-ray lithography

JPS5857731B2
(en)

1978-09-16
1983-12-21
日本電信電話株式会社

Resist composition for plasma etching

GB2122765B
(en)

1981-12-21
1986-03-26
Inst Chimii Akademii Nauk Sssr
Photo-and electron resist

US5324604A
(en)

1991-06-17
1994-06-28
Eastman Kodak Company
Multi-active electrophotographic element and imaging process using free radicals as charge transport material

US6187965B1
(en)

1998-11-06
2001-02-13
International Business Machines Corporation
Process for recovering high boiling solvents from a photolithographic waste stream comprising at least 10 percent by weight of monomeric units

US5994597A
(en)

1998-11-06
1999-11-30
International Business Machines Corporation
Process for recovering high boiling solvents from a photolithographic waste stream comprising less than 10 percent by weight monomeric units

WO2011008417A1
(en)

2009-06-30
2011-01-20
Dow Global Technologies Inc.
Brominated and epoxidized flame retardants

CN105807479B
(en)

2016-05-24
2021-02-19
京东方科技集团股份有限公司
Display panel, manufacturing method thereof and display device

Family Cites Families (7)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

DE1010733B
(en)

1955-04-13
1957-06-19
Hoechst Ag

Stabilizers for polymers or copolymers of trifluorochloroethylene

US3063961A
(en)

1958-10-15
1962-11-13
Du Pont
Mixture of (1) a butadiene-nitrile copolymer, (2) a carboxylic butadiene copolymer and (3) a chlorinated vinylidene polymer and process of blending same

US3341491A
(en)

1963-09-10
1967-09-12
Hercules Inc
Vulcanized epihalohydrin polymers

US3417069A
(en)

1963-10-10
1968-12-17
Wyandotte Chemical Corp
Polyhalogenous epoxy copolymers

US3629110A
(en)

1968-10-02
1971-12-21
Simplex Wire & Cable Co
Solid dielectric polyolefin compositions containing voltage stabilizers

GB1384055A
(en)

1971-04-21
1975-02-19
Ici Ltd
Phenol derivatives and their use as antioxidants

US4209648A
(en)

1973-11-07
1980-06-24
The Goodyear Tire & Rubber Company
Alkylated hydroquinone antioxidants

1977

1977-02-18
JP
JP1623277A
patent/JPS53102025A/en
active
Granted

1978

1978-02-10
FR
FR7803750A
patent/FR2381338A1/en
active
Granted

1978-02-15
GB
GB6018/78A
patent/GB1584912A/en
not_active
Expired

1978-02-15
NL
NLAANVRAGE7801713,A
patent/NL178331C/en
not_active
IP Right Cessation

1978-02-15
US
US05/877,866
patent/US4187205A/en
not_active
Expired – Lifetime

1978-02-17
DE
DE2806928A
patent/DE2806928C3/en
not_active
Expired

Also Published As

Publication number
Publication date

JPS553689B2
(en)

1980-01-26

NL178331B
(en)

1985-10-01

NL7801713A
(en)

1978-08-22

NL178331C
(en)

1986-03-03

DE2806928C3
(en)

1981-07-16

JPS53102025A
(en)

1978-09-06

FR2381338A1
(en)

1978-09-15

DE2806928A1
(en)

1978-08-31

US4187205A
(en)

1980-02-05

FR2381338B1
(en)

1980-02-22

DE2806928B2
(en)

1980-10-09

Contact information