JP2716478B2 - Method for producing polymer crosslinked fine particle dispersion - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a stable non-aqueous dispersion of a vinyl polymer, and more specifically to a fatty acid-modified amount containing 25% by weight containing an aromatic ring in the molecule. % Or less of an oil-free alkyd resin or an alkyd resin containing no fatty acid at all (hereinafter referred to as an oil-free alkyd resin) as a dispersion stabilizer, and a radical polymerizable unsaturated monomer in an organic solution in the presence of the resin. The present invention relates to a method for producing a stable non-aqueous resin solution of polymer particles insoluble in the organic liquid by polymerizing the polymer.

(Problems Solved by Conventional Techniques and Inventions) Alkyd resins are widely used today as coating resins for processing steel plates, building materials, industrial machines, and the like because of their excellent workability.

However, an alkyd resin having a fatty acid modification amount of more than 25% by weight is inferior in abrasion resistance, erosion resistance, stain resistance, and the like because a fatty acid and an oil component work as a plasticizer.
It does not have sufficient performance for the application. In order to remedy this drawback, an alkyd resin having a resin acid modification amount of 25% by weight or less has been used or an attempt has been made to increase the hardness. However, on the other hand, it has become brittle and has reduced workability. That is, hitherto, it has not been possible to simultaneously satisfy both processability and hardness in an alkyd resin. Further, it is conceivable that both the workability and the hardness are satisfied by increasing the molecular weight, but in that case, the coating workability is impaired.

In order to improve processability, a resin of a dispersion system, that is, a resin solution in which particles of an vinyl unsaturated monomer are dispersed in an organic liquid using an alkyd resin as a dispersion stabilizer (hereinafter, such a non-aqueous dispersion resin) The liquid is abbreviated as NAD), but the alkyd resin used as a conventional NAD dispersion stabilizer usually has a fatty acid modification amount of more than 25% by weight. Disadvantage remains as a problem. Although NAD may be used alone, it is generally used by blending with another alkyd resin. However, the alkyd resin has poor oil compatibility unless the oil length is about the same as that of the alkyd resin.
The above-mentioned NAD using an alkyd resin as a dispersion stabilizer can be blended only with an alkyd resin having a fatty acid modification amount of 25% by weight or more. Therefore, there is a problem that a conventional NAD or its blend with an alkyd resin cannot provide sufficient hardness.

(Means for Solving the Problems) The present inventors have made intensive efforts to solve the above-described technical problems, and as a result, can be blended with an alkyd resin having a fatty acid modification amount of 25% by weight or less. NAD, that is, an alkyd resin having a fatty acid modification amount of 25% by weight or less is used as a dispersion stabilizer, and a resin liquid in which gel particles of a polymer of a vinyl-based unsaturated monomer are stably dispersed to achieve the above object. They have found what can be achieved and have completed the present invention.

Thus, according to the present invention, in an organic liquid containing at least 30% by weight of an aromatic solvent, it has at least 0.1 polymerizable double bonds in the molecule on average and the fatty acid modification amount is 25% by weight. In the presence of the following alkyd resins, each contains at least 0.5% by weight of at least two kinds of vinyl monomers each having a complementary functional group capable of reacting and binding to each other or a polyvinyl monomer. There is provided a method for producing a polymer crosslinked fine particle dispersion insoluble in the organic liquid, characterized by copolymerizing a radical polymerizable unsaturated monomer.

The continuous phase of a coating film formed from a paint containing a non-aqueous dispersible resin liquid as a main component obtained by the method of the present invention is mainly composed of an alkyd resin having a fatty acid modification amount of 25% by weight or less as a dispersion stabilizer or an oil-free alkyd. Made of resin. Therefore, the hardness of the coating film is improved by including an aromatic dicarboxylic acid or tricarboxylic acid as an acid component thereof in a certain amount or more, and the action of the polymer gel particles of the non-aqueous dispersible resin liquid causes processing and modification. Can reduce the internal stress of the coating film generated when the force is applied, and thus a coating film satisfying both the required hardness and workability can be obtained. Further, the polymer portion of the dispersion provided by the present invention can prevent the particles from swelling and dissolving even when an aromatic solvent having high solubility for gel particles is used. In addition, conventional alkyd resins and oil-free alkyd resins, which are intended to improve the hardness of the coating film, because of high coating film viscosity, there is a drawback such as reduced coating workability, but the method of the present invention When the non-dispersible resin liquid produced by the above method is used, the coating viscosity is low, so that the coating workability is excellent.

 Hereinafter, the present invention will be described in more detail.

Important features of the present invention, as a dispersion stabilizer of the polymer crosslinked fine particle dispersion, at least 0.1 in the molecule on average,
Alkyd resin having preferably 0.3 to 5.0, more preferably 1.0 to 3.0 polymerizable double bonds and a fatty acid modification amount of 25% by weight or less, preferably 20% by weight or less, more preferably 17% by weight or less (Short oily alkyd resin or oil-free alkyd resin).

Such an alkyd resin uses an aromatic di- or tricarboxylic acid as an essential acid component, and can be used to convert other polybasic acids and polyhydric alcohols, and if necessary, a saturated or unsaturated fatty acid into a known alkyd. In the same manner as in the method for producing the resin, the resin can be produced, for example, by subjecting to a condensation reaction at a temperature of about 150 to about 250 ° C. for about 3 to about 10 hours in the presence of an esterification catalyst.

As the aromatic di- or tricarboxylic acid used as an essential component in the production of the alkyd resin, for example, phthalic acid or an anhydride thereof, isophthalic acid, terephthalic acid, dimethyl terephthalic acid, trimetritic acid,
Examples include trimesic acid and 2-methyltrimellitic acid, which can be used alone or in combination of two or more.

These aromatic di- or tricarboxylic acids are components useful for improving the hardness, stain resistance, weather resistance, erosion resistance, and chipping resistance of the coating film. At least 10% by weight, preferably 20-70% by weight, more preferably 30-60% by weight
It can be used in amounts in the range of weight percent.

In addition, as other polybasic acids that can be used in combination, polybasic acids that are commonly used as an acid component in the production of an alkyd resin can be used in the same manner, for example, adipic acid, maleic acid or its anhydride, azelaic acid, succinic acid Acids or anhydrides thereof, aliphatic dicarboxylic acids such as fumaric acid and sebacic acid; alicyclic polybasic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene hexahydrophthalic acid and hexahydroterephthalic acid; pyromellitic acid Or anhydrides thereof, and the like, and these can be used alone or in combination of two or more.

On the other hand, examples of the polyhydric alcohol that can be used include those having a valency of 3 or more, such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, and pentaerythritol. For example, ethynylene glycol, propylene glycol, 1,4-butanediol, 1,2-pentanediol, 3-methyl-1,2-butanediol, trimethylene glycol, 1,5-pentanediol, 2,4- Pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 1,4-pentanediol, 3-methyl-4,5-pentanediol, 1,4-hexanediol, 2,5-hexanediol, 1, 5-hexanediol, 1,6-hexanediol, and the like.
These polyhydric alcohols can be used alone or in combination of two or more. Further, monoepoxy compounds such as Cardiura E (manufactured by Ciel Chemical Co., Ltd.) can also be used as the dihydric alcohol.

Saturated or unsaturated fatty acids that can be used in the production of the short-oil alkyd resin include saturated or unsaturated fatty acids having 6 to 18 carbon atoms or glycerides thereof, benzoic acid, methylbenzoic acid, pt -Butylbenzoic acid and the like. Also, various natural oils or fatty acids thereof, for example, coconut oil, cottonseed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil and the like, or derived therefrom Fatty acids used can also be used. When a monoepoxy compound such as Cardiura E is used as a dihydric alcohol, the monoepoxy compound contains 6 carbon atoms.
If 〜18 fatty acid residues are included, that fatty acid is also considered to be one of the saturated or unsaturated fatty acids referred to herein.

These fatty acids may be used in an amount such that the fatty acid modification amount of the obtained short oil alkyd resin is within the above-mentioned range, that is, 25% by weight or less, preferably 20% by weight or less, and more preferably 17% by weight or less. it can.

When producing an oil-free alkyd resin, of course, it is not necessary to use such fatty acids.

The condensation reaction between the acid component and the alcohol component is usually carried out in the presence of an esterification catalyst. As such a catalyst, known acid catalysts, base catalysts and metal catalysts can be used. Examples of the acid catalyst include sulfuric acid, phosphoric acid,
Examples include paratoluenesulfonic acid, trichloroacetic acid, trifluoromethanesulfonic acid, monobutyl phosphate, dibutyl phosphate, and boron trifluoride.Examples of the base catalyst include monoethanolamine, diethanolamine, and tributylamine. And, as the metal catalyst, for example, dibutyltin oxide, monobutyltin hydroxide, tetrabutylzirconate, tetrabutyltitanate, stannous chloride, zinc oleate,
Examples include tin oleate and zinc acetate. Of these catalysts, monobutyltin hydroxide is particularly preferred because of its high degree of reaction promotion and little adverse effect when incorporated into coatings. Also, paratoluenesulfonic acid can be a particularly preferable reaction catalyst because it has a curing catalyst function when a curing catalyst is required as a coating composition.

When the aluminide resin prepared as described above is used as a dispersion stabilizer resin according to the present invention, it is advantageous that at least a part of the alkyd resin has a polymerizable double bond in the molecule. The introduction of the polymerizable double bond into the alkyd resin is usually carried out by reacting a glycidyl group-containing unsaturated monomer, such as glycidyl acrylate, glycidyl methacrylate, or allyl glycidyl ether, with a carboxyl group that may be present in the alkyd resin. Can do it. Further, the introduction of a polymerizable double bond can be achieved by using an isocyanate group-containing unsaturated monomer in a hydroxyl group which may be present in an alkyd resin, for example, an equimolar addition product of a hydroxyalkyl acrylate or a hydroxyalkyl methacrylate and a diisocyanate compound. It can also be carried out by reacting in a method. Such a reaction can be carried out by a method known per se, and it goes without saying that the reaction conditions can be changed depending on the catalyst used and the type of the unsaturated monomer. By the reaction as described above, as described above, it is possible to introduce at least 0.1, preferably 0.3 to 5.0, and more preferably 1.0 to 3.0 polymerizable double bonds per molecule on the alkyd resin on average. it can.

The alkyd resins used as dispersion stabilizer resins according to the present invention generally have a weight average molecular weight of about 5,000 to about 200,0.
It can have a molecular weight in the range of 00, preferably from about 10,000 to about 50,000. If the molecular weight is less than about 5,000, the stabilization of the polymer particles becomes insufficient, while the molecular weight is 200,
If it exceeds 000, the viscosity tends to be extremely high and handling tends to be difficult. In the present invention, stable gel polymer dispersed particles are obtained by using an alkyd resin as described above as a dispersion stabilizer and polymerizing a radical polymerizable unsaturated monomer in the presence of such an alkyd resin.

The polymerization does not dissolve the resulting dispersed polymer particles,
The alkyd resin is used in an organic liquid that is a good solvent. The organic liquid contains at least 30% by weight of an aromatic solvent as an essential component.
As the aromatic solvent, for example, benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha (eg, Cosmo Oil Co., Ltd., Swazole 200, 310,
Aromatic hydrocarbons such as 1500 and 1800) can be used alone or as a mixture of two or more. Such an aromatic solvent can be used by being mixed with another organic liquid as needed. Other organic liquids that can be mixed include, for example, aliphatic hydrocarbons such as hexane, heptane, and octane; alcohol solvents such as isopropyl alcohol, n-butyl alcohol, i-butyl alcohol, and octyl alcohol; cellosolve, butyl cellosolve, and diethylene glycol mono. Ether solvents such as butyl ether; ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methylhexyl ketone and ethyl butyl ketone; ethyl acetate, isobutyl acetate;
Ester solvents such as acyl acetate and 2-ethylhexyl acetate are exemplified, and these can be used alone or in combination of two or more kinds with the above aromatic hydrocarbon. When the content of the aromatic solvent in the organic liquid is 30% or less, the solubility of the alkyd resin becomes insufficient. Therefore, the aromatic solvent is preferably 50 to 100% by weight, more preferably 70 to 100% by weight. % Is desirable.

The radical polymerizable unsaturated monomer polymerized according to the present invention in such an organic liquid includes at least two kinds of vinyl monomers each having a complementary functional group capable of reacting and bonding with each other. It may be a monomer mixture containing 0.5% by weight or a polyvinyl monomer containing at least 0.5% by weight.

Examples of the combination of complementary functional groups capable of reacting and binding to each other in the former monomer mixture include (i) an epoxy group / carboxyl group (ii) a hydroxyl group / isocyanate group (iii) an epoxy group / amino Groups (iv) Combinations of isocyanate groups / amino groups and the like. The following are specific examples of combinations of two or more vinyl monomers each having a complementary functional group capable of reacting and binding with each other.

Examples of (i) include a combination of an epoxy group-containing monomer such as glycidyl acrylate or glycidyl methacrylate and a carboxyl group-containing monomer such as methacrylic acid acrylate; Examples of (ii) include hydroxyethyl acrylate A combination of a hydroxyl group-containing monomer such as styrene or hydroxyethyl methacrylate with an isocyanate group-containing monomer such as isocyanate ethyl acrylate or isocyanate ethyl methacrylate or isophorone diisocyanate / hydroxyethyl acrylate or hydroxyethyl methacrylate equivalent adduct; Examples of the combination of the epoxy group-containing monomer and the aminoalkyl acrylate or aminoalkyl methacrylate monomer; (iv) examples of the combination of the isocyanate group-containing monomer and the acrylic Combinations with aminoalkyl acrylate or aminoalkyl methacrylate monomers; and the like.

At least two each having a complementary functional group as described above
Each type of vinyl monomer is present in the monomer mixture at least
It can be present at a concentration of 0.5% by weight or more, preferably in the range of 0.5 to 20% by weight.

The polyvinyl monomer is a compound having at least 2 to 4 polymerizable double bonds in one molecule, for example, divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate and the like can be mentioned, and these can be used alone or in combination of two or more. Such polyvinyl monomers are also at least 0.5% by weight in the monomer mixture, preferably
It can be present at a concentration in the range of 0.5 to 10% by weight. These vinyl monomers are components for cross-linking the prepared dispersed fine particles, and the use and the type or combination of the monomers can be arbitrarily selected according to the desired performance. Preferable examples include a vinyl monomer and a polyvinyl monomer having a combination of the complementary functional groups described in the above (i).

In order to polymerize the radical polymerizable unsaturated monomer in the presence of the dispersion stabilizer resin and the organic solution to obtain gel dispersed particles, glycidyl (meth) acrylate is contained in the radical polymer unsaturated monomer. And (meth) acrylic acid each at 0.
The content may be 5% by weight or more, preferably 0.5 to 20% by weight. If the content is less than 0.5%, sufficient gel-dispersed particles cannot be obtained, resulting in poor storage stability of the dispersed resin liquid, or poor coating film properties and hardness. On the other hand, if the content is more than 20%, the entire resin liquid system is crosslinked or thickened during the production of dispersed particles, which is not preferable. In obtaining the gel-dispersed particles, it is preferable to use a basic catalyst such as a tertiary amine.

The vinyl monomer or polyvinyl monomer having a combination of the complementary functional groups described above can be used in combination with another radically polymerizable unsaturated monomer. Representative examples of other radically polymerizable unsaturated monomers that can be used are as follows.

(A) esters of acrylic acid or methacrylic acid; for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylic ethyl, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, C ₁ ~ ₁₈ alkyl esters of acrylic acid or methacrylic acid such as lauryl methacrylate; allyl acrylate, acrylic acid and allyl methacrylate or C ₂ ~ ₈ alkenyl esters of methacrylic acid; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl meth click relay C ₂ ~ ₈ hydroxyalkyl esters of acrylic acid or methacrylic acid and the like; allyl oxyethyl acrylate, acrylic acid or C ₃ ~ ₁₈ alkenyloxyalkyl esters of methacrylic acid such as allyloxy methacrylate.

(B) vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene,
Vinyl pyridine.

(C) Others: acrylonitrile, methacrylonitrile, methyl isopropenyl ketone; vinyl acetate, peopa monomer (Ciel Chemical), vinyl propionate,
Vinyl pivalate and the like.

The polymerization of the monomer mixture described above is performed using a radical polymerization initiator. Examples of usable radical polymerization initiators include, for example, 2,2-azoisobutyronitrile,
Azo initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile); and peroxide initiators such as benzoyl peroxide, lauryl peroxide and tert-butyl peroctoate. The agents can be used in general in the range of 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the monomers subjected to the polymerization.

The amount of the alkyd resin used as a dispersion stabilizer during the polymerization may vary widely depending on the type of the monomer and the like, but generally, the monomer and the alkyd resin to be polymerized are used. 10 based on total volume
Suitably, it is in the range of -90% by weight, preferably 30-70% by weight. Further, the total concentration of the monomer and the alkyd resin in the organic solution is generally 30 to 70% by weight, preferably 40 to 70% by weight.
~ 60% by weight. The dispersion polymerization method can be carried out using a radical polymerization method known per se, and the reaction temperature during the polymerization is generally about 50 to about 15
The temperature is suitably in the range of 0 ° C.
The reaction can be completed in about 15 hours. Thus, a polymer fine particle dispersion cross-linked inside the dispersed fine particles is obtained, and the polymer cross-linked fine particle dispersion is used as it is, or mixed with an oil-free alkyd resin or a short oil alkyd resin to form a colorant. , A curing agent and the like can be blended and used as a coating composition. Examples of the coloring agent include dyes, organic pigments, and inorganic pigments. As the curing agent, for example, a crosslinking agent such as an amino resin, an epoxy resin, and a polyisocyanate can be used.

(Examples) Hereinafter, the present invention will be described more specifically with reference to examples.
In the examples, all parts and percentages are by weight.

<Production Example> Synthesis of dispersion stabilizer A In a flask equipped with a thermometer, a stirrer, and a moisture device, 513.2 parts of phthalic anhydride neopentyl glycol 214.2〃 ethylene glycol 50.6〃 trimethylolpropane 167.0〃 coconut oil and fat 128.5〃 monobutyl 1.0 of tin hydroxide was charged and heated to 230 ° C. for 4 hours while stirring the contents. After further heating at 230 ° C. for 2 hours, 5% xylene is added to the total charged amount to promote the removal of condensed water produced as a by-product in the esterification reaction, and the temperature is maintained at 230 ° C .; Heating was continued until. When the acid value reached 5, the heating was stopped, and the mixture was diluted with xylene so that the heating residue became 70%. The viscosity of the obtained alkyd resin varnish having a fatty acid modification amount of 12.8% is X, and the weight average molecular weight of the resin is 17,000.
Met. Then, 50.0 parts of a 1: 1 (molar ratio) adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the varnish.
0.1 parts of -tert-butylcatechol was added and reacted at 100 ° C for 3 hours to introduce a copolymer double bond into the molecular chain of the dispersion stabilizer.

Synthesis of dispersion stabilizer B In a flask equipped with a thermometer, a stirrer and an aqueous disperser, phthalic anhydride 473.4 parts adipic acid 133.4 ペ ン neopentyl glycol 239.9〃 ethylene glycol 56.7〃 trimethylolpropane 187.1〃 monobutyltin hydroxide 1.0〃 And heated to 230 ° C. in 4 hours while stirring the contents. After further heating at 230 ° C. for 2 hours, 5% xylene is added to the total charged amount to promote the removal of condensed water produced as a by-product in the esterification reaction, and the temperature is maintained at 230 ° C .; Heating was continued until. When the acid value reached 5, the heating was stopped, and the mixture was diluted with xylene so that the heating residue became 70%. The viscosity of the obtained oil-free alkyd resin varnish was Z, and the weight average molecular weight of the resin was 15,000. Then, 50.0 parts of a 1: 1 (molar ratio) adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the varnish, and 4-tert.
0.1 parts of -butylcatechol was added and reacted at 100 ° C for 3 hours to introduce a polymerizable double bond into the molecular chain of the dispersion stabilizer.

Synthesis of dispersion stabilizer C 680.8 parts of isophthalic acid neopentyl glycol 231.5 水 ethylene glycol 54.7 器 trimethylolpropane 180.6〃 monobutyltin hydroxide 1.0〃 was charged into a flask equipped with a thermometer, a stirrer and a water disperser. Was heated to 230 ° C. for 4 hours while stirring. Hereinafter, the viscosity of the oil-free alkyd resin varnish obtained by the same method as that of the dispersion stabilizer B is Z-1.
The weight average molecular weight of the resin was 16,000. Then, 1 part of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the varnish.
500 parts of a 1: 1 (molar ratio) adduct and 0.1 part of 4-tert-butylcatechol were added and reacted at 100 ° C. for 3 hours to introduce a polymerizable double bond into the molecular chain of the dispersion stabilizer.

Synthesis of dispersion stabilizer D In a flask equipped with a thermometer, a stirrer and a water disperser, terephthalic acid 382.4 parts adipic acid 282.5〃 neopentyl glycol 241.9〃 ethylene glycol 57.1〃 trimethylolpropane 188.7〃 monobutyltin hydroxide 1.0〃 The contents were heated to 230 ° C. in 4 hours while stirring the contents. Hereinafter, the viscosity of the oil-free alkyd resin varnish obtained by the same method as that of the dispersion stabilizer B was Z, and the weight average molecular weight of the resin was 18,000. Then, a one-to-one mixture of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method in the entire amount of the varnish was used.
(Molar ratio) 50.0 parts of the adduct and 0.1 part of 4-tert-butylcatechol were added and reacted at 100 ° C. for 3 hours to introduce a polymerizable double bond into the molecular chain of the dispersion stabilizer.

Synthesis of dispersion stabilizer E In a flask equipped with a thermometer, stirrer and water disperser 439.2 parts of phthalic anhydride neopentyl glycol 194.7〃 ethylene glycol 69.0〃 trimethylolpropane 101.3〃 coconut oil fatty acid 272.6〃 monobutyltin hydroxide 1.0 〃 was charged and heated to 230 ° C. in 4 hours while stirring the contents. After further heating at 230 ° C. for 2 hours, 5% xylene is added to the total charged amount to promote the removal of condensed water produced as a by-product in the esterification reaction, and the temperature is maintained at 230 ° C .; Heating was continued until. When the acid value reached 5, the heating was stopped, and the mixture was diluted with xylene so that the heating residue became 70%. The viscosity of the obtained alkyd resin varnish having a fatty acid modification amount of 27.3% is T, and the weight average molecular weight of the resin is 13,000.
Met. Then, 50.0 parts of a 1: 1 (molar ratio) adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the varnish.
0.1 parts of -tert-butylcatechol was added and reacted at 100 ° C for 3 hours to introduce a polymerizable double bond into the molecular chain of the dispersion stabilizer.

Production Example of Non-Water-Dispersible Resin 1 In a flask equipped with a thermometer and a stirrer, 104.8 parts of xylene, 36.9 parts of heptane, 142.9 parts of dispersion stabilizer A (100 solids) were charged, and heated to 100 ° C. , A polymerization initiator and a basic catalyst were added dropwise over 3 hours, followed by aging for 4 hours.

Methyl methacrylate 60.0 parts Acrylonitrile 20.0 2-Hydroxyethyl acrylate 10.0 Glycidyl methacrylate 7.0 Acrylic acid 3.0 Azobisisobutyronitrile 2.0 Dimethylaminoethanol 1.0 The obtained resin liquid has a nonvolatile content of 52%, viscosity D, Particle size of polymer particles (measured by electron microscope, the same applies hereinafter) 0.2-0.3μ
m dispersion. Even after standing at 50 ° C. for 3 months, there was no generation of precipitates or coarse particles and no change in the properties of the varnish.

Production Examples of Non-Aqueous Dispersible Resin Liquids 2 to 5 Except that the dispersion stabilizer A in the production example of the non-aqueous dispersible resin liquid 1 was changed to Dispersion Stabilizers B, C, D or E, the others were the same in composition and method Non-aqueous dispersible resin liquids were produced, and non-aqueous dispersible resin liquids 2 to 5 each having a nonvolatile content of 52% were obtained. Each of them was a dispersion having a particle size of 0.2-0.3 μm. Even when the dispersion was allowed to stand at 50 ° C. for 3 months, there was no generation of precipitates or coarse particles and no change in the properties of the varnish.

Production example of non-aqueous dispersible resin liquid 6 Xylene 104.8 parts heptane 36.9 {Dispersion stabilizer A 142.9 (solid content 100)} was charged into a flask equipped with a thermometer and a stirrer, and heated to 100 ° C. Was added dropwise over 3 hours, followed by aging for 4 hours.

Methyl methacrylate 70 parts Acrylonitrile 20〃 2-hydroxyethyl acrylate 10〃 The resulting resin solution was a dispersion having a non-gelled dispersion content of 52%, a viscosity D, and a polymer particle size of 0.2-0.3 μm. Was. The particle size is 0.4 when left at 50 ° C for 3 months.
It changed to −0.5 μm, and the formation of a precipitate was observed. Also,
The viscosity was increased to G.

Examples 1 to 7 and Comparative Examples 1 to 2 Oil-free alkyd resin, non-aqueous dispersible resin liquids 1 to 5
And a cross-linking agent were blended at the solid content ratio shown in Table 1 below, applied to each test plate (3.5 mm thick, zinc phosphate treated) and baked at 140 ° C. for 30 minutes to cure (curing) Film thickness 20 to 25 μm). Various test results of the obtained coating film are shown in Table 2 below.

(Note) 1) Flex resistance: The test was performed under the conditions of JIS K5400. When the diameter of the mandrel was 2 mm and the thickness of the auxiliary plate was 4 mm, cracking and peeling of the coating film were observed.

-There is no damage of the coating film such as peeling and peeling: ○-Cracking and peeling occurred: × 2) Impact resistance: Mild steel plate was used as the material. Using a DuPont impact tester, 500 g of a weight was dropped on the coating film at a bombardment point of 1/2 inch φ, and the maximum distance without peeling was examined.
(Cm) 3) Echrysene: Measured with an Echryssen Ekryssen tester (unit: mm).

4) Hardness: evaluated according to JIS K5400.

5) Base: The test was performed under the conditions of JIS K5400.

Separation of cells with Serofan tape, total number 100
Among them, the number of squares remaining without peeling was evaluated.

6) Weather resistance: The material used was an aluminum plate. The Q Panel Company's QUV weather meter (UV fluorescent lamp "No. QF
S-40, UV-8 "wavelength range of 320 to 280 nm).
Irradiation at ~ 70 ℃ (15 minutes) and condensation (15 minutes)
After repeated for 2000 hours, the degree of deterioration of the coating film was observed.

7) Magic stain: apply red paint to the painted surface,
Left at 24 ° C. for 24 hours. Lightly wiped three times with absorbent cotton containing an appropriate amount of ethanol, and the presence or absence of coloring was evaluated.

Without coloring: ○ With coloring: ×

Continuation of the front page (56) References JP-A-49-11979 (JP, A) JP-A-60-20902 (JP, A) JP-A-51-55344 (JP, A) JP-A-51-109942 (JP) , A)

Claims (1)

(57) [Claims] The present invention relates to an alkyd resin having an average of at least 0.1 polymerizable double bond in a side chain of a molecule and having a fatty acid modification amount of 0 to 25% by weight. Polymer particles producing a radically polymerizable unsaturated monomer containing at least 0.5% by weight of at least 0.5% by weight of each of at least two kinds of vinyl monomers each having a complementary functional group or a vinyl monomer Is not dissolved, but is a good solvent for the alkyd resin and the radically polymerizable unsaturated monomer, and is copolymerized in an organic liquid containing at least 30% by weight of an aromatic solvent. A method for producing a polymer crosslinked fine particle dispersion insoluble in an organic liquid.