GB1572678A - Creation of Inventions and Patents with Artificial Intelligence

GB1572678A – Coating compositions comprising polyether triols
– Google Patents

GB1572678A – Coating compositions comprising polyether triols
– Google Patents
Coating compositions comprising polyether triols

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Publication number
GB1572678A

GB1572678A
GB43553/77A
GB4355377A
GB1572678A
GB 1572678 A
GB1572678 A
GB 1572678A
GB 43553/77 A
GB43553/77 A
GB 43553/77A
GB 4355377 A
GB4355377 A
GB 4355377A
GB 1572678 A
GB1572678 A
GB 1572678A
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GB
United Kingdom
Prior art keywords
range
polyol
polyoxypropylene triol
groups
polyaminotriazine
Prior art date
1976-10-20
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
GB43553/77A
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.)

Monsanto Co

Original Assignee
Monsanto Co
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.)
1976-10-20
Filing date
1977-10-19
Publication date
1980-07-30

1977-10-19
Application filed by Monsanto Co
filed
Critical
Monsanto Co

1980-07-30
Publication of GB1572678A
publication
Critical
patent/GB1572678A/en

Status
Expired
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

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

C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule

C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring

C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds

C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen

C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups

C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups

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

C08K5/04—Oxygen-containing compounds

C08K5/05—Alcohols; Metal alcoholates

C—CHEMISTRY; METALLURGY

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

C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS

C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers

C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

C08L61/32—Modified amine-aldehyde condensates

C—CHEMISTRY; METALLURGY

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

C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS

C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

C08L71/02—Polyalkylene oxides

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR

C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers

C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

C09D161/32—Modified amine-aldehyde condensates

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

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/31504—Composite [nonstructural laminate]

Y10T428/31678—Of metal

Y10T428/31688—Next to aldehyde or ketone condensation product

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/31504—Composite [nonstructural laminate]

Y10T428/31942—Of aldehyde or ketone condensation product

Description

PATENT SPECIFICATION ( 11) 1 572 678
X ( 21) Application No 43553/77 ( 22) Filed 19 Oct 1977 ( 19) 3 ( 61) Patent of Addition to No 1572677 Dated 19 Oct 1977 ( 31) Convention Application No 734080 ( 32) Filed 20 Oct 1976 in > ( 33) United States of America (US) Un ( 44) Complete Specification Published 30 Jul 1980 1 E I v P” ( 51) INT CL 3 CO 8 L 61/26 C 091) 3/50 (C 08 L 61/26 71/02) ( 52) Index at Acceptance C 3 R 38 B 2 B 38 B 3 C 38 B 3 D 38 C 38 D 3 A 38 N 2 Q 2 38 N 2 Q 3 A 38 N 2 S 38 N 3 A 38 N 4 C 12 C 8 R L 1 A L 2 X L 6 G ( 54) COATING COMPOSITIONS COMPRISING POLYETHER TRIOLS ( 71) We, MONSANTO COMPANY, a corporation organised under the laws of the State of Delaware United States of America, of 800 North Lindbergh Boulevard, St.
Louis, Missouri 63166, United States of America 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 following statement: 5
This invention relates to coating compositions comprising a polyol, a polyether polyol and an aminoplast and in particular relates to coating compositions comprising a primary polyol, a polyether polyol and a substantially fully etherified substantially completely methylolated polyaminotriazine.
Coating compositions comprising particular hydroxy polyesters and similar hydroxy 10 containing oligomers and polymers and aminoplast curing agents have been proposed.
Thus U S Patents 3449,467 and 3,668,276 suggest organic solutions of hydroxy polyesters of moderately high molecular weight, containing aminoplasts and U S Patents 3,852,375, 3,920,595 and 3959,201 propose high solids coating compositions comprising blends of hydroxy polyesters of moderately low molecular weight and aminoplast curing agents 15 However, in general these compositions are cured at temperatures well in excess of 100 C.
and encompass enormously wide ranges of hydroxy polyester to aminoplast Moreover, they are generally high in viscosity and therefore require some water or solvent to reduce the viscosity to a level adequate for coating applications Coating compositions of suitable viscosity for coating applications may be prepared from certain monomeric polyols and 20 aminoplasts However, many such compositions, when they are applied to substrates, tend to crawl and form coatings of non-uniform thickness, and also tend to form craters and “orange peel” defects when they are cured.
A need, therefore, exists for a high solids coating composition substantially free of solvent to provide high film build per application, to reduce volatile pollutants evolved 25 during the baking cycle and to improve the economics of the coating process.
A need also exists for a high solids coating composition which can be cured at lower temperatures, for example in the temperature range of 70 to 105 C, thus reducing the energy requirements for the curing process.
A need also exists for a high solids coating composition to provide smooth glossy films, 30 which are free from the problems of crawling, cratering, pin hole formation and orange-peel formation.
A need also exists for a high solids coating composition which can be formulated with hydroxy polyester oligomers and hydroxy acrylic oligomers to provide surface coating compositions which can be cured to provide coatings with good water, solvent and stain 35 resistance.
According to the present invention there is provided a liquid composition comprising a polyol, a polyoxypropylene triol of molecular weight in the range of 500 to 1000 and a substantially completely methylolated polyaminotriazine substantially fully etherified with a C, to C 4 alcohol, wherein the polyol has a hydroxyl equivalent of less than 150, and 40 1 572 678 contains at least two methylol groups separated by a radical which is an aliphatic hydrocarbon radical, an alicyclic hydrocarbon radical, an aliphatic ether radical, an alicyclic ether radical, an aliphatic ester radical or an alicyclic ester radical wherein oxygen atoms other than carbonyl oxygen atoms in ester groups in the molecule of the polyol are separated by at least three carbon atoms, wherein the substantially completely methylo 5 lated polyaminotriazine substantially fully etherified with a Cl to C 4 alcohol has a ratio of aminotriazine to combined formaldehyde in the range of 1:2 N 0 5 to 1:2 N where N is the number of amino groups per triazine ring and has a ratio of aminotriazine to alkyl ether groups in the range of 1:2 N 1 to 1:2 n, wherein the weight ratio of polyol to polyoxypropylene triol is in the range of 90:10 to 55:45, and wherein the ratio of hydroxyl groups of the polyol and the polyoxypropylene triol to alkoxymethyl groups of the polyaminotriazine is in the range of 1:0 9 to 1:2.
The term “polyol” is meant to include materials having two or more hydroxyl groups per molecule.
Other aspects of the invention are directed to articles of manufacture comprising 15 substrates coated with a film of the above coating composition cured at a suitable temperature and to the process of coating substrates with a film of the above coating composition and curing the film at a temperature in the range of 60 to 175 C.
Some of the advantages of certain of the disclosed compositions include low temperature curability in the temperature range of 70 to 105 C especially in the presence of an acid 20 catalyst of p Ka less than 5, thus reducing the energy requirements for cure; low viscosity to allow ease of coating without the need for appreciable amounts of solvent thinners thus allowing high film build and reducing volatile pollutants; freedom of the films from crawling which causes non-uniform film thickness; and freedom of the films from cratering, pin-holing and orange peel formation which impair the protection afforded by the coating 25 to the substrate and detract from the appearance of the film.
Polyols suitable for use in the present invention are compounds containing at least two methylol groups per molecule separated by a radical selected from aliphatic and alicyclic hydrocarbon radicals, aliphatic and alicyclic ether radicals and aliphatic and alicyclic ester radicals wherein oxygen atoms other than carbonyl oxygen atoms in ester groups in the molecule of the compound are separated by at least three carbon atoms The polyols have a hydroxyl equivalent or weight per hydroxyl group of less than 150 Suitable polyols can include one or more of the following compounds: 1,3-propanediol, 2-methyl1,3propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1 5-pentanediol, 1,6-hexanediol, 1,2-dimethylolcyclohexane, 1,3dimethylolcyclohexane, 35 1,3-dimethylol-5-t-butylcyclohexane, 1,4-dimethylolcyclohexane, 1,2,3trimethylolcyclohexane, 1,2,4-trimethylolcyclohexane, 1,3,5trimethylolcyclohexane, 1,2,4,5-tetramethylolcyclohexane, 2-butyl-1,3-propanediol, trimethylolethane, trimethylolpropane and 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate The polyol is preferably liquid at a temperature of 50 C so that it can yield blends with the 40 polyoxypropylene triol and polyaminotriazine components which are liquid at room temperature and which are substantially free from the separation of a solid or semi-solid phase Polyols which melt about 50 C can be selected so that their blends are liquid at the desired temperature The preferred polyols include 1,4-butanediol, 1,5pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol trimethylolethane, trimethylolpropane, 1,2 dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4dimethylolcyclohexane, 1,2,4trimethylolcyclohexane, 1,3,5-trimethylolcyclohexane, and 2,2-dimethyl-3hydroxypropyl 2,2-dimethyl-3-hydroxypropionate 1, 4-Dimethylolcyclohexane is especially preferred since it yields blends with the polyoxypropylene triol and polyaminotriazine component which cure to provide films of excellent gloss and hardness.
The polyaminotriazine component of the liquid composition is substantially completely methylolated and substantially fully etherified with at least one Cl to C 4 alcohol Suitable polyaminotriazines contain at least two amino groups per triazine ring and include formoguanamine, acetoguanamine, benzoguanamine and melamine They are reacted with formaldehyde to methylolate the amino groups and are then alkylated or etherified by 55 reaction with the Cl to C 4 alcohol or mixture of alcohols to provide unmixed or mixed ethers These crosslinking agents can be prepared by the method set forth in U S Patent 2.998,411 The etherified methylolated aminotriazines are liquid and are essentially monomeric or at most are oligomeric with an average degree of polymerization of not more than 2, the aminotriazine rings being joined by methylene or methylene ether bridges 6 ( formed by condensation of two methylol groups Thus, the etherified aminotriazines within the scope of the invention possess a ratio of aminotriazine to combined formaldehyde in the range of 1: 2 N 0 5 to 1: 2 N where N is the number of amino groups per triazine ring and possess a ratio of aminotriazine to alkyl ether groups in the range of 1: 2 N -1 to 1: 2 n The preferred aminotriazine is melamine since it has three amino groups per ring and is 6 ‘ 1 572 678 potentially hexafunctional The preferred ethers are methyl ethers because they tend to be more reactive at low temperature and because they generate a relatively small amount of condensation volatiles during the crosslinking reaction with the polyol component of the liquid composition Thus, the more preferred aminotriazine compounds are the methoxymethyl melamines in which the ratio of melamine to combined formaldehyde is in the range 5 of 1: 5 5 to 1: 6 and the ratio of melamine to methoxy groups is in the range of 1: 5 to 1: 6.
Among the more preferred aminotriazine compounds is monomeric hexamethoxymethyl melamine A discussion of the concepts of methylolation and etherification is set forth in U.S Patent 3,471 388.
For improved flexibility of the cured composition, a polyoxypropylene triol of molecular 10 weight in the range of 500 to 1000 is used The triols may be prepared by the base catalyzed addition of propylene oxide to triols such as trimethylolethane, trimethylolpropane, glycerol and 1,2,6-hexanetriol Surprisingly, it has been discovered that other polyether polyols such as polyether polyols of ethylene oxide, high molecular weight polyols of propylene oxide, and polyester polyols formed from caprolactone added to the liquid 15 compositions of the present invention, cause crawling, cratering or crazing in cured films of the composition.
The liquid compositions of the present invention comprise the polyol, the polyoxypropylene triol and the aminotriazine components described hereinabove in a ratio such that the ratio of hydroxy groups in the polyol and polyoxypropylene triol to alkoxymethyl groups in 20 the aminotriazine compound is in the range of 1: 0 9 to 1: 2, preferably 1: 1 to 1: 2 Large excesses and deficiencies of aminotriazine component have been acceptable in prior art solvent systems without detracting from film properties of the cured composition.
However, when insufficient or excess aminotriazine component is used with the polyols and polyoxypropylene triols of the present invention, the cured liquid composition is found to 25 be undesirably soft and readily marred.
The liquid compositions of the present invention can be cured at temperatures in the range of 60 to 170 C for a period of time in the range of several seconds to hours Curing is readily effected in about 10 to 30 minutes at the lower end of the temperature range in the presence of an acid catalyst which is soluble in the liquid composition and has a p Ka at 30 250 C of less than 5 Among the acids which can be used are the mineral acids and sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and the toluenesulfonic acids A preferred catalyst is p-toluenesulfonic acid since it is readily available, relatively non-volatile and easily dissolved in the liquid composition Sufficient catalyst to provide the desired rate of cure at a selected temperature without causing excessively short pot-life is 35 used Generally from 0 1 to ten weight percent of the polyol, polyoxypropylene triol and polyaminotriazine is sufficient For a satisfactory cure rate in the temperature range of 70 to C, from 0 2 to 1 percent of catalyst provides undiluted liquid compositions with a pot-life or shelf-stability of seven ( 7) days or more at 25 C Dilution with solvent can extend the storage stability almost indefinitely 40 In addition to the components above, the compositions can contain other optional ingredients including various pigments, fillers, plasticizers, antioxidants, flow control agents, wetting agents and other agents of the type ordinarily used in surface coatings.
The compositions can be applied to paper, cloth, metal, wood, glass, and plastic substrates by any convenient method such as brushing, dipping, spray, roller coating and 45 dip coating The ability to cure at low temperature is particularly advantageous with paper, cloth and wood substrates.
The invention will be further described and illustrated in the Examples which follow The Examples are illustrative of the invention and should not be construed as limiting the scope to their details All parts and percentages are by weight unless otherwise indicated 50 Example 1
136 Parts of 1 4-dimethylolcyclohexane is melted at 50 C and is blended in turn with 20 parts of a polyoxypropylene triol of hydroxyl equivalent 233 prepared by the addition of propylene oxide to 1,2,6-hexanetriol, and with 193 parts of a methoxymethylmelamine in 55 which the melamine to combined formaldehyde ratio is 1:5 7, the melamine to methoxy ratio is 1:5 0 and the methoxy content is 143 meq per gm The blend is cooled to room temperature and 9 6 parts of a 20 weight percent solution of a ptoluenesulfonic acid in isopropyl alcohol is added The blend is applied to a Bonderized No 37 (Bonderized is a Registered Trade Mark) steel panel with a 75 micron coating blade to provide a dried film 60 thickness of approximately 25 microns after it has been baked for 30 minutes at 93 After cure, the film shows no crawl or retreat of the dried film from the edge of the initial wet film, has a hardness of 2 H (ASTM D 3363-74), a forward impact of 74 cmkg (ASTM D 2794-69): solvent resistance of 200 + and good water spot resistance The solvent resistance is determined by oscillating a Control-Flo Fountain Marking Pencil manufactured by 65 4 1 572 678 4 Diagraph-Bradley Industries, Inc, containing a felt tip of approximately 1 cm diameter, and filled with methyl ethyl ketone, on the coating surface using a uniform moderate pressure The number of double strokes required to erode the film and cause break through to the metal is noted The water spot test is carried out by adding a 05 ml drop of distilled water to the surface of the coating and covering the spot with a watch glass The sample is 5 maintained at room temperature and the spot is examined for blistering, swelling, or whitening If these effects are absent after four hours the film is considered free of water damage.
Examples 2 5 10 Similar coatings are prepared from blends of the methoxymethylmelamine and the polyoxypropylene triol of Example 1 and a series of polyols Curing is effected at 820 C, 93 TC and 1040 C The compositions and coating data are presented in Table I together with the data for Example 1 Examples 1, 2 and 3 are within the scope of the invention and show the superior resistance to crawl at the baking step and the superior film appearance 15 compared with coatings of Control Examples 4 and 5 prepared with secondary polyols.
Un TABLE I
Coatings prepared from a series of polyols Control Examples Example 1 Example 2 A B C A B Example 3
C A B Example 4
C A B 4 Example 5
C A B C Composition, pbw Methoxymethylmelamine Polyoxypropylene triol 1,4-dimethylolcyclohexane DHP DHP 1,5-pentanediol 2-methyl-2,4-pentanediol dipropylene glycol p-TSA Cure, 30 mins.
Temperature C.
Coating Appearance Film Properties Pencil Hardness Forced Impact, cm-kg.
( 12 7 cm diam ball) Solvent Resistance (No of rubs) Water Spot 193 193 193 193 193 193 193 193 193 193 193 193 193 193 193 20 20 20 20 20 20 20 20 20 20 20 20 20 20 136 136 136 170 170 87 87 87 98 98 98 112 112 112 3.3 1 4 1 7 3 3 1 9 1 9 3 3 1 5 1 5 3 3 1 6 1 6 3 3 1 6 1 6 82 93 104 82 93 104 82 93 104 U’1 82 93 104 82 93 104 1 1 1 2 2 1 1 2 2 5 4 4 3 4 4 2 H H 69 74 3 H 2 H 2 H 2 H 2 H 2 H 2 H 2 2 2 2 H 2 H H 69 55 30 23 46 29 52 174 6 H 3 H 2 H 6 H 24 52 92 93 + 80 200 + 200 + 200 + 200 + 200 + 200 + 200 + 200 + 72 200 + 200 + 200 + 200 + 1 1 1 2 1 1 1 1 1 3 1 1 3 1 1 I 6 1 572 678 6 Legend DHP DHP 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate p-TSA p-toluenesulfonic acid Coating Appearance:
1 no crawl, smooth, high gloss 5 2 slight crawl, smooth, high gloss 3 crawl, slight cratering 4 crawl, cratering severe crawl, cratering Water Spot: 10 1 no damage 2 slight damage 3 damage Examples 6 10 15 A series of liquid composition blends is prepared with 1,4dimethylolcyclohexane, the methoxymethylmelamine of Example 1 and a polyoxypropylene triol with a hydroxyl equivalent of 233 The weight ratio of 1,4-dimethylolcyclohexane to polyoxypropylene triol is 6: 1 The various blends contain different ratios of hydroxyl groups of the diol and triol to methoxymethyl groups of the melamine compound The data show that especially in the 20 temperature range of 74 105 C the coatings prepared from the compositions are soft and easily marred when the ratio is appreciably outside the range of 1: 1 to 1: 2.
1 572 678 7 1 572 678 7 TABLE II
Control Examples Example Example Example Example Example 6 7 8 9 10 Composition, pbw Methoxymethylmelamine 1, 4-dimethylolcyclohexane Polyoxypropylene triol p-TSA Ratio OH:methoxymethyl Bake Cycle 74 C.
Pencil Hardness Forward Impact, cm-kg.
Solvent Resistance 58 29 18 69 89 36 36 36 36 36 6 6 0.7 0.6 1 1 1 2 1:1-1 89 1:0 94 1:0 59 1:2 24 1:2 89 F-H F-H 69 25 exc.
exc.
4 B Tacky HB 116 poor poor Bake Cycle 82 C.
Pencil Hardness 3 H H-2 H (chipped) B HB Forward Impact, cm-kg.
Solvent Resistance Bake Cycle 105 C.
Pencil Hardness Forward Impact, cm-kg.
Solvent Resistance 23 58 23 35 exc.
exc.
exc.
H 2 H-3 H HB (chipped) 23 16 23 12 23 exc.
exc.
exc.
Bake Cycle 121 C.
Pencil Hardness Forward Impact, cm-kg.
Solvent Resistance 4 H 4 H (chipped) 9.3 9-11 exc.
exc.
F F F 23 12 12 exc.
exc.
exc.
exc = excellent Examples 11 13 A series of coating compositions similar to the composition of Example 6 is prepared in which the polyoxypropylene triol of Example 6 is substituted with various polyether polyols and polyester polyols Coatings are prepared and subjected to a bake cycle of 30 minutes at C The films were then examined for appearance and hardness The data are presented in Table III and show the superiority of coatings of Example 6 containing polyether triol of molecular weight of 700 compared with the coatings of Example 11 (polyoxypropylene triol from 1,2,6-hexanetriol, MW-4000), Example 12 (polyester diol of caprolactone, PCP-0301, Union Carbide) Example 13 (polyethylene glycol, Carbowax 300, Union Carbide).
F exc.
exc.
HB F exc.
exc.
1 572 678 1 572 678 TABLE III
Comparison of coatings containing polyether polyols Coating Example Polyether Polyol Hardness Appearance 5 6 1,2,6-HT-PO 4 H level, glossy, free MW 700 of imperfections 11 (Control) 1,2,6-HT-PO H crawled, cratered, 10 MW 4000 crazed 12 (Control) PCP-0301 2 H-3 H some crawl, cratering polycaprolactone diol 15 13 (Control) Carbowax 300 2 H crawled

Claims (1)

WHAT WE CLAIM IS:
1 A liquid composition comprising a polyol, a polyoxypropylene triol of molecular weight in the range of 500 to 1000 and a substantially completely methylolated 20 polyaminotriazine substantially fully etherified with a Cl to C 4 alcohol wherein the polyol has a hydroxyl equivalent of less than 150 and contains at least two methylol groups separated by a radical which is an aliphatic hydrocarbon radical, an alicyclic hydrocarbon radical, an aliphatic ether radical, an alicyclic ether radical, an aliphatic ester radical or an alicyclic ester radical, wherein oxygen atoms other than carbonyl oxygen atoms in ester 25 groups in the molecule of the polyol are separated by at least three carbon atoms, wherein the substantially completely methylolated polyaminotriazine substantially fully etherified with a C 1 to C 4 alcohol has a ratio of aminotriazine to combined formaldehyde in the range of l:2 N 0 5 to 1:2 N where N is the number of amino groups per triazine ring and has a ratio of aminotriazine to alkyl ether groups in the range of 1:2 N 1 to 1:2 n, wherein the weight 30 ratio of polyol to polyoxypropylene triol is in the range of 90:10 to 55:45, and wherein the ratio of hydroxyl groups of the polyol and the polyoxypropylene triol to alkoxymethyl groups of the polyaminotriazine is in the range of 1:0 9 to 1:2.
2 A composition according to Claim 1 in which the ratio of hydroxyl groups of the polyol and the polyoxypropylene triol to alkoxymethyl groups of the polyaminotriazine is in 35 the range of 1:1 to 1:2.
3 A composition according to Claim 2 wherein the polyaminotriazine is benzoguanamine or melamine.
4 A composition according to Claim 3 wherein the polyaminotriazine is melamine and the alcohol is methyl alcohol 4 a A composition according to any of the preceding claims wherein the polyol is 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3propanediol, trimethylolethane, trimethylolpropane, 1,2-dimethylolcyclohexane, 1,3dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,2,4-trimethylolcyclohexane, 1,3,5trimethylolcyclohexane or 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate 4 ‘ 6 A composition according to Claim 5 wherein the polyol is 1,4dimethylolcyclohexane and the polyoxypropylene triol is a propylene oxide adduct of 1,2,6hexanetriol.
7 A liquid composition comprising 1,4-dimethylolcyclohexane, a polyoxypropylene triol of molecular weight in the range of 500 to 1000 and a substantially completely methylolated melamine substantially fully etherified with methyl alcohol, wherein the 5 ( weight ratio of 1,4-dimethylolcyclohexane to polyoxypropylene triol is in the range of 90:10 to 55:45 and wherein the ratio of hydroxyl groups of the 1,4dimethylolcyclohexane and the polyoxypropylene triol to methoxymethyl groups of the melamine is in the range of 1:1 to 1:2.
8 A liquid composition comprising a polyol, a polyoxypropylene triol of molecular 5 ‘ weight in the range of 500 to 1000, a substantially completely methylolated polyaminotriazine substantially fully etherified with a Cl to C 4 alcohol and from 0 1 to 10 weight percent, based on the weight of polyol, polyoxypropylene triol and polyaminotriazine, of a soluble acid catalyst of p Ka less than 5, wherein the polyol has a hydroxyl equivalent of less than 150 and contains at least two methylol groups separated by a radical which is an 6 aliphatic hydrocarbon radical, an alicyclic hydrocarbon radical, an aliphatic ether radical, an alicyclic ether radical, an aliphatic ester radical or an alicyclic ester radical, wherein oxygen atoms other than carbonyl oxygen atoms in ester groups in the molecule of the polyol are separated by at least three carbon atoms wherein the substantially completely methylolated polyaminotriazine substantially fully etherified with a Cl to C 4 alcohol has a 6 1 572 678 ratio of aminotriazine to combined formaldehyde in the range of 1:2 N 0 5 to 1:2 N where n is the number of amino groups per triazine ring and has a ratio of aminotriazine to alkyl ether groups in the range of 1:2 N 1 to 1:2 n, wherein the weight ratio of polyol to polyoxypropylene triol is in the range of 90:10 to 55:45, and wherein the ratio of hydroxyl groups of the polyol and the polyoxypropylene triol to alkoxymethyl groups of the 5 polyaminotriazine is in the range of 1:0 9 to 1:2.
9 A composition according to Claim 8 wherein the polyaminotriazine is benzoguanamine or melamine.
A composition according to Claim 9 wherein the polyaminotriazine is melamine and the alcohol is methyl alcohol 10 11 A composition according to Claim 8, wherein the polyol comprises a methylol compound which is 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2dimethyl-1,3propanediol, trimethylolethane, trimethylolpropane, 1,2dimethylolcyclohexane, 1,3dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,2,4trimethylolcyclohexane, 1,3,5trimethylolcyclohexane or 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3 15 hydroxypropionate.
12 A composition according to Claim 9 wherein the polyol is 1,4dimethylolcyclohexane and the polyoxypropylene triol is a propylene oxide adduct of 1,2,6-hexanetriol.
13 A composition according to any of Claims 8 to 12 wherein the acid catalyst is a 20 sulfonic acid.
14 A liquid composition comprising 1,4-dimethylolcyclohexane, a polyoxypropylene triol of molecular weight in the range of 500 to 1000, a substantially completely methylolated melamine substantially fully etherified with methyl alcohol, and from 0 2 to 1 weight percent of toluenesulfonic acid, wherein the weight ratio of 1,4 25 dimethylolcyclohexane to polyoxypropylene triol is in the range of 90:10 to 55:45 and wherein the ratio of hydroxyl groups of the 1,4-dimethylolcyclohexane and the polyoxypropylene triol to methoxymethyl groups of the melamine is in the range of 1:1 to 1:2.
An article of manufacture comprising a substrate coated with the cured liquid composition of Claim 1 30 16 An article of manufacture comprising a substrate coated with the cured liquid composition of Claim 6.
17 An article of manufacture comprising a substrate coated with the cured liquid composition of Claim 8.
18 An article of manufacture comprising a substrate coated with the cured liquid 35 composition of Claim 12.
19 A process of coating a substrate which comprises applying a film of the liquid composition of Claim 1 to the substrate and curing the film at a temperature in the range of about 60 to about 175 C.
20 A process according to Claim 19 in which the liquid composition of Claim 8 is used 40 21 A process according to Claim 20 wherein the temperature is in the range of 70 to C.
22 A process of coating a substrate which comprises applying a film of the liquid composition of Claim 12 to the substrate and curing the film at a temperature in the range of about 60 to about 175 C 45 23 A process according to Claim 22 wherein the temperature is in the range of 70 to C.
24 A liquid composition according to Claim 1 and substantially as hereinbefore described with reference to any of Examples 1, 2, 3, 6 or 7.
25 An article of manufacture according to Claim 15 and substantially as hereinbefore 50 described with reference to any of Examples 1, 2, 3, 6 or 7.
26 A process of coating a substrate according to Claim 19 and substantially as hereinbefore described with reference to any of Examples 1, 2, 3, 6 or 7.
J L PEARSON, 55 Chartered Patent Agent, Monsanto House, 10-18 Victoria Street, London SW 1 H ONQ.
Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1980.
Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY,from which copies may be obtained.

GB43553/77A
1976-10-20
1977-10-19
Coating compositions comprising polyether triols

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US4130692A
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1976-10-20
1976-10-20
Coating compositions comprising alkoxymethylaminotriazines, polyols and polyether triols

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1980-07-30

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1976-10-20
1977-10-19
Coating compositions comprising polyether triols

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US4497764A
(en)

1982-09-30
1985-02-05
Exxon Research & Engineering Co.
Epoxy resin compositions of enhanced creep resistance

US4656061A
(en)

1984-06-14
1987-04-07
Henkel Corporation
High solids coating compositions based on fatty polyols

US4530977A
(en)

1984-07-30
1985-07-23
Desoto, Inc.
Low temperature-curing polyester urethane systems

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US3267174A
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1963-05-10
1966-08-16
Union Carbide Corp
Acrylic coating composition containing an adduct of a triol with an alkylene oxide

US3959201A
(en)

1972-10-26
1976-05-25
Ppg Industries, Inc.
High solids, water thinnable compositions

US3928265A
(en)

1972-10-31
1975-12-23
Bayer Ag
Lacquer systems which are harmless to the environment

US3862072A
(en)

1972-11-16
1975-01-21
Desoto Inc
Thermosetting aqueous coatings containing branched hydroxy functional polyester and hydroxy functional polyether or polyester adducts of an at least trifunctional alcohol

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(en)

1974-04-10
1975-11-18
Ppg Industries Inc
High solids alkyd coating compositions

DE2433489A1
(en)

1974-07-12
1976-01-22
Bayer Ag

BURN-ON LACQUER SYSTEMS WITH HIGH SOLID CONTENT

1976

1976-10-20
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US05/734,080
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1982-03-16

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1978-12-19

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