JPS632283B2 - - 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 non-aqueous dispersion type resin composition comprising a non-aqueous solvent dispersion of a vinyl ester-modified vinyl polymer. In recent years, demands for resource saving and pollution-free technology have been rapidly increasing in the paint field as well. In particular, Heinrid-type paints, which are resource-saving paints with low solvent content and high solid content, have the advantage that conventional paint manufacturing methods or painting equipment can be used as is.
It seems to be used suitably. In addition, considering the recent efforts to regulate the use of solvents due to air pollution issues, it seems that ordinary high-solids paints that use large amounts of aromatic and ester solvents are not industrially desirable. . Furthermore, from the viewpoints of regulations on the use of solvents, which have been further strengthened in recent years, non-pollution in a broad sense, and resource conservation, non-aqueous dispersion paints using aliphatic hydrocarbon solvents as the main solvent have been proposed. 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, In general, coating films obtained from thermosetting non-aqueous dispersion paints using polybutadiene/acrylic resins or the like as a color vehicle do not always have sufficient physical properties. For example, a flexible coating film may have insufficient hardness, and conversely, a hard coating film may have insufficient flexibility, and so on. I couldn't find it. In addition, in terms of salt spray resistance, moisture resistance, water resistance, and secondary physical properties after each test,
It was not always possible to obtain sufficient performance. In addition, a non-aqueous dispersion type resin composition using the above combination as a color vehicle also contains a dispersion stabilizer component (solvation component).
Due to the difference in polarity between the dispersion particle component (produced polymer) and the dispersion particle component (produced polymer), the compatibility between the two decreases, and therefore, the coating film obtained from the composition tends to lack transparency and have reduced gloss, luster, etc. have. For this reason, when a non-aqueous dispersion type resin composition containing the above-mentioned combination as a color vehicle is used for a coating, it is considered to be unsuitable for exterior applications, and has been mainly used for interior applications. In order to obtain an excellent cured coating film, the color vehicle may contain a curing agent such as an aminoformaldehyde resin, a blocked isocyanate compound, an epoxy resin, or a methoxymethylated acrylamide resin in order to react with the functional groups in the vehicle. Used together. These are usually added when making paints, but during long-term storage, the functional groups in the non-aqueous dispersion and the functional groups in the curing agent gradually react, resulting in thickening of the composition. , precipitation due to aggregation was often observed. The inventors of the present invention have made extensive studies to improve the various drawbacks of the known techniques, and have found that by incorporating a dispersion stabilizer and a specific functional group into the dispersed particles, the present inventors can achieve transparency and an excellent finished appearance. We discovered that it is possible to obtain a cured coating film with excellent chemical resistance.
This led to the present invention. That is, in the present invention, monomers (i) to (iv) are dissolved, but vinyl ester,
The vinyl ester-modified vinyl copolymer obtained from monomer (iii) and monomer (iv) is treated with (i) α,β-monoethylenically unsaturated carboxylic acid in an insoluble aliphatic hydrocarbon solvent. (ii) an N-alkoxymethylated amide monomer;
(iii) α,β-monoethylenically unsaturated monomers other than (i) in the presence of 30 to 80% by weight of a solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing α,β-monoethylenically unsaturated monomers. 75 to 97% by weight of a monomer mixture consisting of a hydroxyalkyl ester monomer of an ethylenically unsaturated carboxylic acid and (iv) an α,β-monoethylenically unsaturated monomer other than the above (iii), Obtained by polymerizing 70-20% by weight of a mixture of 3-25% 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. The present invention relates to a non-aqueous dispersion type resin composition of a vinyl ester-modified vinyl polymer. The solvent used in the present invention, that is, the above-mentioned "aliphatic hydrocarbon solvent" has the following characteristics. In other words, α,β-monoethylenic monomers (i), (ii), (iii) and (iv), which will be described later, dissolve, but monomer (i)
ii),
The "vinyl ester-modified vinyl copolymer" obtained from (iv) and vinyl ester does not dissolve. Specifically, for example, mixtures containing aliphatic hydrocarbons such as hexane, hepetane, octane, cyclohexane, cycloheptane, methylcyclohexane, ethylcyclohexane, and dimethylcyclohexane, as well as mineral spirits, aliphatic naphtha, etc. as main components are used. can be lost. Next, generally speaking, the above-mentioned "solvent-soluble vinyl resin dispersion stabilizer" used as the dispersion stabilizer of the present invention can be said to contain (i) α, β-
an N-alkoxymethylated monomer of monoethylenically unsaturated carboxylic acid amide, and (ii) α other than the above (i),
It is obtained by polymerizing β-monoethylenically unsaturated monomer. In addition, in this specification, the term "solvent soluble" means
It refers to the property of being dissolved or partially dissolved in the aliphatic hydrocarbon solvent. The N-alkoxymethylated monomer of (i) α,β-monoethylenically unsaturated carboxylic acid amide is preferably 5 to 30% by weight in the monomer mixture [(i)+(ii)]. is preferably reacted in a proportion of 8 to 25% by weight. If the content of this component is less than 5% by weight within the above range, it will be difficult to obtain a transparent coating film, and
When the composition of the present invention is used as a thermosetting composition, the crosslinking reaction of the α,β-monoethylenically unsaturated carboxylic acid with the hydroxyalkyl ester component in the dispersed particle component becomes insufficient, resulting in poor solvent resistance of the coating film. tends to decrease. On the other hand, if it exceeds 30% by weight, it is not preferable because gelation occurs in the polymerization reaction step during the production of dispersed particles. Specific examples of component (i) include 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-
Examples include N-alkoxymethylated products of α,β-monoethylenically unsaturated carboxylic acid amides such as isobutoxymethyl (meth)acrylamide; or N-methylolated products thereof. These may be used alone or as a mixture of two or more. When the composition of the present invention is used as a thermosetting composition, the component (i) is a combination of the hydroxyalkyl component (iii) of the α,β-monoethylenically unsaturated carboxylic acid used as a component of the dispersed particles. In addition to being necessary for the crosslinking reaction, it is essential that the component (iii) be present in the composition at the same time in order to make the cured coating film obtained from the composition of the present invention transparent. . In the present invention, the α,β-monoethylenically unsaturated monomer (ii) other than the above (i) may be obtained by dissolving or partially dissolving a vinyl resin as a dispersion stabilizer in the aliphatic hydrocarbon solvent. Any monomer can be used as long as it can be dissolved. 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. This monomer is particularly preferred because it dissolves or partially dissolves the dispersion stabilizer in the solvent. A monomer having such a specific general formula is
α,β-monoethylenically unsaturated monomer mixture [(i)
+(ii)], it is preferably used in a proportion of 5 to 60% by weight. 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,
Undesirable. On the other hand, if it exceeds the upper limit of 60% by weight, it is similarly undesirable because coating film properties such as hardness and impact resistance tend to deteriorate. A specific example is 2-ethylhexyl (meth)
Esters such as acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are used. these are,
They can be used singly or as a mixture of two or more. The α,β-monoethylenically unsaturated monomer mixture [(i)+(ii)] is the N-alkoxymethylated monomer of the α,β-monoethylenically unsaturated carboxylic acid amide. (Component (a)) and other monomers other than the monomer shown by the above general formula (component (b))
(iii) may be used in the monomer mixture [(i)+(ii)] in an amount of 10 to 90% by weight. Specific examples of such monomer (c) 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
Acrylate, isobutyl (meth)acrylate, N,N'-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate,
Dialkyl esters of fumaric acid such as cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, and dibutyl fumarate, monomers such as styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate. I get punched. These may be used alone or as a mixture of two or more. If a hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid containing a hydroxyl group is used as the other monomer [component (iii)], α,β-monoethylenically unsaturated carboxylic acid amide In the presence of N-alkoxymethylated monomer,
As the dispersion stabilizer becomes difficult to dissolve in the solvent,
This is undesirable because it tends to increase the viscosity, and therefore it is preferable to avoid using hydroxyalkyl monomers of α,β-monoethylenically unsaturated carboxylic acids as component (iii). The solvent-soluble vinyl resin (hereinafter abbreviated as "vinyl resin" if necessary) used as the dispersion stabilizer of the present invention is produced by normal solution polymerization of the components (i) and (ii). . For example, a method in which the remaining monomer (mixture) and a polymerization initiator are dropped into a mixture of a part of the monomer (mixture) and a polymerization solvent, and then polymerized; A method in which a polymerization initiator is added dropwise and polymerized is applicable. 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-butyl peroxybenzoate, t-
- Organic peroxides such as butyl peroxyoctoate and lauroyl peroxide, or azo compounds such as azobisisobutyronitrile are 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 the vinyl resin as a dispersion stabilizer dissolved (or partially dissolved) in the aliphatic hydrocarbon obtained as described above, (iii)
α,β-monoethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer, (iv) other α,β-monoethylenically unsaturated monomers other than the above (iii),
and a vinyl ester component to obtain a non-aqueous dispersion of a vinyl ester-modified vinyl polymer. The non-aqueous dispersion of the vinyl ester-modified vinyl polymer makes the formed coating film transparent.
And when heating during coating film formation, the N-alkoxymethylated monomer (i) of α,β-monoethylenically unsaturated carboxylic acid amide contained in the dispersion stabilizer and In order to carry out a crosslinking reaction (self-crosslinking reaction), it is necessary to contain a hydroxyl group in the molecule. Therefore, the monomer mixture [(iii)
+(iv)] is a hydroxyalkyl ester monomer (iii) of an α,β-monoethylenically unsaturated carboxylic acid. By the way, the monomer (iii) has strong polarity. Therefore, copolymers containing this monomer as one component are difficult to dissolve in aliphatic hydrocarbon solvents, and are therefore suitable for forming dispersed particles. In addition, such a monomer is added in the α,β-monoethylenically unsaturated monomer mixture [(iii)+(iv)] so that the hydroxyl value of the dispersed particle component is approximately 8 to 140. 3～
Use in a range of 30% by weight. In the weight range in the above mixture, said monomer (iii)
However, if it is less than 3% by weight, it will be difficult to obtain a transparent coating film, and the crosslinking density will decrease during the reaction process with the crosslinkable monomer (i) when heating the coating film, resulting in a coating film that is difficult to obtain. This is not preferable because it lowers the solvent resistance. On the other hand, if it is used in an amount exceeding 30% by weight, the non-aqueous dispersion of the present invention becomes highly viscous, which impairs workability, which is not preferable. In addition, when the composition of the present invention is used as a thermosetting composition, the crosslinking density becomes too high, which tends to reduce the flexibility, water resistance, etc. of the coating film, which is also not preferred. Specific examples of this type of monomer (iii) 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. In addition, in the presence of a dispersion stabilizer, the monomer (iv) other than the hydroxyalkyl ester of the α,β-monoethylenically unsaturated carboxylic acid used for copolymerization is a monomer mixture [( iii)＋(iv)〕70～97
Use within the range of % by weight. Specific examples of the monomer (iv) 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
- Alkyl esters of acrylic acid or methacrylic acid such as hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate. Class; Other N,
Dialkyl esters of fumaric acid such as N'-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, dibutyl fumarate, styrene, vinyltoluene, α-methyl styrene,
(Meth)acrylonitrile, vinyl acetate, etc. are exposed. 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 (iv), 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, "vinyl ester-modified vinyl resin polymer" used as a dispersed particle component
is the vinyl ester, the monomer (iii) and the monomer
(iv), thus imparting to the resulting coating film 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 (iii) and (iv) 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.
#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., Ciba 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) A product obtained by reacting a phenol with ethylene oxide or propylene oxide, etc., and epichlorohydrin or methylepichlorohydrin, such as a product name manufactured by Asahi Denka Co., Ltd.
You can punch EP #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
It reacts by heating in the range of 180℃. 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 esterification reaction catalyst used is
It is sufficient to use about 0.001 to 5.0 parts by weight per 100 parts by weight, but good results are obtained with about 0.005 to 1.0 parts by weight. Furthermore, when a solvent or a polymerizable monomer is added 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 (iii) and part of monomer (iv) are used as a solvent for vinyl ester production as described above, but such polymerizable monomers are naturally used in the vinyl ester-modified vinyl polymer. Since it is a raw material component, the amount used is such that the total amount of the polymerizable monomer and other monomers (iii) and monomer (iv) is 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, PS-6120S
etc., product name Prominate P- manufactured by Takeda Pharmaceutical Co., Ltd.
310, P-311, etc., Dow Chemical Co., Ltd.'s product name Delakane 411, 411C, 470, 510, etc., Sumitomo Chemical Co., Ltd.'s product name Smearp EVR-911, etc., and these are one type or It can be used as a mixture of two or more types. 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 (iii) and (iv). 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 value, 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 30 to 80% by weight of a vinyl resin [copolymer of monomers (i) and (ii)] as a dispersion stabilizer. a mixture consisting of monomer (iii), monomer (iv) and vinyl ester in the presence of 70 to 20
It is obtained by polymerizing % 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. 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. In addition, in the non-aqueous dispersion type resin composition of the present invention, a known catalyst for promoting the crosslinking reaction (self-crosslinking) of the vinyl ester-modified vinyl polymer can be used in combination, if necessary. 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 hydrocarbon solvents such as heptane, octane, mineral spirits, toluene and xylene, alcohol solvents such as propyl alcohol and butanol, ethyl acetate,
These include ester solvents such as butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and organic solvents such as alcohol esters and ether esters.The type of solvent is particularly limited as long as it does not impair the stability of the non-aqueous dispersion. There isn't. In addition, to the non-aqueous dispersion type resin composition of the present invention, if necessary, inorganic or organic coloring pigments, metal powder pigments such as aluminum flakes, extender pigments, and additives normally used in paints can be added. and 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 composition of the present invention can form a film by simply evaporating the solvent after coating (so-called drying at room temperature).
Good coating performance can be obtained, but in order to obtain a coating film with even higher performance, it is preferable to heat cure. Heat curing conditions vary depending on the content of crosslinkable functional groups in the composition, film thickness, etc., but are usually cured at an appropriate temperature in the range of 60 to 200°C for 10
A cured coating film can be obtained by heat treatment for ~40 minutes. 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 moisture resistance and water resistance. The present invention will be explained below using specific examples.
In addition, "part" or "%" represents "weight part" or "weight %." [Method for manufacturing vinyl resin dispersion stabilizer] (1) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, add 100 ml of mineral spirit.
and the temperature was raised to 90°C. Then, the following monomer and initiator mixture was added dropwise over 3 hours. 17 parts of isobutyl methacrylate, 35 parts of butyl methacrylate, 5 parts of methyl methacrylate,
5 parts of ethyl acrylate, 8.5 parts of styrene, 2
-19 parts of ethylhexyl acrylate, Nn-
8 parts butoxymethylacrylamide, 2.5 parts methacrylic acid, 2 parts benzoyl peroxide. After dropping, add benzoyl peroxide 1,2
The reaction was continued for an additional 4 hours at the same reaction temperature. Thus, acid value 18.0, weight average molecular weight
55700 and a non-volatile content of 50.0%, the viscosity was 15.9 Stokes/20°C. This was designated as VA-1. (2) Put 100 parts of mineral spirits into the same reaction vessel as the one used to synthesize VA-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. 48 parts of butyl methacrylate, 8 parts of t-butyl methacrylate, 22 parts of 2-ethylhexyl methacrylate, 3 parts of butyl acrylate, N-n
-19 parts of butoxymethylacrylamide, 0.2 parts of dodecyl mercaptan, 2.5 parts of benzoyl peroxide, 0.5 parts of azobisisobutyronitrile
Department. 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 carried out for an additional 4 hours, thus giving an acid value of 1.8.
A resin solution with a weight average molecular weight of 65,300 and a non-volatile content of 49.7% was obtained. The viscosity was 16.7 Stokes/20°C. This was designated as VA-2. (3) Put 100 parts of mineral spirits into a reaction vessel similar to that in which VA-1 was synthesized, and lower the temperature.
After raising the temperature to 90°C, the following monomer and initiator mixture was added dropwise over 3 hours. 4 parts of methyl methacrylate, 20 parts of isobutyl methacrylate, 20 parts of 2-ethylhexyl methacrylate, 15 parts of styrene, 30 parts of butyl methacrylate, 10 parts of N-n-butoxymethylacrylamide, 1 part of methacrylic acid, 2 parts of benzoyl peroxide, azobisiso 1 part butyronitrile. 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 54,100, and a nonvolatile content of 50.0% was obtained. The viscosity was 13.5 Stokes/20°C. VA−
It was set as 3. (4) Put 100 parts of mineral spirits into a reaction vessel similar to that in which VA-1 was synthesized, and lower the temperature.
After raising the temperature to 85°C, the following monomer and initiator mixture was added dropwise over 3 hours. 10 parts of methyl methacrylate, 15 parts of 2-ethylhexyl acrylate, 10 parts of styrene, 15 parts of 2-ethylhexyl methacrylate, 33.5 parts of isobutyl methacrylate, 15 parts of N-t-butoxymethylacrylamide, 1.5 parts of acrylic acid, 2 parts of benzoyl peroxide, azo 1 part bisisobutyronitrile. After finishing the dripping, add 1.2 benzoyl peroxide.
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 13.3, a weight average molecular weight of 67,700, and a non-volatile content of 49.8%. The viscosity was 18.4 Stokes/20°C. This was designated as VA-4. (5) In the production of VA-3, except for N-n-butoxymethylacrylamide, 100 parts of mineral spirit was changed to 90 parts, 2 parts of benzoyl peroxide and 1 part of azobisisobutyronitrile were added.
The reaction was carried out in the same manner except that 1.2 parts of benzoyl peroxide was used, and the acid value was 7.9.
Weight average molecular weight 36300 and non-volatile content 49.9%
A resin solution was obtained. The viscosity was 10.6 Stokes/20°C. This was designated as VA-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 had a color number (Gardner method) of 3 and a viscosity of 5.3 poise/25°C. 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 parts (3 equivalents), hydroquinone 0.231 parts, 2,4,
Add 3.1 parts of 6-tris(dimethylaminomethyl)phenol and heat at 120 to 125℃ in an air atmosphere.
After 2 hours and 30 minutes of reaction, the acid value was 4.7.
So I started cooling and heated the styrene to 100℃.
336 parts (30%) was added and cooled to room temperature to complete the reaction. The obtained vinyl ester resin has 8 colors,
The viscosity was 4.2 poise/25°C. This is VE-2
And so. Example 1 100 parts of mineral spirits and 300 parts of dispersion stabilizer (VA-1) were placed in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and cooling tube, and the temperature was raised to 95°C.
After raising the temperature to 100%, the following monomer, vinyl ester resin, and initiator mixture was added dropwise over 3 hours. 38 parts of methyl methacrylate, 26.8 parts of styrene,
7 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, vinyl ester resin (VE
-1) 18.2 parts, 3.5 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 reaction temperature for 5 hours.
The reaction product is a milky white dispersion with an acid value of 11.3 and a hydroxyl value.
22, and the non-volatile content was 50.1%. The obtained non-aqueous dispersion type resin composition was designated as VD-1. Example 2 In a reaction vessel similar to that in which VD-1 was synthesized,
99 parts of mineral spirits, dispersion stabilizer (VA-
2) After adding 201 parts and raising the temperature to 95°C, the following monomer, vinyl ester resin and initiator mixture was added dropwise over 3 hours. Vinyl ester resin (VE-2) 18.6 parts, butyl methacrylate 12 parts, methyl methacrylate 33 parts
parts, 14.4 parts of styrene, 8 parts of butyl acrylate,
13 parts of 2-hydroxypropyl methacrylate, 1 part of methacrylic acid, 2 parts of benzoyl peroxide
parts, 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 4.5, a hydroxyl value of 33, and a non-volatile content of 50.3%. The obtained non-aqueous dispersion type resin composition was designated as VD-2. Example 3 In a reaction vessel similar to that in which VD-1 was synthesized,
100 parts of mineral spirits, dispersion stabilizer (VA-
3) After adding 260 parts and raising the temperature to 95°C, the following monomer, vinyl ester resin and initiator mixture was added dropwise over 3 hours. Butyl methacrylate 15 parts, methyl methacrylate 21 parts, styrene 18 parts, vinyl ester resin (Lipoxy R-806) 13 parts, 2-hydroxyethyl methacrylate 9 parts, butyl acrylate 19 parts
parts, 4 parts ethyl acrylate, 1 part methacrylic acid
parts, 2.5 parts of benzoyl peroxide, and 1.0 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 reaction temperature for 5 hours. The reaction product was a milky white dispersion with an acid value of 7.7, a hydroxyl value of 20, and a nonvolatile content of 49.9%. The obtained non-aqueous dispersion type resin composition was designated as VD-3. Example 4 The reaction was carried out in the same manner as in the production of VD-3 except that 400 parts of the dispersion stabilizer (VA-3) was used. The reaction product is a milky white dispersion with an acid value of 7.6, a hydroxyl value of 16, and a non-volatile content of 49.7.
It was %. The obtained non-aqueous dispersion type resin composition was designated as VD-4. Example 5 In a reaction vessel similar to that in which VD-1 was synthesized,
99 parts of mineral spirits, dispersion stabilizer (VA-
4) After adding 341 parts and raising the temperature to 95°C, the following monomer, vinyl ester resin and initiator mixture was added dropwise over 3 hours. 29 parts of methyl methacrylate, 10.2 parts of isobutyl methacrylate, 7.3 parts of vinyl ester resin (Lipoxy H-600), 10 parts of 2-hydroxyethyl methacrylate, 1.5 parts of methacrylic acid, 18 parts of butyl methacrylate, 14 parts of styrene, 10 parts of butyl acrylate, 3.5 parts 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 reaction temperature for 5 hours. The reaction product is a milky white dispersion with an acid value of 13.5.
The hydroxyl value was 20 and the nonvolatile content was 50.0%. The obtained non-aqueous dispersion type resin composition was designated as VD-5. Comparative Example 1 In Example 3, the vinyl ester resin (Lipoxy R-806) was removed, the dispersion stabilizer (VA-3) was replaced with (VA-5), and 7 parts of methyl methacrylate and styrene were used as monomer components. 6
The reaction was carried out in the same manner except that 1.5% was added. The reaction product was a milky white dispersion with an acid value of 7.4, a hydroxyl value of 17, and a nonvolatile content of 49.6%. The obtained non-aqueous dispersion type resin composition was designated as VD-6. Comparative Example 2 In Example 1, mineral spirits
100 parts was replaced with 150 parts, and 300 parts of the dispersion stabilizer (VA-1) was replaced with 250 parts of a soybean oil-modified alkyd resin solution having an acid value of 11, a hydroxyl value of 101, an oil length of 30%, and a non-volatile content of 60%. Then, the following monomer and initiator mixture was added dropwise and reacted in the same manner. 38 parts of methyl methacrylate, 7 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 35 parts of styrene,
1 part benzoyl peroxide. The reaction product was a milky white dispersion with an acid value of 7.7, a hydroxyl value of 79, and a non-volatile content of 49.7%. The obtained non-aqueous dispersion type resin composition was designated as VD-7. The present invention (VD-1 to VD-1) obtained as described above
5) and the non-aqueous dispersion resin compositions of Comparative Examples (VD-6 to 7) were air-sprayed onto a polished mild steel plate (0.8 x 70 x 150 mm) to a film thickness of 30 to 35 microns, and the mixture was heated at room temperature. After leaving it for 20 minutes, it was heated and dried at 160°C for 20 minutes. The results of the coating film performance comparison test of the obtained test pieces were
Shown in the table.

【table】

【table】

[Table] It is clear from the above comparative test results that the coating film obtained from the non-aqueous dispersion type resin composition of the present invention has excellent transparency, no yellowing, and good hardness, flexibility, impact resistance, and resistance. The secondary adhesion after chemical resistance, moisture resistance, water resistance, and salt spray resistance tests was very good, and the storage stability of the composition was also very good.

Claims (1)

[Claims] 1 Monomers (i) to (iv) are soluble, but a vinyl ester-modified vinyl copolymer obtained from vinyl ester, monomer (iii), and monomer (iv) is In an insoluble aliphatic hydrocarbon solvent, (i) an N-alkoxymethylated monomer of an α,β-monoethylenically unsaturated carboxylic acid amide; and (ii) the above-mentioned
Solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing with α,β-monoethylenically unsaturated monomers other than (i)...In the presence of 30 to 80% by weight, (iii)α,β - 75 to 97% by weight of a monomer mixture consisting of a hydroxyalkyl ester monomer of a monoethylenically unsaturated carboxylic acid and (iv) an α,β-monoethylenically unsaturated monomer other than the above (iii); , a mixture 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 of a vinyl ester-modified vinyl polymer obtained by polymerizing 70 to 20% by weight. 2. The solvent-soluble vinyl resin dispersion stabilizer contains (a) N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide...5 to 30% by weight, (b) 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, and (c) the above (a) and an α,β-monoethylenically unsaturated monomer other than (b) ……10 to 90% by weight, the non-aqueous dispersion type resin composition according to claim 1, which is a copolymer obtained from thing. 3 The α,β-monoethylenically unsaturated monomer represented by the general formula [Formula] is:
2-ethylhexyl (meth)acrylate, n-
The non-aqueous dispersion resin 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. Composition. 4 (iii) the hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid; and (iv)
Regarding α,β-monoethylenically unsaturated monomers other than (iii) above, the former (iii) is 3 to 30% by weight, while the latter (iv) 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 subjected to an esterification reaction at a ratio of (b) 0.6 to 1.2 moles of carboxyl groups of an unsaturated monocarboxylic acid to 1 mole of epoxy groups of an epoxy compound having one or more epoxy groups in the molecule. The non-aqueous dispersion type resin composition according to claim 1, which is a reaction product obtained at least.