JPH0530860B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a non-aqueous dispersion type resin composition. More specifically, the present invention relates to a thermosetting non-aqueous dispersion type resin composition comprising a mixture of a non-aqueous solvent dispersion of a vinyl ester-modified vinyl polymer and a crosslinking agent. In recent years, there has been an increasing demand for resource saving and pollution-free technology in the paint field as well. In particular, high-solids paints, which are resource-saving paints with low solvent content and high solid content, are preferred because they can be used with conventional paint manufacturing methods or painting equipment. ing. Furthermore, considering recent measures to regulate the use of solvents due to air pollution problems, it seems that ordinary high-solids paints that use large amounts of aromatic or ester solvents are not industrially desirable. Furthermore, in view of the regulations on the use of various solvents that have been tightened in recent years, and broadly speaking from the viewpoint of non-pollution and resource conservation, various non-aqueous dispersion paints that use aliphatic hydrocarbon solvents as the main solvent have been proposed. It is being done. However, conventionally known non-aqueous dispersion compositions of this type, such as dispersion stabilizer/dispersion particle combinations such as decomposed natural rubber/acrylic resin, acrylic resin/acrylic resin, oil-modified alkyd resin/acrylic resin, Coating films obtained from thermosetting non-aqueous dispersion paints using polybutadiene/acrylic resins or the like as a color vehicle generally do not have sufficient physical properties. For example, a flexible coating film is insufficiently hard, and conversely, a hard coating film is insufficiently flexible; we have not found anything that has both properties at the same time. . In addition, it was not always possible to obtain sufficient performance in salt spray resistance, moisture resistance, water resistance, and secondary physical properties after each test. The inventors of the present invention have made extensive studies to eliminate or improve the various drawbacks mentioned above, and as a result, have arrived at the present invention. That is, in the present invention, monomers (i) to (iii) are dissolved, but vinyl ester,
The vinyl ester-modified vinyl copolymer obtained from monomer (ii) and monomer (iii) is dissolved in an aliphatic hydrocarbon solvent in which (i) α,β-monoethylenically unsaturated monomer (ii) a hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid; ) said above
75 to 97% by weight of a monomer mixture consisting of α,β-monoethylenically unsaturated monomers other than (ii); (a) an epoxy compound having one or more epoxy groups in the molecule; and (b) ) A mixture of 3 to 25% by weight of vinyl ester obtained from unsaturated monocarboxylic acid...
The present invention relates to a non-aqueous dispersion type resin composition consisting of a non-aqueous dispersion of a "vinyl ester-modified vinyl polymer" obtained by polymerizing 70 to 20% by weight, that is, component (A), and (B) a crosslinking agent. The "aliphatic hydrocarbon solvent" used in the present invention has the following characteristics.
That is, although α,β-monoethylenically unsaturated monomers (i), (ii) and (iii), which will be detailed later, are soluble,
The "vinyl ester-modified vinyl copolymer" obtained from vinyl ester, monomer (ii), and monomer (iii) has the property of not being soluble. Specifically, for example, a mixture containing aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, mineral spirits, aliphatic naphtha, etc. as main components. Can be mentioned. Next, the "solvent-soluble vinyl resin (dispersion stabilizer)" (hereinafter abbreviated as "soluble vinyl resin" if necessary) used as the dispersion stabilizer of the present invention is:
Generally speaking, it is obtained by copolymerizing component (i), that is, an α,β-monoethylenically unsaturated monomer, in the aliphatic hydrocarbon solvent mentioned above. The α,β-monoethylenically unsaturated monomer (i) may be any one that makes the soluble vinyl resin as a dispersion stabilizer soluble or semi-soluble in the aliphatic hydrocarbon solvent. Even such monomers can be substantially used. In addition, especially the general formula [In the formula, R is H or CH ₃ , and n is an integer of 6 to 18] It is preferable to use a part of the α,β-monoethylenic monomer. Such monomers are particularly preferred because they render the dispersion stabilizer soluble or semi-soluble in the solvent. Monomer (a) having such a specific general formula is
In a particular example, it is used in a proportion of 5 to 60% by weight of the α,β-monoethylenically unsaturated monomer (i).
In the above range, if it is less than the lower limit of 5% by weight, the effect of improving the solubility of the dispersion stabilizer in the solvent tends to decrease, which is not preferable. On the other hand, if it exceeds the upper limit of 60% by weight,
It is also unfavorable because it tends to reduce coating film performance such as hardness and impact resistance. A specific example is 2-ethylhexyl (meth)
Examples include esters such as acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. these are,
They can be used singly or as a mixture of two or more. In addition, the α,β-monoethylenically unsaturated monomer
As for (i), other monomer (b) other than the monomer (a) represented by the above general formula is added to the monomer (i) from 40 to 95
It can be used in a range of % by weight. Specific examples of such monomers include acrylic acid,
α, β-monoethylenically unsaturated carboxylic acids such as methacrylic acid, itaconic acid, maleic acid, fumaric acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate acrylate,
n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2
-Hydroxyethyl (meth)acrylate, 2-
Hydroxypropyl (meth)acrylate, 3-
Hydroxypropyl (meth)acrylate, 2-
Hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth) Acrylate, 3-butoxy-2hydroxypropyl (meth)acrylate, 2-hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, and other N,N' dimethylaminoethyl ( Dialkyl esters of fumaric acid such as meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, dibutyl fumarate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile , vinyl acetate, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-n-butoxymethyl ( meth)acrylamide, N-sec-
Butoxymethyl (meth)acrylamide, N-t
-butoxymethyl(meth)acrylamide, N-
isobutoxymethyl(meth)acrylamide,
N-alkoxymethylated products of α,β-monoethylenically unsaturated carboxylic acid amides such as these; or N-methylolated products thereof. These monomers can be used alone or as a mixture of two or more. Among the above monomers, N-alkoxymethylated monomers of α,β-monoethylenically unsaturated carboxylic acid amides and hydroxyalkyl ester monomers of α,β-monoethylenically unsaturated carboxylic acids If used simultaneously, the dispersion stabilizer becomes difficult to dissolve in the aliphatic hydrocarbon solvent and tends to increase in viscosity, which is not preferable. The soluble vinyl resin used as the dispersion stabilizer of the present invention is produced by a conventional solution polymerization method. For example, the remaining monomers (mixture) and a polymerization initiator are added dropwise into a mixture of a part of the monomers (mixture) and a polymerization solvent, and the remaining monomers (mixture) and a polymerization initiator are polymerized, or the monomers (mixture) Also applicable are methods of dropping a polymerization initiator and polymerizing. In any case,
The present invention is not intended to be limited to a specific solution polymerization method. The solvent used in this solution polymerization method is the aliphatic hydrocarbon solvent described above. In addition, as a polymerization initiator, for example, benzoyl peroxide, t-butyl perbenzoate, t-
An organic peroxide such as butyl peroxybenzoate, t-butyl peroxyoctoate, lauroyl peroxide, or an azo compound such as azobisisobutyronitrile is used. Further, these polymerization initiators may be used alone or in an appropriate mixture of two or more. In the present invention, if necessary, a chain transfer agent such as dodecyl mercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride, etc. may be used to adjust the molecular weight. In the present invention, in the presence of a soluble vinyl resin as a dispersion stabilizer dissolved (or partially dissolved) in the aliphatic hydrocarbon solvent obtained as described above, α,β-monoethylene Hydroxyalkyl ester monomers of unsaturated carboxylic acids, i.e. (ii)
A "vinyl ester-modified vinyl polymer" (non-aqueous dispersion). The nonaqueous solvent dispersion of the vinyl ester-modified vinyl copolymer needs to contain a hydroxyl group in the molecule in order to undergo a crosslinking reaction with the crosslinking agent (B) described below. Therefore, the monomer mixture [(ii)+(iii)]
As one of the components, hydroxyalkyl ester monomer (ii) of α,β-monoethylenically unsaturated carboxylic acid is used. By the way, this monomer (ii) has strong polarity. Therefore,
A copolymer containing this monomer as one component is difficult to dissolve in aliphatic hydrocarbon solvents, and is therefore suitable for forming dispersed particles. In addition, such monomer (ii) is mixed with an α,β-monoethylenically unsaturated monomer mixture [(ii)+(iii) so that the hydroxyl value in the dispersed particle component is approximately 8 to 140. )〕During,
It is used in a range of 3 to 30% by weight. If monomer (ii) is less than 3% by weight within the above weight% range, the crosslinking density will decrease during the reaction process with the crosslinking agent (B), resulting in poor solvent resistance of the coating film. This is not desirable as it becomes low. On the other hand, if the amount exceeds 30% by weight, the non-aqueous dispersion of the vinyl ester-modified vinyl copolymer will have too high a viscosity, which will impede workability. Moreover, the crosslinking density after the thermosetting reaction becomes too high, which tends to reduce the flexibility, water resistance, etc. of the coating film, which is also undesirable. Specific examples of this type of monomer (ii) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate. , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy- Examples include 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, etc. These can be used alone or as a mixture of two or more. May be used. Furthermore, in the presence of a dispersion stabilizer, the monomer (iii) other than the hydroxyalkyl ester of the α,β-monoethylenically unsaturated carboxylic acid used for copolymerization is a monomer mixture [( ii)＋(iii)〕70～97
Use within the range of % by weight. Specific examples of the monomer (iii) include α,β-monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; methyl (meth)acrylate, ethyl (meth)acrylate; ) acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate n-
Butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate
Acrylate, lauryl (meth)acrylate,
Alkyl esters of acrylic acid or methacrylic acid such as tridecyl (meth)acrylate and stearyl (meth)acrylate; other N,N'-
Dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate,
Dialkyl esters of fumaric acid such as benzyl methacrylate and dibutyl fumarate, styrene,
Vinyltoluene, α-methylstyrene, (meth)
Examples include acrylonitrile and vinyl acetate. These may be used singly or in an appropriate combination of two or more depending on the purpose and use of the coating composition. Furthermore, as the monomer component (iii), it is recommended to avoid using an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide, as this causes thickening during the production of dispersed particles. is preferred. In the present invention, the "vinyl ester-modified vinyl copolymer" used as a dispersed particle component is obtained by polymerizing vinyl ester with the monomer (ii) and monomer (iii), In this way, the resulting coating film can be provided with the excellent alkali resistance, acid resistance, salt water resistance, and salt water spray resistance that vinyl esters have. The vinyl ester used in the present invention is a reaction product of (a) an epoxy compound having one or more epoxy groups in the molecule and (b) an unsaturated monocarboxylic acid,
All known ones may equally be used. The vinyl ester can be synthesized by a known esterification reaction. For example, an esterification reaction catalyst between an epoxy compound and an unsaturated monocarboxylic acid in an air atmosphere,
If necessary, in the presence of a polymerization inhibitor, a solvent, or one of the monomers (ii) and monomers (iii) that can be used as a solvent for the esterification reaction (hereinafter referred to as a polymerizable monomer). The reaction is carried out by heating, and then diluted with a solvent or a polymerizable monomer as necessary for synthesis. When synthesizing these, the reaction ratio of the epoxy compound having one or more epoxy groups in the molecule and the unsaturated monocarboxylic acid is used in the range of 0.6 to 1.2 moles of carboxyl group per mole of epoxy group. A more preferable range is around 1 mol. It is also possible to replace a part or most of the unsaturated monocarboxylic acid with another carboxylic acid or carboxylic anhydride. Further, the amount of the polymerization inhibitor, solvent, or polymerizable monomer to be used can be appropriately selected depending on desired workability, coating performance, etc. The epoxy compound that can be used to synthesize the vinyl ester is (1) synthesized by the reaction of bisphenol A and epichlorohydrin or methylepichlorohydrin. For example, the product name Epicote #827, #828, #834, #1001 manufactured by Ciel Corporation,
#1004, #1007, #1009, etc., Union Carbide product name ERL #2772, #2774, EKR2002, etc.
Product name: Araldite GY-#250, manufactured by Ciba Corporation.
#260, #280, #6071, #6084, #6099, etc., product name AER #330, #331, #332, manufactured by Asahi Kasei Corporation.
#661, #664, etc., manufactured by Dainippon Ink & Chemicals Co., Ltd., product name: Epiclon #800, #1000, #4000, etc. (2) Novolak obtained by reacting phenols and formaldehyde under an acidic or alkaline catalyst. Or, products obtained by reacting resol with epichlorohydrin or methylepichlorohydrin, such as DEN #431, #438 manufactured by Dow Chemical Co., Ltd.
#448 etc., Teva product name ECN #1235, #1273,
#1280, #1290, etc. (3) Products obtained by reacting halogenated phenols with epichlorohydrin or methylepichlorohydrin, such as Dow Chemical Co., Ltd. product name DER #511, #542, #580, etc., Ciba Co., Ltd. product name Product name: Araldite #8011, #8047, etc.
(4) Obtained by reacting phenols with ethylene oxide or propylene oxide, etc., and epichlorohydrin or methylepichlorohydrin. For example, product name EP manufactured by Asahi Denka Co., Ltd.
Examples include #4000, #4001, etc. These may be used alone or in mixtures. Examples of the unsaturated monocarboxylic acid to be reacted with the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, etc. In addition, monoesters of unsaturated polyhydric carboxylic acids such as maleic acid monoethyl ester may also be used. I can do it. These may be used alone or in mixtures. Polymerization inhibitors used in the synthesis of vinyl esters include hydroquinones such as hydroquinone, quinones such as benzoquinone, hydroquinone monomethyl ether, phenols such as α-naphthol, and organic or inorganic copper such as copper naphthenate. Examples include salts, amidines such as acetamidine acetate, and quaternary ammonium salts such as trimethylbenzylammonium chloride and laurylpyridinium chloride. These may be used alone or in mixtures. The amount of polymerization inhibitor to be used is in the range of about 0.001 to 0.5 parts by weight per 100 parts by weight of the reactants, but good results can be obtained in the range of about 0.005 to 0.05 parts by weight. Furthermore, tertiary amines such as triethylamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, etc. are included as reaction catalysts for vinyl ester synthesis, and these may be used alone or as a mixture. The method for synthesizing the vinyl ester is to react 1 mole of the epoxy group of an epoxy compound with 0.6 to 1.2 moles of carboxyl group of an unsaturated monocarboxylic acid at a temperature of 50 to
The reaction is carried out by heating in the range of 180°C. Preferably, the reaction temperature is in the range of 80 to 140°C.
The amount of polymerization inhibitor used in this reaction is within the range described above. In addition, the amount of the esterification reaction catalyst used is approximately 0.001 to 5.0 parts per 100 parts by weight of the reactants.
Parts by weight are sufficient, but good results are obtained with about 0.005 to 1.0 parts by weight. Furthermore, when adding a solvent or a polymerizable monomer during the reaction, it is advantageous from the viewpoint of reaction rate to use as little as possible, although it depends on the reactants.
The end point of the reaction can be determined by measuring the acid value. From the viewpoint of performance, it is generally desirable that the acid value at the end of the reaction be 20 or less. When the resulting resin reaches the end point of the reaction, a polymerization inhibitor is added if necessary and after it is completely dissolved, cooling is started. After cooling is started, a solvent or a polymerizable monomer is added as needed, and once dissolved, the mixture is cooled to room temperature.
At this time, the amounts of the solvent and polymerizable monomer to be used are determined depending on the desired viscosity, workability, curability, etc. The amount of polymerizable monomer is usually 10 to 70% by weight based on the total amount of vinyl ester and polymerizable monomer. In this case, monomer (ii) and part of monomer (iii) are used as a solvent for vinyl ester production as described above, but such polymerizable monomers are naturally also used in the vinyl ester-modified vinyl copolymer. Since it is a raw material component, the amount used is such that the total amount of the polymerizable monomer and other monomers (ii) and monomer (iii) falls within the specified blending range described below. Must. Such polymerizable monomers may be used alone or as a mixture of two or more. Furthermore, any solvent may be used in the esterification reaction as long as it does not interfere with the production of dispersed particles. Examples of such organic solvents include hydrocarbon solvents such as heptane, octane, mineral spirits, toluene, and xylene, alcohol solvents such as propyl alcohol and butyl alcohol, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, etc. Organic solvents such as ketone solvents, other alcohol ester solvents, and ether ester solvents are not particularly limited as long as they do not impair the stability of the non-aqueous dispersion. The vinyl ester used in the present invention is a reaction product obtained as described above, but commercially available vinyl esters can also be used without any problem. Examples of commercially available products include Lipoxy R802, Lipoxy R806, and Lipoxy H-600 (manufactured by Showa Kobunshi Co., Ltd.), Deitzkrite UE- (trade name) manufactured by Dainippon Ink and Chemicals Co., Ltd.
5101, UE-5210, UE-3520, etc., Nippon Shokubai Kagaku Co., Ltd. product name: Epolack RF-1001, etc., Nippon U-Pica Co., Ltd. product name: Neopol 8250L, 8250H, UE-3520, etc.
8411L, 8411H, etc., manufactured by Hitachi Chemical Co., Ltd. Product names: Polyset 6000K, 6100, 6200, RS-6120S
etc., product name Prominate P- manufactured by Takeda Pharmaceutical Co., Ltd.
310, P-311, etc., Delakane 411, 411C, 470, 510, etc. manufactured by Dow Chemical Co., Ltd., Smearp EVR-911, manufactured by Sumitomo Chemical Co., Ltd. These include one or two products. Can be used as a mixture of more than one species. In the present invention, the vinyl ester-modified vinyl resin as the dispersed particle component contains 3 to 25% by weight of the vinyl ester and the α,β-monoethylenic monomers (ii) and (iii). The mixture consists of 75-97% by weight of polymerization reactants. As mentioned above, the amount of modification of vinyl ester is 3 to 25
It is preferably in the range of 5 to 20% by weight. In the above, if it is lower than 3% by weight,
The advantages of vinyl ester resins, such as their excellent alkali resistance, acid resistance, salt water resistance, and salt water spray resistance, cannot be fully utilized. Conversely, 25% by weight
If it exceeds this range, the weather resistance, stain resistance, etc., which are the characteristics of vinyl resins, may be impaired, and the viscosity may increase during the production of dispersed particles, which is likewise undesirable. Furthermore, the nonaqueous solvent dispersion of the vinyl ester-modified vinyl polymer in the composition of the present invention contains a vinyl resin [copolymer of monomer (i)] 30 to 30% as a dispersion stabilizer.
It is obtained by polymerizing 70 to 20% by weight of a mixture consisting of monomer (ii), monomer (iii) and vinyl ester in the presence of 80% by weight. In the above, the vinyl resin, which is a dispersion stabilizer, is
When the amount is less than % by weight, it becomes difficult to obtain a stable non-aqueous solvent dispersion. On the other hand, if it exceeds 80% by weight, it becomes difficult to obtain a non-aqueous solvent dispersion, which is also not preferred. The above copolymerization temperature is determined by the type of polymerization initiator and polymerization solvent used. Usually 50℃～
The temperature is preferably between 200°C and 60°C to 150°C. The reaction time varies depending on the temperature and other factors, but is generally about 4 to 20 hours. As the polymerization initiator, the above-mentioned organic peroxides or azo compounds are preferably used. In addition, in order to adjust the molecular weight, the chain transfer agent shown above can also be used. Next, the crosslinking agent as component (B) used in the composition of the present invention will be explained. The crosslinking agent may be one that forms a coating film by crosslinking with functional groups such as hydroxyl groups, carboxyl groups, amino groups, methylol groups, etc., contained in the non-aqueous dispersion of the vinyl ester-modified vinyl polymer. Any of these can be used. Particularly preferred is a crosslinkable copolymer resin containing as one component an aminoformaldehyde resin, a blocked isocyanate compound, and an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide. Specific examples of the aminoformaldehyde resin include melamine, formaldehyde resin, urea-formaldehyde resin, benzoguanamine-formaldehyde resin, resinous condensates produced by reacting various triazine derivatives with formaldehyde, or etherified products thereof. . In the production of the etherified product, alcohols used as etherification agents include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol, and benzyl. Examples include alcohol, lauryl alcohol, and the like. However, it is preferable to use an alcohol having 1 to 4 carbon atoms. Further, the amino formaldehyde resin may be used alone or in an appropriate combination of two or more depending on the purpose and use of the coating composition. In the present invention, the nonaqueous solvent dispersion of the vinyl ester-modified vinyl polymer (component A) and the aminoformaldehyde resin (component B) are used in a solid weight ratio of 50/50 to 90/10. is preferred. If the amino formaldehyde resin is less than 10% by weight in the above usage ratio, the crosslinking properties of the coating film will be insufficient, and solvent resistance, coating surface smoothness, coating film hardness, etc. will tend to decrease. Conversely, when the amino formaldehyde resin is more than 90% by weight,
The characteristics of vinyl ester resins, namely, alkali resistance, acid resistance, salt water resistance, and salt water spray resistance are impaired. Furthermore, the crosslinking density becomes too high, which may upset the balance between hardness and flexibility, which is unfavorable in terms of durability. In addition, the blocked isocyanate compound as the crosslinking agent has two isocyanate groups in one molecule.
This is a blocked isocyanate compound having at least one isocyanate group, and all of its isocyanate groups are masked with a blocking agent. Such blocked isocyanate compounds are
It is necessary for the crosslinking reaction with a nonaqueous solvent dispersion of a vinyl ester-modified vinyl polymer, and is also characterized by providing the excellent weather resistance and chemical resistance of urethane resins. As the blocked isocyanate compound, 1
Polyisocyanate compounds having two or more isocyanate groups in the molecule, such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4 -Trilene-
Diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4, Polyisocyanates such as 4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, lysine isocyanate and an excess of said isocyanate compounds, such as ethylene glycol, propylene glycol, 1 , 3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl 1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc. Examples include isocyanate compounds obtained by blocking with a blocking agent a bifunctional or more functional polyisocyanate obtained by a corresponding reaction, a polyisocyanate having a Biuret structure, a polyisocyanate having an allophanate bond, etc. Further, the blocking agent may include phenol,
Phenols such as cresol, alcohols such as methanol, benzyl alcohol, ethylene glycol monoethyl ether, methyl acetoacetate,
Active methylene series such as malonic acid and dimethyl, acid amide series such as acetanilide and acetate amide, other imide series, amine series, imidazole series, urea series, carbamate series, imine series, oxime series, mercaptan series, and sulfite series , lactams, etc. As mentioned above, the crosslinking reaction of the composition of the present invention is carried out by the reaction between the hydroxyl groups of the non-aqueous solvent dispersion of the vinyl ester-modified vinyl polymer and the isocyanate groups of the blocked isocyanate compound. In the present invention, the blocked isocyanate compound is (hydroxyl group in the non-aqueous dispersion of the vinyl ester-modified vinyl polymer)/(isocyanate group of the blocked isocyanate compound)=1/1.3 to 1/
It is preferable to use a ratio of 0.5 (equivalent ratio).
When the ratio of (hydroxyl groups in the non-aqueous dispersion of the vinyl ester-modified vinyl polymer)/(isocyanate groups in the blocked isocyanate compound) is greater than 1/0.5, the crosslinking will not be sufficient and the coating film will have resistance. Solvent properties, chemical resistance, etc. tend to decrease, while when it is less than 1/1.3, properties such as water resistance of the coating film due to unreacted isocyanate groups decrease, and it is also economically unfavorable. Furthermore, the crosslinkable copolymer resin used as the crosslinking agent includes α and β as one of the copolymer components.
-N- of monoethylenically unsaturated carboxylic acid amide
An alkoxymethylated monomer (1) is used. Component (1) is an essential component for the crosslinking reaction with the non-aqueous solvent dispersion of the vinyl ester-modified vinyl polymer. Component (1) is preferably included in the crosslinkable copolymer resin, which will be explained in more detail later, in an amount of 5 to 30% by weight, preferably 10 to 25% by weight. In the above, if the amount of component (1) is less than 5% by weight, the crosslinking reaction with the vinyl ester-modified vinyl polymer will be insufficient, resulting in a decrease in solvent resistance.
On the other hand, if it exceeds 30% by weight, gelation occurs during the production of the crosslinkable copolymer resin, which is not preferable. Specific examples of such component (1) include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, and N-isopropoxymethyl (meth)acrylamide. Acrylamide, N-n-
Butoxymethyl (meth)acrylamide, N-
sec-butoxymethyl(meth)acrylamide,
N-alkoxymethylated products of α,β-monoethylenically unsaturated carboxylic acid amides such as N-t-butoxymethyl (meth)acrylamide and N-isobutoxymethyl (meth)acrylamide; or N-methylolated products thereof, etc. can be mentioned. These may be used alone or as a mixture of two or more. As one component of the crosslinkable copolymer resin used in the present invention, it is particularly preferable to use α,β-monoethylenically unsaturated carboxylic acid (2) in a range of 0.5 to 10% by weight. Such a monomer has the effect of improving the compatibility between the crosslinkable copolymer resin and the nonaqueous solvent dispersion of the vinyl ester-modified vinyl polymer, and also promoting the crosslinking reaction. If it is less than 0.5% by weight within the above range,
Its effect becomes weaker. On the other hand, if it exceeds 10% by weight, the performance of the cured coating film will deteriorate, which is not preferable. Specific examples of such components include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. these are,
They may be used alone or as a mixture of two or more. In addition to the above raw materials for the crosslinkable copolymer resin used in the present invention, a copolymerizable α,β-monoethylenically unsaturated monomer (3) may be reacted in a proportion of 60 to 90% by weight. is preferred. Specific examples of such component (3) include methyl (meth)acrylate,
Ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec
-Butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-
Alkyl esters of acrylic acid or methacrylic acid such as ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxy Pentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-phenylethyl (meth)acrylate, polypropylene Glycol mono(meth)acrylate, glycerin mono(meth)acrylate, other N,N'-dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, cyclohexyl(meth)acrylate
acrylate, phenyl methacrylate, benzyl methacrylate, fumaric acid dialkyl esters such as dibutyl fumarate, styrene,
Vinyltoluene, α-methylstyrene, (meth)
Examples include monomers such as acrylonitrile and vinyl acetate. The above monomers may be used singly or in a suitable combination of two or more depending on the purpose and use of the coating composition. Incidentally, if a large amount of a monomer containing a hydroxyl group is used as the component (3), it is not preferable because it causes thickening and gelation during the production of the crosslinkable copolymer resin. In addition, when it is necessary to solubilize the crosslinkable copolymer resin only in an aliphatic hydrocarbon solvent,
It is preferable that 10 to 70% by weight of the α,β-monoethylenically unsaturated monomer (3) be occupied by the specific monomer (a) represented by the general formula. The crosslinkable copolymer resin is produced by a conventional solution polymerization method. The polymerization solvent used in the solution polymerization method is mainly the aliphatic hydrocarbon solvent mentioned above, and if necessary, alcohol solvents such as propyl alcohol and butyl alcohol, ethyl acetate,
Ester solvents such as butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and other solvents such as alcohol ester solvents and alcohol ether solvents are used in combination. especially,
It is preferable to use a strongly polar solvent such as an ester-based or ketone-based solvent to the extent that it does not impair the stability of the non-aqueous dispersion which is component (A) of the present invention. Further, as the polymerization initiator used for polymerizing the crosslinkable copolymer resin, the above-mentioned organic peroxide or azo compound is used. Furthermore, in order to adjust the molecular weight, the chain transfer agent described above can also be used. The weight average molecular weight of the crosslinkable copolymer resin is approximately
It is desirable that the number is in the range of 10,000 to 70,000, preferably 2,000 to 60,000. In the above range, if the weight average molecular weight is less than 10,000, the coating performance will be insufficient, while if the weight average molecular weight exceeds 70,000, the smoothness of the coated surface will be impaired. . In addition, for resin solutions with a weight average molecular weight greater than 70,000, when the solid content concentration is increased,
This is not preferred because it tends to increase the viscosity. In the present invention, the non-aqueous solvent dispersion of the vinyl ester-modified vinyl polymer (component A) and the crosslinkable copolymer resin (component B) have a solid content weight ratio of 10/90.
~Use at a ratio of 90/10. If the crosslinkable copolymer resin is less than 10% by weight in the above usage ratio, the crosslinkability of the coating film will be insufficient, and solvent resistance, coating surface smoothness, coating film hardness, etc. will tend to decrease. be.
Conversely, if the crosslinkable copolymer resin exceeds 90% by weight, the characteristics of the vinyl ester resin, namely, alkali resistance, acid resistance, salt water resistance, and salt water spray resistance are impaired. The non-aqueous dispersion type resin composition of the present invention may optionally contain a vinyl ester-modified vinyl polymer (A
It is also possible to use a known catalyst such as an acid catalyst or a dissociation catalyst in order to promote the crosslinking reaction between the component B) and the crosslinking agent (component B). Moreover, in addition to the organic solvent contained in each component, the composition of the present invention may further contain an organic solvent, if necessary, to an extent that does not impair the stability of the composition. Such an organic solvent may be the same as or different from the organic solvent contained in each component. Organic solvents that can be used include heptane, octane, mineral spirits, hydrocarbon solvents such as toluene and xylene, propyl alcohol,
These include alcohol solvents such as butanol, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and organic solvents such as alcohol esters and ether esters. There is no particular restriction on the type of solvent as long as it does not cause damage. In addition, the non-aqueous dispersion type resin composition of the present invention may contain, if necessary, an inorganic or organic coloring pigment, a metal powder pigment such as aluminum flakes, an extender pigment, and additives normally used in paints. can be used. Methods for coating the non-aqueous dispersible resin composition of the present invention include brush coating, spray coating, electrostatic coating,
Various known coating methods such as curtain flow coating, shower coating, and roll coating can be used. Furthermore, it is also possible to apply the paint by heating it (30 to 60°C), such as by hot spraying. In addition, the heat curing conditions after coating the composition of the present invention include the type of crosslinking agent and the content of crosslinkable functional groups,
Although it varies depending on the film thickness, etc., when aminoformaldehyde resin is used as a crosslinking agent, the temperature is usually 80 to 200℃,
When a blocked isocyanate compound or a crosslinkable copolymer resin is used as a crosslinking agent, a cured coating film can be obtained by heat treatment for 10 to 40 minutes at an appropriate temperature usually in the temperature range of 120 to 200°C. . The cured coating film thus obtained has the excellent alkali resistance, acid resistance, salt water resistance, and salt water spray resistance of the vinyl ester resin, and the hardness and stain resistance of the vinyl copolymer resin. It also has coating film performance with excellent secondary physical properties after testing, such as salt spray resistance, moisture resistance, and water resistance. The present invention will be explained below using specific examples.
Note that "parts" or "%" represent "parts by weight" or "% by weight." [Method for producing vinyl resin dispersion stabilizer] (1) 67 parts of mineral spirits were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, and the temperature was raised to 90°C. Then, the following monomer and initiator mixture was added dropwise over 3 hours. 40 parts of isobutyl methacrylate, 7 parts of methyl methacrylate, 8 parts of ethyl acrylate, 18 parts of styrene, 2-ethylhexyl acrylate
25 parts, 2 parts of acrylic acid, 1.2 parts of benzoyl peroxide. After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was continued for an additional 4 hours at the same reaction temperature. Thus, acid value 16.0, weight average molecular weight
35500, and a resin solution with a non-volatile content of 60.1% and a viscosity of 12.5 Stoke poise (at 20°C)
It was hot. This was designated as AT-1. (2) Put 67 parts of mineral spirits into a reaction vessel similar to that in which AT-1 was synthesized, and lower the temperature to 85%.
After raising the temperature to 0.degree. C., the following monomer and initiator mixture was added dropwise over 3 hours. 37 parts of butyl methacrylate, 40 parts of 2-ethylhexyl methacrylate, 5 parts of butyl acrylate, 18 parts of styrene, 0.7 parts of azobisisobutyronitrile. Azobisisobutyronitrile 1.2 after completion of dripping
1.5 ml was added, and the reaction temperature was raised to 90°C. Next, the reaction was carried out for an additional 4 hours, thus obtaining a resin solution with a weight average molecular weight of 40,100 and a non-volatile content of 59.8%. The viscosity is 14.7 Stokes Poise (20
℃). This was named AT-2. (3) Put 67 parts of mineral spirits into a reaction vessel similar to that in which AT-1 was synthesized, and lower the temperature to 90°C.
After raising the temperature to 0.degree. C., the following monomer and initiator mixture was added dropwise over 3 hours. 7 parts of methyl methacrylate, 30 parts of isobutyl methacrylate, 20 parts of 2-ethylhexyl acrylate, 35 parts of styrene, 7 parts of butyl acrylate, 1 part of acrylic acid, 1 part of benzoyl peroxide. After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added and the reaction was continued for another 4 hours at the same temperature.
A resin solution with an acid value of 8.0, a weight average molecular weight of 33,900, and a nonvolatile content of 59.2% was obtained. The viscosity was 11.1 Stokes poise (20°C). AT this
-3. (4) Put 67 parts of mineral spirits into a reaction vessel similar to that in which AT-1 was synthesized, and lower the temperature to 85%.
After raising the temperature to 0.degree. C., the following monomer and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 7 parts, 2-ethylhexyl acrylate 25 parts, styrene 19 parts, 2-ethylhexyl methacrylate 5 parts, isobutyl methacrylate 35 parts, ethyl acrylate 7.5 parts
parts, 1.5 parts of methacrylic acid, and 0.8 parts of benzoyl peroxide. After finishing the dripping, add 1.2 benzoyl peroxide.
1.5 ml was added, and the reaction temperature was raised to 90°C. Next, the reaction was further carried out for 4 hours to obtain a resin solution having an acid value of 9.9, a weight average molecular weight of 47,600, and a non-volatile content of 59.6%. The viscosity was 18.7 Stokes poise (20°C). This was named AT-4. (5) Put 67 parts of mineral spirits into a reaction vessel similar to that in which AT-1 was synthesized, and lower the temperature to 90°C.
After raising the temperature to 0.degree. C., the following monomer and initiator mixture was added dropwise over 3 hours. 5 parts of methyl methacrylate, 22 parts of styrene,
25 parts of 2-ethylhexyl methacrylate, 33 parts of isobutyl methacrylate, 10 parts of lauryl methacrylate, 5 parts of ethyl acrylate, 1 part of benzoyl peroxide. After the dropwise addition, 1.2 parts of benzoyl peroxide was added and the reaction was carried out at the same temperature for 4 hours to determine the acid value.
1.2, weight average molecular weight 39700 and non-volatile content 59.7
% resin solution was obtained. The viscosity was 13.2 Stoke poise (20°C). This was named AT-5. [Method for producing vinyl ester resin] (1) In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 470 parts (1 equivalent) of Epicoat #1001, 86 parts (1 equivalent) of methacrylic acid, and 0.2 parts of hydroquinone were added.
When the reaction was carried out at 145-155℃ for 1 hour and 10 minutes in an air atmosphere, the acid value reached 2.5, so cooling was started.
456 parts (45%) of styrene was added at 130°C, and the reaction was completed by cooling to room temperature. The obtained vinyl ester resin has a color number (Gardner method) of 3 and a viscosity of 5.3 poise (25°C).
It was hot. This was designated as VE-1. (2) In a reaction vessel similar to that in which VE-1 was synthesized,
AER#330, 561 parts (3 equivalents), acrylic acid 216
part (3 equivalents), hydroquinone 0.231 part, 2,
Add 3.1 parts of 4,6-tris(dimethylaminomethyl)phenol to 120 ~
When the reaction was carried out at 125°C for 2 hours and 30 minutes, the acid value reached 4.7, so cooling was started, 336 parts (30%) of styrene was added at 100°C, and the mixture was cooled to room temperature.
The reaction has ended. The obtained vinyl ester resin has 8 colors,
The viscosity was 4.2 poise (25°C). VE-
It was set as 2. [Method for producing a non-aqueous dispersion of a vinyl ester-modified vinyl polymer] (1) Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, 132 parts of mineral spirits,
After adding 133 parts of a dispersion stabilizer (AT-1) and raising the reaction temperature to 90°C, the following monomer, vinyl ester resin and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 38 parts, styrene 26.8 parts
7 parts ethyl acrylate 10 parts 2-hydroxyethyl methacrylate, 8.2 parts vinyl ester resin (VE-1), benzoyl peroxide
3.5 parts. After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same reaction temperature for 5 hours. The reaction product was a milky white dispersion with an acid value of 8.9, a hydroxyl value of 30, and a non-volatile content of 49.8%. The obtained non-aqueous dispersion type resin composition was designated as KD-1. (2) In the production of KD-1, 333 parts of dispersion stabilizer (AT-1) and mineral spirits were added.
The reaction was carried out in the same manner except that 172 copies were used. The reaction product is a milky white dispersion with an acid value
11.9, hydroxyl value 20, and nonvolatile content 49.9%. This was designated as KD-2. (3) Put 154 parts of mineral spirits and 251 parts of dispersion stabilizer (AT-5) into a reaction vessel similar to that in which KD-1 was synthesized, raise the temperature to 90°C, and then add the following monomers: The vinyl ester resin and initiator mixture were added dropwise over a period of 3 hours. Vinyl ester resin (VE-2) 18.6 parts, butyl methacrylate 12 parts, methyl methacrylate 33 parts, styrene 14.4 parts, butyl acrylate 8 parts, 2-hydroxypropyl methacrylate
13 parts, 1 part of methacrylic acid, 2 parts of benzoyl peroxide, 1.5 parts of azobisisobutyronitrile. After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same temperature for 5 hours. The reaction product was a milky white dispersion with an acid value of 5.1, a hydroxyl value of 26, and a non-volatile content of 50.0%. The obtained non-aqueous dispersion type resin composition was designated as KD-3. (4) Put 138 parts of mineral spirits and 167 parts of dispersion stabilizer (AT-2) into a reaction vessel similar to that in which KD-1 was synthesized, raise the temperature to 90°C, and then add the following monomers. , vinyl ester resin and initiator mixture were added dropwise over 3 hours. 15 parts of butyl methacrylate, 21 parts of methyl methacrylate, 18 parts of styrene, 13 parts of vinyl ester resin (Lipoxy R-806), 9 parts of 2-hydroxyethyl methacrylate, 19 parts of butyl acrylate, 4 parts of ethyl acrylate, 1 part of methacrylic acid, 2.5 parts of benzoyl peroxide,
1.0 part of azobisisobutyronitrile. After finishing the dripping, add 1.2 benzoyl peroxide.
The reaction was continued at the same reaction temperature for an additional 5 hours. The reaction product is a milky white dispersion with an acid value of 4.8.
The hydroxyl value was 24 and the nonvolatile content was 49.6%. The obtained non-aqueous dispersion type resin composition was designated as KD-4. (5) Put 142 parts of mineral spirits and 203 parts of dispersion stabilizer (AT-3) into a reaction vessel similar to that in which KD-1 was synthesized, raise the temperature to 90°C, and then add the following monomers. , vinyl ester resin and initiator mixture were added dropwise over 3 hours. 39 parts of metal methacrylate, 18.2 parts of vinyl ester resin (VE-1), 9 parts of 2-hydroxyethal methacrylate, 0.5 parts of acrylic acid, 26.3 parts of styrene, 7 parts of ethyl acrylate, and 3.5 parts of benzoyl peroxide. After finishing the dripping, add 1.2 benzoyl peroxide.
The reaction was continued for an additional 5 hours at the same reaction temperature. The reaction product is a milky white dispersion with an acid value
7.9, hydroxyl value 24, and nonvolatile content 49.7%. The obtained non-aqueous dispersion type resin composition was designated as KD-5. (6) In the production of KD-5, 338 parts of dispersion stabilizer (AT-3) and mineral spirits were added.
The reaction was carried out in the same manner except that 167 parts were used. The reaction product is a milky white dispersion with an acid value
8.2, hydroxyl value 18, and nonvolatile content 49.7%. The obtained non-aqueous dispersion type resin composition was designated as KD-6. (7) Put 138 parts of mineral spirits and 167 parts of dispersion stabilizer (AT-1) into a reaction vessel similar to that in which KD-1 was synthesized, raise the temperature to 90°C, and then add the following monomers. , vinyl ester resin and initiator mixture were added dropwise over 3 hours. 18 parts of n-butyl methacrylate, 10.2 parts of i-butyl methacrylate, methyl methacrylate
29 parts, styrene 14 parts, butyl acrylate 10 parts
parts, 2-hydroxyethyl methacrylate 10
1.5 parts of methacrylic acid, 7.3 parts of vinyl ester resin (Lipoxy H-600), 2 parts of azobisisobutyronitrile, and 1.5 parts of benzoyl peroxide. After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same temperature for 5 hours. The reaction product was a milky white dispersion with an acid value of 13.1, a hydroxyl value of 26, and a non-volatile content of 49.6%. This was named KD-7. (8) Put 153 parts of mineral spirits and 252 parts of dispersion stabilizer (AT-4) into a reaction vessel similar to that in which KD-1 was synthesized, raise the temperature to 90°C, and then add the following monomers. , vinyl ester resin and initiator mixture were added dropwise over 3 hours. Methyl methacrylate 41.5 parts, styrene 24.2 parts
8 parts of butyl acrylate, 12 parts of 2-hydroxypropyl methacrylate, 14.3 parts of vinyl ester resin (VE-2), and 3.5 parts of benzoyl peroxide. After finishing the dripping, add 1.2 benzoyl peroxide.
The reaction was continued for an additional 5 hours at the same reaction temperature. The reaction product is a milky white dispersion with an acid value
7.6, hydroxyl value 25, and nonvolatile content 49.9%. This was named KD-8. (9) In the production method (8) above, a dispersion stabilizer (AT
The reaction was carried out in the same manner except that -4) was replaced with 336 parts and the mineral spirit was replaced with 169 parts. The reaction product is a milky white dispersion with an acid value of 7.9.
It had a hydroxyl value of 22 and a non-volatile content of 50.1%. This was designated as KD-9. (10) In the above manufacturing method (4), 138 parts of mineral spirits were replaced with 135 parts, vinyl ester resin (Lipoxy R-806) was removed, 13 parts of styrene was added as a monomer component, and azobisisobutylene was added. The reaction was carried out in the same manner except that lonitrile was removed and 2.5 parts of benzoyl peroxide was replaced with 1.5 parts. The reaction product was a milky white dispersion with an acid value of 4.1, a hydroxyl value of 19, and a nonvolatile content of 50.0%. This was designated as KD−10. (11) In the above manufacturing method (3), 154 parts of mineral spirits are changed to 151 parts, and a dispersion stabilizer (AT-5) is added.
251 parts was added to a soybean oil modified alkyd resin solution with an acid value of 11, a hydroxyl value of 101, an oil length of 30%, and a non-volatile content of 60%.
To 250 parts, 2 parts of benzoyl peroxide and 1.5 parts of azobisisobutyronitrile were replaced with 1.5 parts of benzoyl peroxide, and the vinyl ester resin (VE-2) was removed and 18.6 parts of styrene was added as a monomer component. All other reactions were carried out in the same manner. The reaction product was a milky white dispersion with an acid value of 9.5, a hydroxyl value of 80, and a nonvolatile content of 49.8%. This was designated as KD-11. [Method for producing aminoformaldehyde resin solution] (1) Put 60.05 parts of isobutanol and 26.43 parts of paraformaldehyde (86%) into a reaction vessel equipped with a stirrer, thermometer, and water separator, and raise the temperature to 80°C.
After further adding 13.51 parts of melamine and 0.01 part of phthalic anhydride, the temperature was raised, and reflux dehydration was continued for 7 hours. Excess isobutanol was replaced with xylene, and the non-volatile content was 65% and the viscosity was 7.3. An amino formaldehyde resin solution (AH-1) of Stoke's drop (20°C) was obtained. (2) Put 60.37 parts of n-butanol and 26.09 parts of paraformaldehyde (86%) into a reaction vessel similar to that in which AH-1 was synthesized, raise the temperature to 80°C, and then add 13.46 parts of melamine and 0.07 parts of formic acid. was further added, the temperature was raised, and reflux dehydration was continued for 7 hours. Excess n-butanol was replaced with xylene to create an aminoformaldehyde resin solution (AH -2) was obtained. [Method for producing crosslinkable copolymer resin solution] (1) Put 66.7 parts of mineral spirits into a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and cooling tube, raise the temperature to 90°C, and then proceed as follows. of monomer and initiator mixture was added dropwise over 3 hours. 20 parts of methyl methacrylate, 33 parts of styrene,
25 parts of 2-ethylhexyl acrylate, N-n
-20 parts of butoxymethylacrylamide, 2 parts of acrylic acid, 1.5 parts of dodecylmercaptan, 2.5 parts of azobisisobutyronitrile. After completion of dripping, azobisisobutyronitrile 1.2
of the acid value was added and reacted for 4 hours at the same temperature.
18.2, weight average molecular weight 51200 and non-volatile content
A 59.9% resin solution was obtained. The viscosity was 10.1 Stokes poise (20°C). This was designated as NH-1. (2) Put 66.7 parts of mineral spirits into the same reaction vessel as the one used to synthesize NH-1, and raise the temperature to 85°C.
After raising the temperature to 100%, the following monomer and initiator mixture was added dropwise over 3 hours. 12.5 parts of methyl methacrylate, 25 parts of styrene
parts, 35 parts of 2-ethylhexyl methacrylate,
10 parts of ethyl acrylate, 15 parts of N-n-butoxymethylacrylamide, 2.5 parts of methacrylic acid,
0.2 parts of dodecyl mercaptan, 28 parts of azobisisobutyronitrile. After finishing dropping, azobisisobutyronitrile
After adding 1.2 parts and raising the reaction temperature to 90°C, the reaction was carried out for 4 hours to obtain a resin solution having an acid value of 16.3, a weight average molecular weight of 47,600, and a non-volatile content of 60.2%. The viscosity was 8.4 stoke poise (20°C). This was designated as NH-2. Example 1 Titanium dioxide was added to 23 parts of resin solution (AH-1).
81.8 parts, 6 parts of mineral spirits, and 6 parts of xylene were added, and after kneading and dispersing in a sand mill to a particle size of 10 microns or less (measured with a grind gauge; the same applies hereinafter),
15.5 parts of resin solution (AH-1), 151 parts of nonaqueous solvent dispersion (KD-1), 12 parts of mineral spirits, and 4 parts of xylene were added and mixed with stirring to obtain a uniform pigment dispersion. Further, 2 parts of para-toluenesulfonic acid (30% ethylene glycol monobutyl ether solution) were added and mixed uniformly with a stirrer. The obtained non-aqueous dispersion resin composition of the present invention was air-sprayed onto a polished mild steel plate (0.8 x 70 x 150 mm) to a film thickness of 35 to 40 microns, and allowed to cool to room temperature.
After being left for 20 minutes, each sample was heated and dried at a predetermined temperature to obtain a test piece. Table 2 shows the heating drying conditions and performance test results for the coating film. Examples 2 to 4 and Comparative Examples 1 to 2 A non-aqueous dispersion type resin composition was prepared in the same manner as in Example 1 with the formulation shown in Table 1, and was applied to the test liquid in the same manner as in Example 1. It was subjected to a performance test. The results are shown in Table-2.

【table】

【table】

[Table] Example 5 81.8 parts of titanium dioxide, 15 parts of mineral spirits, and 6 parts of xylene were added to 70 parts of non-aqueous solvent dispersion (KD-2), and the mixture was milled with a sand mill to a diameter of 40 microns or less (measured with a grind gauge; the same applies hereinafter). ), a kneaded dispersion, 49 parts of blocked isocyanate compound [trade name: Takenate B820NSU, effective NCO43%: manufactured by Takeda Pharmaceutical Co., Ltd.], 71 parts of non-aqueous solvent dispersion (KD-2)
1 part, 9 parts of mineral spirits, and 2 parts of xylene were added and mixed with stirring to obtain a uniform pigment dispersion. In addition, dibutyltin dilaurate (dissociation catalyst) 0.8
1 part and mixed uniformly with a stirrer. The obtained non-aqueous dispersion composition was polished on a mild steel plate (0.8
x 70 x 150 mm) with air spray coating to a film thickness of 35 to 40 microns, left at room temperature for 20 minutes, then heated and dried at a predetermined temperature to obtain a test piece. Table 4 shows the heating and drying conditions for the coating film and the performance test results. Examples 6 to 8 and Comparative Examples 3 to 4 Non-aqueous dispersion type resin compositions were prepared in the same manner as in Example 5 using the formulations shown in Table 3, and in the same manner as in Example 5,
A test plate was coated and subjected to a coating film performance comparison test. The results are shown in Table 4.

【table】

[Table] The test conditions for each test item are the same as in Table-2. Example 9 Titanium dioxide was added to 67 parts of resin solution (NH-2).
Add 81.8 parts, 10 parts of mineral spirits, and 10 parts of xylene, and after kneading and dispersing with a sand mill to a particle size of 10 microns or less (measured with a grind gauge; the same applies hereinafter),
16 parts of the resin solution (NH-2), 100 parts of the nonaqueous solvent dispersion (KD-3), 10 parts of mineral spirits, and 2 parts of xylene were added and mixed with stirring to obtain a uniform pigment dispersion. Furthermore, 2 parts of para-toluenesulfonic acid (30% ethylene glycol monobutyl ether solution) was added and mixed uniformly with a stirrer. The resulting non-aqueous dispersion resin composition of the present invention was air-sprayed onto a polished mild steel plate (0.8 x 70 x 150 mm) to a film thickness of 35 to 40 microns, and allowed to cool to room temperature.
After being left for 20 minutes, each sample was heated and dried at a predetermined temperature to obtain a test piece. Table 6 shows the heating drying conditions and performance test results for the coating film. Examples 10 to 13 and Comparative Examples 5 to 6 A non-aqueous dispersion type composition was prepared in the same manner as in Example 9 using the formulations shown in Table 5, and was coated on a test panel in the same manner as in Example 9. It was subjected to a comparative test. The results are shown in Table-6.

【table】

【table】

[Table] It is clear from the comparative test that the coating film obtained from the non-aqueous dispersion type resin composition of the present invention has good hardness, flexibility, impact resistance, chemical resistance, moisture resistance, water resistance, and salt water resistance. It was characterized by very good secondary density after sprayability.

Claims (1)

[Claims] 1 (A) Monomers (i) to (iii) are soluble, but the vinyl ester-modified vinyl copolymer obtained from vinyl ester, monomer (ii) and monomer (iii) is A solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing (i) an α,β-monoethylenically unsaturated monomer in an aliphatic hydrocarbon solvent in which the polymer does not dissolve…30 to 80% by weight (ii) a hydroxyalkyl ester monomer of an α,β-monoethylenically unsaturated carboxylic acid; and (iii) an α,β-monoethylenically unsaturated monomer other than the above (ii). 75 to 97% by weight of a monomer mixture consisting of; 3 to 25% by weight of a vinyl ester obtained from (a) an epoxy compound having one or more epoxy groups in the molecule; and (b) an unsaturated monocarboxylic acid. A non-aqueous dispersion type resin composition comprising a non-aqueous dispersion of a vinyl ester-modified vinyl polymer obtained by polymerizing a mixture of 70 to 20% by weight, and (B) a crosslinking agent. 2 (i) α,β-monoethylenically unsaturated monomer has the following general formula: [In the formula, R is H or CH ₃ , n is an integer of 6 to 18] α,β-monoethylenically unsaturated monomer represented by the following: 5 to 60% by weight (b) (b) above (a) The non-aqueous dispersion type resin composition according to claim 1, which is a mixture with 40 to 95% by weight of an α,β-monoethylenically unsaturated monomer other than the above. 3 The α,β-monoethylenically unsaturated monomer represented by the general formula [Formula] is
2-ethylhexyl (meth)acrylate, n-
The non-aqueous dispersion type according to claim 2, which is at least one compound selected from octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. Resin composition. 4 (ii) the hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid; and (iii)
The α,β-monoethylenically unsaturated monomer other than (ii) above is 3 to 30% by weight of the former (ii), while the latter (iii) is 70% by weight.
The non-aqueous dispersible resin composition according to claim 1, which is a monomer mixture in a proportion of ~97% by weight. (5) The vinyl ester is an ester in a ratio of 0.6 to 1.2 mole of carboxyl group of (b) unsaturated monocarboxylic acid per mole of epoxy group of (a) epoxy compound having one or more epoxy groups in the molecule. The non-aqueous dispersible resin composition according to claim 1, which is a reaction product obtained by a chemical reaction. 6 (B) The crosslinking agent is an aminoformaldehyde resin, and the solid ratio of (A)/(B) is 50 to 90/50 to 10.
(weight ratio), the non-aqueous dispersion type resin composition according to claim 1. 7. The crosslinking agent according to claim 1, wherein the crosslinking agent (B) is a blocked isocyanate compound, and the ratio of hydroxyl group in component (A)/isocyanate group in component (B) is 1/1.3 to 1/0.5. Non-aqueous dispersion type resin composition. 8 (B) The crosslinking agent is (1) an N-alkoxymethylated monomer of an α,β-monoethylenically unsaturated carboxylic acid amide, and (2) an α,β-monoethylenic monomer other than the above (1). It is a crosslinkable copolymer resin solution obtained from an unsaturated monomer, and the solid ratio of (A)/(B) is 10 to 90/90 to
10 (weight ratio), the non-aqueous dispersion type resin composition according to claim 1. 9 The crosslinkable copolymer resin is (1) N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide...5~
30% by weight, (2) α,β-monoethylenically unsaturated carboxylic acid…
...0.5 to 10% by weight, and (3) α,β-monoethylenically unsaturated monomer other than the above (1) and (2) ...60 to 90% by weight. A non-aqueous dispersion type resin composition according to claim 8.