JPS6221026B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compositions of partially or fully alkylated glycolurils and non-self-crosslinking polymers containing one or more carboxyl, alcoholic hydroxyl or amide groups as reactive groups. and the group is present in an amount of 0.5 to 25% by weight, based on the weight of the polymer, and 0.5 to 5.0% by weight, based on the total weight of the glycoluril and polymer. The composition may be an aqueous dispersion if the polymer is water dispersible, or it may be organic solvent soluble if the polymer is soluble in an organic solvent. Organometallic finishes have been commercially available for many years. Coatings using natural substances such as linseed oil were finally replaced by synthetic polymeric substances. Often these initial substances are dissolved in organic solvents,
It is deposited onto the metal substrate by any of a number of conventional methods and dried or baked to form the desired coating on the metal substrate. Some of these early coating compositions were not as strong or chemically resistant to solvents and acids as desired. As a result, blends of crosslinkable polymers were further developed and used with crosslinking agents. When the composition was used as a coating on a metallic substrate and then baked, the crosslinkable polymer and crosslinker were converted to a thermoset state, providing a strong chemically resistant film. Currently, the most commonly used crosslinking agents are based on ureas and thioureas, including triazines such as melamine, benzoguanamine, or urea itself. however,
These crosslinkers do not satisfy all current demands and newly developed coating applications. These newly developed coatings require complete functionality, in some cases superior to that currently achievable with known crosslinking agents. More recently, from an ecological point of view, it has become less desirable to provide aqueous systems that provide aqueous dispersions of mixed substances. It is not intended, however, that such supplies completely replace the solvent system. The present invention is in the field of coating resins and includes certain partially or fully alkylated glycoluril derivatives and certain organic solvent or water dispersible non-gelling, non-self-crosslinking compounds. and provide organic solvent solutions or aqueous dispersions of acid-catalyzed mixtures of polymers that can be processed in a number of ways, including coating, spraying, dipping, brushing, roller coating, electrocoating, etc. After coating the coating composition on the metal substrate, the coated substrate is heated at a suitable temperature such that the crosslinking agent crosslinks the polymer with the aid of an acid catalyst. It can be baked to produce a strong and chemical resistant film. According to the present invention, an organic solvent solution or aqueous dispersion of a mixture consisting of (A), (B) and (C) having the following composition is provided. That is, about 2 to about 50% by weight of a glycoluril derivative (A) having the following structural formula: (In the formula, n is an integer from 2 to 4; m is an integer from 0 to 2; n+m is an integer from 2 to 4; each R is either hydrogen or an alkyl group having 1 to 4 carbon atoms. ); (B) Corresponding approximately 98 to approximately
50% by weight organic solvent soluble or water dispersible, non-gelling, normally non-self-crosslinking (under normal calcination conditions) polymer. provided that the polymer contains one or more carboxyl, alcoholic hydroxyl, or amide groups as reactive groups in an amount of at least about 0.5% and more than about 25% by weight of the total weight of the polymer. and (C) (A)
and about 0.05 to 5.0% by weight, based on the total weight of (B), as an acid catalyst. Here, the reactive group (B) is thermally reactive with (A), and the weight percentage of (A) and (B) that totals 100% is (A)
and (B) based on the total solid weight. Typical baking conditions for these coatings are generally 200°C or less for 30 minutes or less. During the last decade, dramatic changes have occurred in organic coating technology. Waterborne emulsions, paints floating on water (Waterborne)
More and more emphasis has been placed on non-polluting paints such as coatings, electro coatings, powder coatings, and ultraviolet curing coatings. Existing crosslinking agents based on melamine, guanamine including benzoguanamine or urea and substituted ureas do not meet all the demands of the current paint market. The glycoluril derivative used in the present invention is a new type of crosslinking agent, and its raw material is glycoluril.
It is known as acetylene diurea, which is produced by reacting with moles of glyoxal. Glycoluril can be partially or completely methylolated by reacting 1 mole of glycoluril with 1 to 4 moles of formaldehyde. When glycoluril is completely methylolated, the methylolated product is tetramethylol glycoluril. Methylolated glycolurils can be partially or fully alkylated, depending on whether the glycoluril is partially or fully methylolated, and further depending on whether partial or complete alkylation is desired. . If tetramethylol glycoluril is combined with a selected amount of 1 to 6 carbon atoms,
If reacted with a monohydric aliphatic or cycloaliphatic alcohol containing 2, we can, for example, produce a tetra(alkoxymethyl)glycoluril or a partially alkylated glycoluril. These monohydric alcohols may be primary or secondary alcohols. Monohydric alcohols that can be used to accomplish this alkylation include methanol,
Ethanol, n-propanol, n-butanol, n-amyl alcohol, n-hexyl alcohol, isobutanol, isopropanol, secondary
These include butanol, cyclohexanol, etc. Although some of these glycoluril derivatives are already recognized in the chemical literature, the following examples are included to illustrate how to make them. All parts herein are parts by weight unless otherwise indicated.
These examples are set forth primarily for illustrative purposes, and any specific numerical details contained herein should be construed as limiting the invention, except as indicated in the appended claims. isn't it. Method for Preparing Glycoluril Into a suitable reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 765 parts of urea and 875 parts of water were introduced. Fill this slurry with 282 parts of concentrated sulfuric acid,
The mixture was heated to 70°C. 605 parts glyoxal at 70°C (40% aqueous solution, formaldehyde free)
is slowly added to the clear solution so as to maintain the reaction temperature at 75-80°C, and after the addition of glyoxal the reaction mixture is kept at 75°C for 1 hour and then cooled. Separated crystalline glycoluril,
Wash with water and dilute alkaline solution. The glycoluril obtained after drying had a melting point of 298-300°C and a yield of 88% (525 parts). Preparation of tetramethylol glycoluril Into a suitable reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 688 parts (10 mol) of an aqueous formaldehyde solution (44%) are introduced, and the pH is adjusted to 22 parts.
It was adjusted to 8.7 with 0.5N-NaOH solution. In this solution
284 parts (2 moles) of glycoluril were added at 40°C. While the reaction is occurring, the reaction temperature is 55℃
I let it rise to the top. At this stage most of the glycoluril was dissolved. After about 15 minutes, add 5 parts of PH.
It was adjusted to 8.0 with 0.5N-NaOH. A clear pale yellow solution was obtained. This clear solution was heated at 50°C under reduced pressure.
Water was removed by distillation until the contents of the reaction vessel were reduced to approximately 640 parts. The syrup in the container was poured into 800 parts of methanol. A white crystalline precipitate was filtered and dried. The total yield of tetramethylol glycoluril was 483 parts (92% yield) with a melting point of 132-136°C. Preparation of Tetrabutoxymethylglycoluril Into a suitable reaction vessel equipped with a stirrer, a thermometer and a reflux condenser were introduced 1000 parts (13.5 mol) of n-butanol, 7.0 parts of concentrated nitric acid and 20 parts of water. .
Add 200 parts (0.76 mol) of tetramethylol glycoluril to this mixture and heat the reaction mixture at 40°C.
The mixture was stirred for 2 hours. The reaction mixture became a clear solution. This was then distilled under reduced pressure at 45-50°C to remove the butanol/water azeotrope. 260 copies of n-
After removing the butanol/water mixture, 260 parts of n-butanol was added to the clear solution and the reaction temperature was adjusted to 22-25
lowered to ℃. This solution was neutralized to pH 9-10 with 10% caustic solution, and then a large amount of n-butanol/
The water mixture was removed. The residue was filtered through a filter. The aqueous white syrup produced is Y-Z (25
It had a Gardner-Holdt viscosity value of (°C). Pan solids content {refers to the solids content measured by the following method: The resin composition is placed in a small shallow pan and dried to a constant weight. The solids content, which is the ratio of the final weight to the initial weight before drying, is called bread solids. } is 95% (105
Foil solid content (refers to solid content according to the following measurement method) Weigh out a few drops of the resin composition onto a suitable aluminum flake,
Next, fold this thin piece to enclose the resin.
Apply pressure to the folded thin piece by applying a large weight to it.
Distribute the resin widely over the flakes. The folded flakes are spread out and then dried to constant weight.
Same as in bread solid} is 97% (45% at 45℃
minute). Gel layer chromatography showed that 85% of the product was monomer. The magnetic resonance (nmr) of the product confirmed the structure of the monomer to be tetrabutoxymethyl glycoluril. Method for producing tetrabutoxymethylglycoluril 344 parts (5 mol) of an aqueous formaldehyde solution (44%) was introduced into a suitable reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and its pH was adjusted to 0.5N-
Adjusted to 7.5 using 6 parts of NaOH solution. To this solution was added 142 parts (1 mol) of glycoluril and the reaction mixture was heated to 80°C. 2nd part 0.5N
-NaOH solution was added to adjust the pH to 7.0. Within 30 minutes the reaction mixture became a clear solution. It was then cooled to 25°C and its pH was adjusted to 7.4 with 3 parts of 0.5N NaOH solution. The clear pale yellow solution was then distilled under reduced pressure at 55°C to remove water. After removing 150 parts of water, 740 parts (10 moles) of n-butanol and 1 part of concentrated nitric acid were added to the resulting syrup. The mixture was heated to reflux with stirring. about 10
After a few minutes the reaction mixture became clear, watery white and the reflux temperature was 95-98°C. The water produced during the reaction was decanted using standard decanter equipment. 150 in about 3 hours
Part of the decant (8% n-butanol in water) was collected. The reaction temperature after this period was 115-116°C. When the water stopped coming out by decanting, the solution was cooled to 22-24°C and neutralized with 10 parts of 0.5N NaOH solution. Excess butanol was removed under atmospheric pressure and later under reduced pressure, and the remaining syrup was passed over activated carbon and a superagent. The yield of produced ship is
The amount was 410 parts (yield approximately 87%). Other physical properties are as follows: Thin solid: 96.4%; Bread solid:
94.7%; Gardner-Holdt viscosity value (25℃): P-
Q; Gardner color: 1; water solubility: 321 Preparation of partially methylated glycoluril In a suitable reaction vessel equipped with a stirrer, thermometer and reflux condenser, 950 parts (30 moles) of methanol and
40 parts of concentrated hydrochloric acid were introduced. Add 262 parts (1 mole of tetramethylol glycoluril) to this mixture.
was added and the reaction mixture was stirred at 25-30°C. about
All of the tetramethylol glycoluril went into solution in 15-20 minutes. After 30 minutes, the reaction mixture
Neutralization was carried out using 140 parts of sodium bicarbonate and 20 parts of sodium carbonate at 22-23°C. PH after neutralization is approximately 8
It was hot. I passed this salt. 60 ml of liquid under reduced pressure
Concentrate at °C. The yield of syrup product after salting was 290 parts, which was reduced to 90% solids with cellosolve.
diluted to The properties of the product were as follows: lamellar solid: 91.4%; bread solid: 82.2%; Gardner-Holdt viscosity value (25°C): Z ₁ . Infrared analysis (IR) of the product showed that the methylated product had a large amount of unreacted methylol groups. Preparation of Tetramethoxymethylglycoluril In a suitable reaction vessel equipped with a stirrer, thermometer and condenser, 640 parts (20 moles) of methanol and 20 parts of 70
% concentrated nitric acid. In this acidic methanol,
262 parts (1 mol) of tetramethylol glycoluril were added and the reaction mixture was heated to 40° C. with stirring. All of the tetramethylol glycoluril was dissolved in about 20 minutes. When the reaction mixture became clear, it was cooled to 22°C and 45 parts of 20% sodium hydroxide solution was added to neutralize the reaction mixture.
The pH was set to 7-8. Neutralized clear solution at 50-55℃
and 450 parts of methanol were removed under slightly reduced pressure. The residue in the flask crystallized upon standing for several hours. The crystalline solid was filtered and washed with a little water. The liquid was then vacuum distilled at 70-80°C to remove all water. The solid residue was then dissolved in benzene and undissolved salts were filtered off. The benzene solution was mixed with the initial product of solid crystals, and more benzene was added to dissolve and filter again. Removal of benzene yielded 310 parts of tetramethoxymethyl glycoluril (TMMGU). The yield was 97%. This was recrystallized from benzene. The recrystallized product had a melting point of 116-118°C.
The structure of TMMGU was confirmed by IR, NMR, and nitrogen analysis. Method for Preparing Dimethoxymethyldiethoxymethylglycoluril After stirring, in a suitable reaction vessel equipped with a thermometer and a condenser, 320 parts (10 moles) of methanol, 460 parts (10 moles) of ethanol and 20 parts of 70% Loaded with nitric acid. To this acidic alcoholic mixture was added 262 parts (1 mol) of tetramethylol glycoluril and the reaction mixture was heated to 40° C. with stirring. All of the tetramethylol glycoluril dissolved within about 20 minutes. When the reaction mixture became clear, it was cooled to 22°C and 45 parts of 20% sodium hydroxide solution was added to neutralize the reaction mixture to pH 7-8. Saturate the neutralized clear solution under reduced pressure.
Heating to 105°C removed substantially all of the alcohol-water mixture. The resulting syrup was filtered at 80°C to remove inorganic salts and other impurities. The yield of syrupy dimethoxymethyldiethoxymethylglycoluril was 320 g. The structure of this product was confirmed by NMR. bread solids
The solid content was 95.0%, and the thin solid content was 98.5%. The Gardner-Holdt viscosity value was Z ₃ -Z ₄ (25°C). The glycoluril materials used in the compositions of the present invention are fixed as glycoluril derivatives, despite the fact that many of the materials used in this field will be modified glycoluril compounds. On the other hand, in the production of derivatives of glycoluril that produce dimers, trimers, tetramers, etc. that fall into the category of these condensation products or resinous products, a certain degree of self-condensation occurs. Maybe. However, low molecular weight compounds, resinous materials or condensation products, ie with molecular weights from about 200 to 2000, are preferred for this application. When the glycoluril derivative is a polymer, the glycoluril moieties are linked by methylene bridge units, and the number of methylene bridge units depends on the number of ether groups (CH ₂ OR). These glycoluril derivatives may contain 2 to 4 methylol groups, or they may contain 2 to 4 alkoxymethyl groups or 2 to 4 alkoxymethyl groups or
may contain a combination of up to 4 methylol and alkoxymethyl groups. Glycoluril derivatives that can be used as crosslinkers in the compositions of the invention include dimethylol glycoluril, trimethylol glycoluril, tetramethylol glycoluril, monomethyl ether of dimethylol glycoluril, dimethyl ether of dimethylol glycoluril, tetramethylol Examples include trimethyl ether of glycoluril, tetramethyl ether of tetramethylol glycoluril, tetrakisethoxymethylglycoluril, tetrakispropoxymethylglycoluril, tetrakisbutoxymethylglycoluril, and the like. If desired, a diether of tetramethylol glycoluril,
Mixed ethers such as dimethyl ether, diethyl of tetramethylol glycoluril, dipropyl ether, dibutyl diethyl ether of tetramethylol glycoluril, diethyl and dihexyl ether of tetramethylol glycoluril, etc. can be used. If water solubility is desired, lower alkoxy derivatives such as tetrakismethoxymethylglycoluril are preferably used. On the other hand, when a colloidal dispersion of an emulsion dispersion is used, higher alkoxy derivatives such as tetrakisbutoxymethylglycoluril can be used. Although these crosslinking agents may be used alone or in conjunction with others if desired, it is generally preferred to use these crosslinking agents alone. The amount of glycoluril derivative used in the compositions of the present invention varies between about 2 and 50% by weight, based on the total solid weight of the glycoluril derivative and the water-dispersible, non-gelling, non-self-crosslinking polymeric material. It is possible. It is preferred to use glycoluril derivatives in weight percentages varying between about 10 and 40% by weight on the same basis. And obviously there will be from about 50 to about 98% by weight of the non-self-crosslinking polymeric material on the same basis in the composition, and preferably from about 60 to 90% by weight of the polymer on the same basis. The weight percentages of glycoluril derivative and polymer here are 100% in total and are based on the total solid weight of glycoluril derivative and polymerization. Component (B) used in the compositions of the present invention is an organic solvent soluble or water dispersible non-gelling, non-self-crosslinking polymeric material containing either carboxyl groups, alcoholic hydroxyl groups or amide groups. Contains certain reactive groups, including one or more. The amount of such groups present in the polymer can vary from about 0.5% to up to about 25% by weight, based on the total weight of the polymer. For most technical purposes these reactive groups will be the only reactive groups in the polymeric material. Any one of these reactive groups may be present in the polymer to the exclusion of the other reactive groups, or all three of these reactive groups may be present in the polymer at the same time. These polymers may be anionic or nonionic. These polymers include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,
-benzoyl acrylic acid; α/β-ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, mesaconic acid, aconitic acid; and halogenated acids such as halogenated maleic acid, especially chloromaleic acid, etc. It may be any one of many vinyl polymers that can be produced by polymerizing a polymerizable monomer containing a reactive carboxylic acid group such as. These carboxyl group-containing monomers can be used alone or in combination with others in the required amount, and can be used together with other polymerizable monomers containing reactive alcoholic hydroxyl groups or reactive amide groups. Also available are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate,
Does not contain carboxyl groups such as ethyl methacrylate, butyl methacrylate, heptyl methacrylate, decyl methacrylate, propyl crotonate, butyl crotonate, nonyl crotonate, etc., and does not contain reactive groups other than reactive ethylenic double bonds. It can be used with other monomers. These polymerizable monomers, which do not have any reactive groups, can be used alone or in combination with other monomers when copolymerized with monomers containing the above types of reactive groups. I can do it. Furthermore, styrene, o
o-, m-, p-alkylstyrenes such as -, m-, p-methyl, ethyl, propyl and butylstyrene, 2,4-dimethylstyrene. 2.3-
Dimethylstyrene, 2,5-dimethylstyrene,
vinylnaphthalene, methyl vinyl ether, n-
Butyl vinyl ether, phenyl vinyl ether, acrylonitrile, methacrylonitrile, α
-Chlorostyrene. Styrene substituted with halogen in the ring or side chain such as o-, m-, p-chlorostyrene, 2,4-dichlorostyrene, 2,3-dichlorostyrene, 2,5-dichlorostyrene, α-methylstyrene, α-ethyl Other polymerizable compounds that do not contain reactive groups such as alkyl side chains such as styrene can be used, such as styrene. If it is desired to produce a polymer as component (B) using a polymerizable monomer containing a reactive alcohol group, α such as acrylic acid, methacrylic acid, ethacrylic acid and chloro and other halogen-substituted acrylic acids can be used. - Polymerizable vinyl monomers such as hydroxyalkyl esters of β-unsaturated monocarboxylic acids can be used. These esters may contain either primary or secondary hydroxyl groups. Examples of the types of compounds that can be used to prepare polymers containing reactive alcoholic hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 8-hydroxyoctyl acrylate, 2-hydroxyethyl methacrylate, 5-hydroxyhexyl methacrylate, methacryl 6-hydroxyoctyl acid, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl methacrylate, 3-crotonic acid
-Hydroxypropyl, 4-hydroxyamyl crotonate, 5-hydroxyamyl crotonate, 6-hydroxyhexyl crotonate, 7-hydroxy crotonate
-hydroxyheptyl, 10-hydroxydecyl crotonate, etc. These hydroxy esters can be used alone or in combination with others, or with polymerizable vinyl monomers that also do not have reactive groups, such as those mentioned in the discussion of carboxyl group-containing monomers. good. Obviously, these hydroxy ester monomers can be used in conjunction with the counter-reactive carboxyl group-containing monomers described above. Amide group-containing monomers that can be used to make the same polymer as component (B) include acrylamide, methacrylamide, ethacrylamide, and the like. These polymerizable acrylamides can be used together with any carboxyl group-containing monomer and/or hydroxyl group-containing monomer, or with the above-mentioned polymerizable acrylamides containing no reactive group, in order to produce the polymer used in the present invention. It can be used with any monomer.
These polymers contain active carboxyl groups and/or reactive alcoholic hydroxyl groups and/or
or an anionic polymer, whether or not it contains a reactive amide group. Furthermore, it is possible to use polyester resin compositions which are non-gelling polymers dispersible in organic solvents.
Organic solvent dispersible alkyd resins, whether oil-free or containing glyceride oils, can be used;
And a large number of these materials are commercially available and known to those skilled in the art, so that they essentially combine polyhydric alcohols with polycarboxylic acids or anhydrides such as phthalic anhydride, maleic anhydride, etc. There is no need for a lengthy explanation of such substances since they are produced by reaction. Furthermore, polyester resin compositions which are water-dispersible, non-gelling anionic polymers can be used. Water-soluble or water-dispersible alkyd resins, whether oil-free or containing glyceride oils, can be used; many of these materials are commercially available and well known to those skilled in the art; There does not seem to be any need for a lengthy explanation of these materials since they are basically prepared by reacting polyhydric alcohols with polycarboxylic acids or anhydrides such as phthalic anhydride, maleic anhydride, etc. Additionally, certain polyether polyols can be used, such as those made by reacting 1 mole of bisphenol A and/or hydrogenated bisphenol A with at least 2 moles of ethylene oxide and/or propylene oxide. The following examples illustrate various organic solvent soluble, non-gelling, non-self-crosslinking polymers that can be used in the compositions of the present invention. Polyester Resin A This oil-free saturated polyester resin is commercially available and is prepared using conventional esterification methods to obtain isophthalic acid.
Manufactured by reacting adipic acid and propylene glycol. The polyester resin is identified as a saturated polyester resin unless it contains non-benzenoid unsaturation. The polyester made for coil coating has the following properties: 70% solids in the high-boiling hydrocarbon solvent Solbetuso 150; Gardner-Holdt viscosity (25°C) Z ₁ - _{Z 3} ; highest acid value
10; Hydroxyl value 30. Resin B Resin B is a polyether glycol and is commercially available. Resin B is produced by reacting 1 mole of bisphenol A with 4 moles of ethylene oxide.
This polyether polyol has a hydroxyl value of approximately 260−
It is 270. Acrylic Resin C Acrylic Resin C is a commercially available anionic acrylic polymer that is prepared by dissolving 55 parts of n-butyl acrylate in an inert organic solvent such as 2-ethoxyethanol.
It is prepared by standard polymerization techniques such as copolymerizing 30 parts styrene and 15 parts acrylic acid.
The polymer produced at the final stage of polymerization is treated with n-butanol.
Dilute to 75% solids. The average molecular weight of the polymer is approximately
10,000 to 20,000, and the acid value is 115. This polymer is intended for use in water-based paints and electrocoatings. At 75% solids, at 25°C it has a Gardner-Holdt viscosity Z ₆ +. Resin D After stirring, 668 parts neopentyl glycol, 96 parts trimethylolpropane, 509 parts isophthalic acid and 448 parts adipine in a suitable reaction vessel equipped with a thermometer, inert gas inlet/outlet line and dephlegmator. Acid was introduced. The reactants were heated to 230° C. under nitrogen gas while being constantly shaken to remove water from esterification. After 7 hours, the acid value of the reaction mass was 9. The reaction mass was cooled to 150°C and diluted to 90% solids with a 1:1 mixture of n-butyl acetate and cellosolve acetate. The final product was 90% solids and had a Gardner-Holdt viscosity of Z ₆ +. The resin had a hydroxyl value of 88 and an acid value of 9. The following examples illustrate various water-dispersible, non-gelling, non-self-crosslinking polymers that can be used in the compositions of the present invention. Polyester Resin E In a suitable reaction vessel equipped with a stirrer, thermometer, inert gas inlet tube and dephlegmator, 866 parts neopentyl glycol, 56 parts trimethylolpropane, 74 parts
part of dimethylolpropionic acid, 303 parts of adipic acid and an oligomer containing approximately 70% by weight trimer acid, 13% by weight dimer acid, and 17% by weight monomer acid (this oligomer is primarily 240 parts of a mixture of oleic acid and linolenic acid (derived from tall oil fatty acids), 74 parts of dipropylene glycol, and 1087 parts of isophthalic acid were added. The reactants were blanketed with nitrogen and heated to a temperature of about 165-190°C while continuously removing water of esterification with constant agitation. Heating was then increased and the temperature gradually rose to about 230°C as the isophthalic acid reacted. When the reaction mass became clear, the acid number was about 20-25 and the temperature rapidly dropped to about 190°C. and 64
g of trimellitic anhydride was added. Add more reaction mass
After holding at 185°C for 30 minutes, the acid value was 44. The resin was diluted to 75% resin solids content using a mixture of n-butanol and 2-butoxyethanol. This diluted resin solution had a viscosity of Gardner-Holdt values Z ₆ -, Z ₇ at 25°C. Acrylic Emulsion F Acrylic Emulsion F is a commercially available acrylic emulsion polymer prepared by polymerizing a monomer mixture of 55 parts n-butyl acrylate, 30 parts styrene, and 15 parts acrylic acid. This emulsion has an acid number of 90-100 on a solids basis and a final solids content of about 48%. Acrylic Emulsion G Acrylic Emulsion G is prepared by standard aqueous emulsion polymerization techniques using a monomer mixture of 45 parts n-butyl acrylate, 32 parts methyl methacrylate, 21 parts acrylonitrile, and 2 parts methacrylic acid. did. For this emulsion polymerization, 0.42 parts of ammonium persulfate and 2 parts of alkyl sulfosuccinate were used as initiator and surfactant, respectively. Emulsion polymerization is
It was carried out at 80°C. The final product has a solids content of 50%,
The acid value was 13. Acrylic Emulsion H Acrylic Emulsion H was made in a very similar manner to that used to make Acrylic Emulsion G. In this polymerization method, the monomer composition is 45 parts n-butyl acrylate, 28 parts methyl methacrylate,
It was a mixture of 19 parts acrylonitrile, 3 parts methacrylic acid and 5 parts 2-hydroxyethyl acrylate. The final product has a solids content of 43% and an acid value
It had a hydroxyl value of 19 and a hydroxyl value of 24. Polyether Polyol I Polyether Polyol I was prepared by reacting 1 mole of bis-phenol A (4,4'-isopropylidene diphenol) with 6 moles of ethylene oxide. The product had a viscosity of 2840 centipoise and a hydroxyl value of 215. Polyether polyol I
The molecular weight of the compound was approximately 520. Polyether polyol I was a liquid material. The third essential component (component C) used in the compositions of the invention is an acid catalyst. This catalyst is (A) and
from about 0.05% by weight based on the total solids weight of (B) to about
Used in amounts varying between 5.0% by weight. It is preferably used at between about 0.1% and 2.5% by weight on the same basis. Preferred acid catalysts that can be used in the compositions of the invention include trismethylsulfonylmethane, trishexylsulfonylmethane, p-toluenesulfonic acid, n-dodecylbenzenesulfonic acid, naphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, and the like. be. Acid catalytic activity can also be created in the coating composition of the invention by incorporating sulfonic acid groups into the polymer (B). This can be accomplished by copolymerizing from about 0.1% to about 5.0% (based on total monomer weight) of monomers such as 2-sulfoethyl methacrylate, styrene sulfonic acid, and the like. It is also possible to use alkyl esters of phosphoric acid or alkylphosphonic acids as acid catalysts in the coating compositions of the invention. Weak organic acids such as formic acid, acetic acid, phthalic acid, etc. can be used but are not preferred. This is because these acids can be dissolved in a reasonable amount of time, such as about 30 minutes or less.
This is because it is not effective in promoting crosslinking reactions at temperatures below 175°C. Inorganic acids such as nitric acid, sulfuric acid, phosphoric acid, hydrohalic acids, Lewis acids, etc. can also be used. In order to enable a more complete understanding of the inventive concept, the following examples are included, in which all parts are parts by weight unless otherwise indicated. These examples are set forth primarily for illustrative purposes, and any specific numerical values of details contained therein should not be construed as limitations on the invention except as indicated in the appended claims. do not have. Examples 1 and 2 and Comparative Example 3 The three coating compositions shown in Table 1 below were made with oil-free saturated polyester resin A and in Examples 1 and 2 with tetrabutoxymethyl glycoluril (TBMGU). Comparative Example 3 was produced using a crosslinking agent that was hexakismethoxymethylmelamine (HMMM). In Examples 1 and 2, the resin crosslinker ratios were 76/24 and 83/17, respectively. In Comparative Example 3, the resin-crosslinking agent (HMMM) ratio was 90/10. Experience has determined that the best films are obtained when using this HMMM content and a curing temperature of 230°C for 60 seconds. These organic solvent soluble enamel paints were manufactured using a three roll mill. Enamel paint made in this way
A 0.002" spreading blade was used to spread the film onto an aluminum panel treated with Allodyne 1200S. Some of the films were cured at 230°C for 600 seconds and others at 260°C for 60 seconds. See below. The second table is 3
The properties of the membrane obtained from the seed composition are shown. Table 2 shows that enamel paints made from TBMGU outperform those made from HMMM in: (a) either in case of excessive firing or exposure to moisture; However, the paint does not flake off in thin fibrous flakes in areas subjected to impact testing. (b) superior wetting resistance; (c) better formability as demonstrated by good bending T-O. Enamel paints based on TBMGU show good retention of oven bake gloss and better accelerated exposure test results.

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[Table] Example 4 A high solids content, organic solvent-based enamel paint was prepared using polyether polyol B and acrylic resin C in combination with tetrabutoxymethylglycoluril (TBMGU). 33 parts of polyether polyol B, 34 parts of acrylic resin C and 33 parts of tetrabutoxymethyl glycoluril were mixed in a suitable mixer. To this mixture was added 0.5 part of n-dodecylbenzenesulfonic acid, 1.0 part of dimethylaminoethanol and 90%
Add part of titanium dioxide pigment. Cowles Pigments
It was dispersed into the mixture using a dissolver. The dispersed pigment paste was diluted to 75% solids with cellosolve. At 75% paint solids, the food cup 4th viscosity is approx.
It was hot in 60 seconds. This enamel paint was sprayed onto a cold rolled steel plate pretreated with iron phosphate and cured at 150°C for 20 minutes. The cured film has the following properties: Film Thickness 1.0 Mil Pencil Hardness H-2H Knoop Hardness (KHN ₂₅ ) 12.0 Gloss 60° 77 Initial Impact Resistance (Reverse), lbs. 60 Cleveland Humidity Test (Impacted) The enamel remained stable after 1 hour, 2 hours after 2 hours at 60 pounds, 24 hours after 24 hours at 50 pounds, and 3 weeks of storage at 55 degrees C. at 55 degrees Celsius. Example 5 332 parts of titanium dioxide pigment dispersed with 233 parts of acrylic resin C are placed in a three-roll mill. This pigment paste was dissolved in 133 parts of acrylic resin C, 92 parts of tetrabutoxymethylglycoluril (TBMGU), 194 parts of xylene, 23 parts of cellosolve acetate, 23 parts of n-butanol and 12 parts of isopropanol. - Add 8 parts of toluenesulfonic acid and mix thoroughly using a mechanical stirrer. The organic soluble paint produced had a food cup viscosity of 62 seconds at 25°C. Paint solids was 68%. The membrane was spread using a 0.002'' spreading blade onto a cold rolled steel plate pretreated with zinc phosphate and the coated panel was cured at 175° C. for 20 minutes.
The properties of the membrane were as follows. Film Thickness, Mil 1.0 Gloss 60° 76 Gloss 20° 50 Pencil Hardness F-H Knoop Hardness 6.0 Impact Resistance (Reverse), lbs 50-50 MEK Resistance (Two-Way Rub) >200 Moisture Resistance (Cleveland Humid Chamber, 60 ℃)
No change in gloss after 10 days Salt spray resistance (ASTM #B117-64) Creep along the scratch line for 240 hours Less than 1/32" Bubbles None Example 6 346 parts of titanium dioxide pigment in a 3-roll mill
210 parts of polyester resin D and 10 parts of cellosolve acetate were introduced and the three components were dispersed with each other to form a pigment paste. This pigment paste
103 parts of polyester resin D, 115 parts of tetrabutoxymethylglycoluril (TMBGU), 3.1 parts of dinonylnaphthalene disulfonic acid, 117 parts of n
- Add butanol and 88 parts of butyl acetate.
The charge was thoroughly mixed with a mechanical stirrer. The resulting paint had a No. 4 Ford Cup viscosity of 60 seconds at 25°C. Paint solids was 73%. The membrane was spread using a 0.002″ spreading blade onto a cold rolled steel plate pretreated with zinc phosphate, and the panel was heated at 175°C for 20 seconds.
The coating was cured by baking. The properties of this film were as follows. Film Thickness 1.0 mil Gloss 60° 86 Gloss 20° 52 Pencil Hardness 2H-3H Knoop Hardness 11.4 Reverse Impact Resistance, lbs 140+ MEK Resistance (Reciprocating Rub) >200 Humidity Resistance (Cleveland Humid Chamber, 60°C)
No change in gloss after 10 days Salt spray resistance (ASTM #B117-64) Creep along the scratch line for 240 hours Less than 1/32" Bubbles None Example 7 and Comparative Example 8 Coating compositions in Table 3 below were prepared using acrylic resin C and a crosslinking agent. The crosslinking agent was tetrabutoxymethylglycoluril (TBMGU) in the first case and hexakismethoxymethylmelamine (HMMM) in the second case. Both compositions The resin-to-crosslinker ratios in the compositions were the same.The amounts and types of ingredients used in the compositions were as shown in Table 3.These water-based enamels were manufactured using a three-roll mill and a Cowles dissolver. The enamel paint thus produced was spread using a 0.003 inch spreading blade onto cold rolled steel pretreated with zinc phosphate.The film was cured at 175°C for 20 minutes. The properties of membranes obtained from two compositions are shown. TBMGU-based membranes have higher reverse impact resistance of 30-40 in-lbs versus 10-20 in-lbs for HMMM-based membranes. Humidity and salt spray resistance are as shown in Table 3.
In the case of TBMGU it is better. for example
Salt spray test (ASTM) on membranes based on TBMGU
No. B-117-64) was applied for 500 hours, and no air bubbles were formed, and there was no cleavage on the scratched lines.

【table】

Table Example 9 204 parts of titanium dioxide pigment were dispersed in 164 parts of polyester resin E, 5 parts of acrylic resin C and 8 parts of dimethylaminoethanol using a 3-roll mill. In this pigment mill, 109 parts of polyester E, 50 parts of TBMGU, 0.5 parts of p.
-Toluenesulfonic acid and 7 parts of dimethylaminoethanol were added and mixed using a high speed disperser, then 441 parts of deionized water were added. The resulting aqueous enamel was approximately 46% solids and had a fourth force cup viscosity of 60 seconds. The enamel thus produced was spread using a 0.003" spreading blade on cold rolled steel pretreated with iron phosphate. The film was cured at 175°C for 20 minutes. The properties of the film were as follows: The thickness of the cured films was 1.0 mil. They were hard and resistant to organic solvents such as acetone, methyl ethyl ketone, etc. The properties of the films were: 60° gloss 96; Knoop Hardness 6.2; reverse impact resistance
After 240 hours of 120 Kn-lbs and salt spray exposure, there was no blistering on the membrane and little creep on the scratch lines. The moisture resistance after two weeks (Cleveland Humid Room, 60°C) was excellent. There was no blistering on the film and no loss of any gloss. The overbake stability of the film was excellent. Examples 10, 11 and 12 The coating compositions shown in Table 4 were prepared using acrylic resin C and the crosslinking agent tetramethoxymethyl glycoluril (TMMGU). The three compositions are 75/25, 70/30 and 70/30 respectively on a solid basis.
Made with a resin/crosslinker (TMMGU) ratio of 65/35. Pigment-binder ratio in all compositions is 80/100
and dimethylaminoethanol was used to neutralize 60% of the active carboxyl groups of the acrylic resin. p-Toluenesulfonic acid was used as a catalyst. An aqueous enamel was prepared by the same procedure as described in Example 7 using a three roll mill. The final paint solids and viscosities of these enamels are shown in Table 4. The enamel thus produced,
The film was spread on cold rolled steel pretreated with zinc phosphate using a 0.003″ spreading blade. The film was cured at 175°C for 20 minutes. Table 4 shows the properties of the film. shows the results of salt spray resistance with varying content of crosslinker (TMMGU).Table 4 shows the excellent membrane properties.The best corrosion resistance of the membrane is determined by the resin-crosslinker ratio, respectively.
Obtained at 75/25 and 70/30.

【table】

【table】

[Table] Example 13 Coating composition 245 parts of acrylic emulsion F, 95 parts of deionized water,
103 parts dimethoxymethyldiethoxymethylglycoluril, 308 parts titanium dioxide pigment and
4.1 parts of dimethylamine ethanol was sand milled. After the pigment was well dispersed, another 245 parts of acrylic emulsion F were gradually added, followed by 0.72 parts of p-toluenesulfonic acid dissolved in 1 part of isopropanol, 4.1 parts of dimethylaminoethanol, and 45 parts of dehydration. Added ionized water. The resulting aqueous enamel had a solids content of 61% and a fourth force cup viscosity of 50 seconds at 25°C. This film was spread on cold rolled steel pretreated with zinc phosphate using a 0.002″ spreading blade and cured at 175°C for 20 minutes. The properties of the film were as follows: Film thickness 1.0 mil gloss 60° 92 gloss 20° 79 Knoop hardness 14.4 Pencil hardness H-2H Impact resistance (reverse), lbs. It had good stability. There was no pigment precipitation and there was no change in the film properties of coatings made from aged enamel. Example 14 A clear water-based varnish was prepared using a high-speed stirrer at 3.3 parts. Tetramethoxymethyl glycoluril, 1.2
1 part dimethylaminoethanol and 0.06 parts of the same amount of isopropanol. It was prepared by mixing p-toluenesulfonic acid and 10 parts deionized water. The resulting varnish was spread using a No. 22 wire cator on an aluminum panel (Allodyne 1200S treatment) and a cold-rolled steel plate that had been separately treated with iron phosphate, and the film was heated at 150℃ for 20 minutes.
Cured at 260°C for 60 or 90 seconds. The properties of this film are as follows. Substrate: Allodyne 1200S Curing conditions 150℃/20 minutes 260℃/60 seconds Film thickness 0.65 mils 0.6 mils Knoop hardness 6.9 7.4 Pencil hardness H-2H H-2H MEK resistance (reciprocating friction) >200 >200 Impact resistance (reverse) ), Bond ＞60 ＞60 Substrate: Cold rolled steel treated with iron phosphate Hardening conditions 150℃/20 minutes 260℃/90 seconds Film thickness 0.75 mil 0.8 mil Knoop hardness 6-8 6-8 Pencil hardness H-2H H- 2H MEK resistance (reciprocating rub) 90 >200 Example 15 Clear water-based varnish contains 67 parts of acrylic emulsion H,
It was prepared by mixing 10 parts of tetramethylol glycoluril dissolved in 5 parts of water and 0.21 parts of 50% p-toluenesulfonic acid aqueous solution. The initial viscosity of the varnish was 15 centipoise and the pH was 4.75. This varnish was spread on aluminum (treated with Allodyne 1200S) using a No. 34 wire cutter. This film was cured at 125°C for 20 minutes and at 260°C for 1 minute.
The properties of the membrane were as follows. Curing Conditions 125°C / 20 minutes 260°C / 1 minute Film Thickness 1.0 mil 1.0 mil Knoop Hardness 3.3 4.8 MEK Resistance (Reciprocating Rub) 200 200 A 1.0 mil control varnish film made without any tetramethylol glycoluril 2.3
It had a Knoop hardness of 9 times and a rub resistance of less than 9 rubs. Even after aging the varnish containing tetramethylol glycoluril at 55°C for 3 weeks, there was no coagulation or phase separation in the varnish. The Bruckfield viscosity remained unchanged and the pH was 3.5. The aged varnish cured similarly to the initial composition. Example 16 60 parts of polyether polyol, 40 parts of dimethoxymethyldiethoxymethylglycoluril, and 90 parts of titanium dioxide were dispersed in a high speed Kauls dissolver. This dispersed pigment paste
1.2 parts p- dissolved in 1.8 parts isopropanol
Toluenesulfonic acid was added and mixed on a high speed stirrer before 17 parts of deionized water was added. The resulting aqueous high solids content enamel had a fourth force cup viscosity of 60 seconds at 25°C. This film was spread on a zinc phosphate cold rolled steel plate using a 0.003″ spreading blade and heated at 125°C.
Cured for 20 minutes. The properties of the membrane were as follows. Film Thickness 1.1 mil Gloss 60° 94 Gloss 20° 79 Knoop Hardness (25 g) 11.7 Pencil Hardness H-2H Impact Resistance (Reverse), lbs 100-120 MEK Resistance (Reciprocating Rub) >200 Water-based high solids content enamel It had good storage stability. There were no significant changes in the properties of the coatings produced from the enamel after aging at 55°C for two weeks. The compositions of the present invention also find utility in the field of electrodeposition when used in the presence of acid catalysts. The following examples are examples of coating compositions useful in electrocoating. Example 17 77 parts of acrylic resin C (75% solids), 22 parts of TBMGU, 11.5 parts of diisopropanolamine (50% solution) and 22 parts of titanium dioxide pigment were introduced into a high speed disperser. These materials were dispersed in a high speed disperser and the dispersed pigment paste was diluted by slowly adding up to 1000 parts of deionized water to produce a 10% paint solids solution. To the 10% aqueous paint was added 0.5 part of dinonyl naphthalene disulfonate, which had been previously neutralized with diisopronolamine. Ten%
The water-based paint had a pH of 8.2 and an electrical conductivity of 780 johm ^-1 cm ^-1 . 1 at ambient temperature with constant stirring of the paint.
Ripened late. 150 Zinc Phosphate Pretreated Cold Rolled Steel Sheet
Electric paint with volt for 60 seconds. The electrocoated steel plates were rinsed with deionized water and then cured at 175°C for 20 minutes. The thickness of the cured film was 0.8 mil.
It was resistant to methyl ethyl ketone abrasion and other organic solvents. The Knoop hardness was 7.4 (KHN ₂₅ ) and the reverse impact resistance was 20-30 inch-lbs. When exposed to a 240 hour salt spray resistance test, this enamel developed a scratch line of 2-3 mm of creep and no air bubbles on the surface. In the composition of the present invention, component (B) was confirmed to be a non-gelling, non-self-crosslinking polymer that is soluble in organic solvents or dispersible in water, and this polymer has carboxyl groups and alcohol as reactive groups. containing one or more of hydroxyl groups or amides, the amount of these groups accounting for at least about the total weight of the polymer.
0.5% by weight, and up to about 25% by weight. British Patent No. 1,146,858 and corresponding French Patent No. 1,486,213 (Florus et al.) teach the use of certain glycoluril derivatives in combination with self-crosslinking polymers. Component (B) of the Florus et al. patent contains 10 to 0 parts by weight of polymerized units of an ester of acrylic acid and/or methacrylic acid with a monohydric alcohol having 1 to 20 carbon atoms and 3 to 6 carbon atoms. α・β-Ethylenically unsaturated carboxylic acid polymer unit 2
It is a copolymer containing from 0 to 15 parts by weight of polymerized units of at least one other ethylenically unsaturated comonomer. These patents disclose that their copolymers contain N-methylol acrylamide and/or N-methylol methacrylamide and ethers of these amides with monohydric alcohols having 1 to 10 carbon atoms, preferably 3 to 4 carbon atoms. It teaches about 0.5 to 40 and especially 5 to 20 parts by weight. The copolymers are self-crosslinking when they contain either methylol acrylamide or an alkyl ether of these methylol acrylamides. These foreign patent polymers range from 20 to approx.
Self-crosslinking will occur under normal curing conditions at about 150-175°C for a period of 60 minutes. The tetrabutoxymethylglycoluril in the coating compositions of Florus et al. does not act as a crosslinking agent for the polymer at a curing temperature of 150°C. Rather, it only plasticizes with the membrane and does not act as an effective crosslinking agent, but only as an additive to improve corrosion resistance. On the other hand, the compositions of the present invention are not self-crosslinking but contain -COOH, -OH and/or as the only reactive groups.
or -CONH ₂ and these groups are 20
Contains a water-dispersible polymer that does not self-condense under practical curing conditions of 150°C to 175°C for times of 60 minutes to 60 minutes. The presence of an acid catalyst is required to achieve an effective crosslinking reaction of the glycoluril derivative with a non-self-crosslinking polymer of the type used in the composition of the present invention. The British and French patents mentioned above do not disclose, teach, or suggest the use of any acid catalyst in their compositions. Two acrylic resins were prepared to illustrate the contrasting differences between the compositions of Florus et al. and the compositions of the present invention. That is, acrylic resin J and acrylic resin K, and acrylic resin J is
The compositions were essentially the same, except that the acrylic resin contained no isobutoxymethylacrylamide, whereas it contained 125 parts of isobutoxymethylacrylamide. In other words, their compositions were the same. The monomer composition in each acrylic resin composition is as follows.

Table: These acrylic resins J and K were prepared separately in a reaction vessel equipped with a stirrer reflux condenser and a nitrogen inlet tube. Although acrylic resin J has very insignificant differences, it is
It has a monomer composition similar to that described in No. 1486213. Isobutoxymethylacrylamide and 2-hydroxybutylacrylamide were used instead of N-butoxymethylacrylamide and 4-hydroxybutylacrylate, respectively.
-Hydroxyethyl acrylate was used.
Acrylic Resin K had the same monomer composition as Acrylic Resin J except that isobutoxymethylacrylamide was not present. The general method of resin production was as follows. Add 200 parts of isobutanol to a suitably equipped reaction vessel and add 100 parts of isobutanol.
Heated to -105°C. A monomer mixture containing about 2% by weight t-butyl perbenzoate, based on total monomer weight, and 2% by weight n-dodecyl mercaptan, based on total monomer weight, is added to the heated solvent. The additive is loaded into the reactor over a period of 2 hours while maintaining the temperature of the solvent at about 100-105°C. After the monomer addition is complete, the reaction temperature is maintained at about 105°C for 1 hour. Another part of t-butyl perbenzoate is added and the reaction is maintained at 105°C for an additional hour. Afterwards, each resin syrup was cooled and diluted with isobutanol for 65 minutes.
Adjust to % solids content. These acrylic resin polymers were combined with Resins J and K in the amounts shown in Table 5 below in four coating compositions.
Prepared by mixing TBMGU and p-toluenesulfonic acid with or without addition. The thickness of the spread film was approximately 1 mil and was spread on cold rolled steel plate that had been pretreated with zinc phosphate. A total of 24 plates were manufactured. these boards
105°C for 30 minutes, 150°C for 60 minutes and 175°C for 20 minutes
Bake for a minute. The properties of the films on these plates are shown in Table 6.

【table】

【table】

[Table] In water-dispersible or water-dispersed coating compositions, if the polymer contains carboxylic acid groups:
It is important to use ammonia or a water-soluble organic amine in the composition to achieve water dispersibility of the entire composition. The amount of ammonia or organic amine required is dictated by the amount of carboxyl groups present in the polymer. Generally, an amount of amine equivalent to carboxyl groups is sufficient to make the polymer and coating composition water-dispersible. It is also possible to use as little as 10% to 20% of the amine equivalent to the carboxyl groups of the polymer to obtain a water-dispersible composition. For example, water-soluble lower organic amines such as primary, secondary or tertiary amines such as ethylamine, diethylamine, triethylamine, diethanolamine, N-N-dimethylethanolamine, diisopropanolamine, etc. or ammonia can be used. . Although not required, in some cases the use of anionic or nonionic surfactants can assist in obtaining stable aqueous dispersions of these organic coating compositions. Examples of anionic surfactants include sulfosuccinates, sodium dioctylsuccinate, sodium cyclohexylsuccinate, and the like. A large number of these anionic surfactants are commercially available. Nonionic surfactants include ethoxylated alkylphenols. The amount of surfactant typically used is up to about 4% by weight of the total paint solids weight. Although the paints of the present invention are primarily used to coat metals such as steel, aluminum, etc., these paints can also be used on other substrates such as wood, glass, plastic, paper, textiles, etc. I can do it.

Claims (1)

[Claims] 1 (A): 2% to 50% by weight of a glycoluril derivative having the following structural units; (In the formula, n is an all integer from 2 to 4; m is from 0 to 2
(n+m is an all integer of 2 to 4; each R is either hydrogen or an alkyl group having 1 to 4 carbon atoms) (B): 98% to 50% by weight water dispersibility or a normally non-self-crosslinking polymer soluble in organic solvents. However, this polymer has either a carboxyl group, an alcoholic hydroxyl group, or an amide group as a reactive group.
(A) in an amount of at least 0.5% and not more than 25% by weight of the total weight of the polymer; and the reactive group is thermally reactive with (A). (C): 0.05% to 5.0% by weight of an acid catalyst based on the total weight of (A) and (B); A coating composition comprising a mixture of (A), (B) and (C). However, the percentage of (A) and (B) above is 100 as a whole.
% by weight and is based on the total solid weight of (A) and (B).