JPS6151003A - Production of fine polymer particle - Google Patents

Abstract

PURPOSE:To produce fine polymer particles having a high gel content and suited as a flow modifier, by simultaneously effecting nonaqueous polymerization of an epoxy group-containing vinyl monomer and intragranular crosslinking with a specified compound. CONSTITUTION:Nonaqueous polymerization of a vinyl monomer (e.g., methyl methacrylate) containing an epoxy group-containing vinyl monomer (e.g., glycidyl methacrylate) is effected in the presence of a nonpolar organic solvent in which the formed polymer is not soluble (e.g., hexane) and a dispersion stabilizer [e.g., n-butyl (meth)acrylate] and a compound having at least two carboxyl groups in the molecule (e.g., polyester resin) and/or a polycarboxylic acid anhydride (e.g., phthalic anhydride) and at the same time the intragranular crosslinking is effected.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a new and useful method for producing fine particle polymers, and more particularly, to In addition, a compound having two or more carboxyl groups in one molecule (hereinafter also referred to as a polycarboxylic acid compound) and/or a polycarboxylic acid anhydride is used to perform non-aqueous dispersion polymerization. The present invention relates to a method for producing a highly gelled fine particle polymer by a non-aqueous dispersion polymerization method, which is useful as an organic pigment, an organic filler, a flow control agent, or the like.

[Conventional technology]

The technology of preparing highly gelled particulate polymers by non-aqueous dispersion polymerization is well known, and the particulate polymers obtained using the Koushitomo technology can be added, for example, to high solids paints. and its use as a flow regulator is being considered.

By the way, the gelling particulate polymer in the prior art is produced by simultaneously non-hydrolytically associating a monomer mixture having two types of functional groups (polar groups) that can react with each other, such as glycidyl methacrylate and methacrylic acid. It has been obtained by reacting or by coexisting a polyfunctional vinyl compound such as ethylene glycol dimethacrylate in a monomer mixture and polymerizing it.

[Problems to be Solved by the Invention] However, fine particle polymers obtained according to such conventional methods have a soluble portion of the gelled fine particle polymer eluted by a good solvent such as tetrahydrone, and are substantially resistant to good solvents. Because the degree of gelation, defined as the fraction (weight ratio) of the measured weight to the weight before extraction, is low, for example, this gelled fine particle polymer is extracted with a high solid content. When added to type coatings, the solvents used in ordinary high solids type coatings are generally good solvents for the fine particle polymers, and dissolve the gelled fine particle polymers. ), it does not result in an increase in the viscosity of the system, and it only acts as a disadvantage for high solid content type paints.

On the other hand, although it is believed that increasing the degree of gelation can be achieved by increasing the concentration of functional groups (polar groups) used for crosslinking, in such cases it is not limited to the inside of the particles, but rather As a result, the crosslinking reaction between the two processes becomes more likely to proceed, and the entire system eventually becomes a gel, so it cannot be said that this is a preferable method.

[Means for solving problems]

However, in view of the various shortcomings in the 1xJ conventional technology mentioned above, the inventors have conducted extensive studies on the mold.
A gelled fine particle polymer obtained by performing intraparticle cross-linking of dispersed particles with an epoxy group-containing vinyl monomer and a polycarboxylic acid compound and/or polycarboxylic acid anhydride as the compound to be crosslinked is highly effective. We have completed the present invention by discovering that it has a high degree of gluing.

That is, in the present invention, a vinyl monomer containing EBOKI 5, a silica group is used as an essential vinyl monomer, and the vinyl monomer is treated in the presence of a dispersion stabilizer in an organic solvent that does not dissolve the polymer formed by the vinyl monomer. , a novel and useful method comprising non-aqueous dispersion polymerization of the vinyl-based carmer and also intraparticle crosslinking of the dispersed particles using a polycarboxylic acid compound and/or polycarboxylic acid anhydride. A method for producing a particulate polymer is provided.

In an organic solvent that does not dissolve the vinyl monomer dipolymer, in the presence of a dispersion stabilizer, the vinyl monomer is polymerized in a non-aqueous manner, and at the same time, the vinyl monomer is crosslinked within the particles. Microparticle polymer, which is a cross-linked non-aqueous dispersion polymer.
In the method for producing klJ5, non-aqueous dispersion polymerization is carried out using an epoxy group-containing vinyl monomer as an essential monomer, while intraparticle crosslinking is carried out using a polycarboxylic acid compound and/or polycarboxylic acid anhydride. A method for producing a particulate polymer is provided.

Here, the vinyl monomer is dissolved in the non-aqueous dispersion polymer, but when the vinyl monomer is non-aqueous dispersion polymerized, the resulting polymer is not dissolved. Among them, it is obtained by polymerizing the vinyl monomer in the presence of a dispersion stabilizer, and as is known, it is obtained by polymerizing the vinyl monomer in a solvent such as an aliphatic or alicyclic hydrocarbon solvent. In the presence of a dispersion stabilizer having both a soluble segment and an insoluble or swellable segment in such a solvent, the resulting polymer is insoluble, but on the other hand, the monomer is soluble. monomer [hereinafter referred to as 2'Lf:
It is abbreviated as a cutting die mass. ] By polymerizing it and chemically or physically bonding it to the above-mentioned dispersion stabilizer, it can be stably dispersed in the above-mentioned solvent.
A polymer whose particle shape is entirely different from each other is divided into symmetry.

The specific method for preparing the non-aqueous dispersion polymer is as follows.

First, the solvent to be used is non-polar or has a small specific dissolving power, and although it does not dissolve the polymer produced from the above-mentioned cutting die polymer (hereinafter abbreviated as the core monopolymer), it does not dissolve the dispersion stabilization. Any solvent that can dissolve or swell the agent can be used, but typical examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; petroleum benzine, ligroin, and minerals. The boiling point of spirits, petroleum naphtha, kerosene, etc. is 3.
Hydrocarbon mixtures in the range from 0 to 300°C; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, or mixtures thereof.

In some cases, these aliphatic hydrocarbons, hydrocarbon mixtures, and /-1: +1 of the alicyclic hydrocarbons may contain aromatic hydrocarbons up to about 70"M% of the total solvent. Hydrogen-based, ester-based, alcohol-based, ketone-based, or ether-based compounds including polar compounds may also be used.

The appropriate amount of the solvent to be used is within a range such that the solid temperature content of the resulting non-aqueous dispersion polymer is 30 to 70% by weight, preferably 40 to 60% by weight.

Next, typical examples of the dispersion stabilizer include (1) unsaturated bond-containing polymers such as polybutadiene and polyisoprene; - Addition reaction of an unsaturated bond-containing epoxy compound such as glycidyl (meth)acrylate to the carboxyl group in the latter graft copolymer to the graft copolymer or heptad copolymer obtained by polymerization. At least obtainable diatonic graft copolymer;
■Alkyd fat: 0C6~C1! An alkyl etherified melamine resin condensate etherified with alkyl alcohol and soluble in the various solvents listed above; the terminal position of a self-condensed polyester of a hydroxyl group-containing saturated fatty acid such as 012-hydroxystearic acid The terminal unsaturated bond-containing polyester resin obtained by adding the above-mentioned unsaturated bond-containing epoxy compound to the carboxyl group in A graft copolymer obtained by copolymerizing 28 or more, and a copolymer obtained by copolymerizing the unsaturated bond-containing polyester resin with an essential polymer (mentioned below) and methane acrylic acid. An unsaturated bond-containing graft copolymer obtained by addition reaction of the unsaturated bond-containing epoxy compound 'I!llJ to the group: or n-butyl (meth)acrylate, 1so-butyl (methanoacrylate, The main component is alkyl esters of (meth)acrylic acid esterified with C4 or higher alkyl alcohols such as 2-ethylhexyl (methanoacrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate), and other components as necessary. A polymer obtained by combining the vinyl monomer t-(co)'N,
Esterified with the above C4 or higher alcohol (mainly composed of alkyl esters of methane acrylic acid, obtained by total copolymerization with (meth)acrylic acid and other vinyl monomers as necessary) A copolymer having an unsaturated bond obtained by subjecting the carboxyl group in a copolymer containing an epoxy group to an epoxy group-containing vinyl J4''m gold addition reaction, or a copolymer having an unsaturated bond obtained by subjecting the carboxyl group in a copolymer containing an epoxy group to the carboxyl group in the copolymer containing The carboxyl group in the graft copolymer obtained by combining the polymer and the gold aggregate 1, or the copolymer obtained by copolymerizing such an unsaturated bond-containing copolymer, the essential polymer, and (meth)acrylic acid. There are graft copolymers having unsaturated bonds obtained by addition reaction of epoxy group-containing vinyl monomers.

Among these, the above-mentioned sor't-f:'n■ and 0
When using each dispersion stabilizer of the group 0, when using a terminal unsaturated bond-containing polyester resin as a dispersion stabilizer in the above-mentioned group 0, and when using the dispersion stabilizer of the above-mentioned group 0. The curing agent is derived from (co)polymers or core (co)polymers which are esterified with a C1 or higher alkyl alcohol and whose main component is an alkyl ester of (meth)acrylic acid. When using unsaturated bond-containing copolymers as a dispersion stabilizer, all of the dispersion stabilizers must not have segments that are insoluble in the various solvents listed above. However, in the subsequent preparation of non-aqueous dispersion polymers using these types of dispersion stabilizers, segments that are insoluble in the above-mentioned solvents are formed at the initial stage of polymerization of the essential polymer, and the purpose is A non-aqueous dispersion polymer is obtained.

Here, the above-mentioned essential polymers include methyl (meth)acrylate, ethyl (meth)acrylate, n-
Examples include esters of (meth)acrylic acid esterified with alcohols such as propyl (meth)acrylate and 1ao-propyl (C1-C, such as methane acrylate); On the other hand, other monomers that can be copolymerized with these essential monomers include butyl (methane acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.). (alkyl esters of methane acrylic acid: sialkyl esters of unsaturated dicarboxylic acids such as maleic acid, 7-malic acid, itaconic acid and monohydric alcohols; vinyl acetate, benzoic acid) Vinyl acid, various vinyl esters such as "Peova" (vinyl ester manufactured by Shell in the Netherlands): "Visco-" 8F
, 8FM, 3F or 3FMJ (fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Chemical ■), perfluorocyclohexyl (meth)acrylate, Seeperfluorocyclo to Φ silhumare)1. cdN-iso-7'o
(Per)fluoroalkyl group-containing vinyl esters such as pilperfluorooctanesulfonamide ethyl (meth)acrylate; vinyl halides (vinylidene) such as vinyl chloride, vinylidene chloride, vinyl butylene fluoride, vinylidene fluoride: ethylene, α-olefins such as fluoropylene, trifluoroethylene; aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene, 0-methylstyrene, p-methylstyrene; maleic anhydride Acids, monomers containing acid anhydride groups such as phosphoric acid; (methanoacrylamide,
N-alkoxymethyl (meth)acrylamide, diacetone acrylamide, N-methylolated (carboxylic acid amide group-containing monomers such as methanoacrylamide; α, such as (meth)acrylic acid hydroxyalkyl ester,
Phosphoric ester bond-containing monomers obtained by the condensation reaction of hydroxyalkyl esters of β-ethylene ref saturated carboxylic acid and phosphoric acid or phosphoric esters; sulfones such as 2-acrylamido-2-methyl-propanesulfonic acid Related group-containing monomers or their organic amine salts; 2-hydroxyethyl (methane acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (methane acrylate), 4-hydroxybutyl (methane acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol mono (meth)acrylate (hydroxyalkyl esters of methanoacrylic acid; the above) unsaturated bond-containing hydroxyalkyl esters such as heptano- or di-hydroxyalkyl esters of polyhydric carboxylic acids obtained by the addition reaction of acid anhydride group-containing monomers with glycols such as ethylene glycol; ;@7:
Examples include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether.

The epoxy group-containing vinyl monomer used for intraparticle crosslinking of the non-aqueous dispersion polymer of formula n1 used together with the cutting molder as listed above is glycidyl (meth)a II).
These are used as essential vinyl monomers in the method of the present invention.

Next, in carrying out the method of the present invention, first of all the polycarboxylic acid compound and/or polycarboxylic anhydride, which is the other component to be used for intraparticle crosslinking of the non-aqueous dispersion polymer. The polycarboxylic acid anhydride preferably has at least one acid anhydride group in one molecule and is soluble in the aliphatic or alicyclic solvents listed above. Any substance can be used as long as it satisfies each of the following conditions, but representative examples include phthalic anhydride, 3-methyl phthalic anhydride, tetrahydrophthalic anhydride, and 3-methyltetrahydro anhydride. Phthalic acid, hexadrophthalic anhydride, 3-
These include methylhexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, or methylcyclohexentricarboxylic anhydride.

Among these, 3-methyltetrahydrophthalic anhydride or 3-methylhexahydrophthalic anhydride is particularly desirable from the viewpoint of solubility in the various solvents mentioned above.

When using the polycarboxylic acid anhydride as a crosslinking agent, it is of course necessary to introduce a hydroxyl group-containing monomer into the above-mentioned cutting mold polymer.

On the other hand, the polycarboxylic acid compound refers to a compound having at least two carboxyl groups in one molecule.

Therefore, any number of such compounds can be used, but the solubility in the various solvents mentioned above and the glass size required for the preparation of all such compounds,
Polyester resins and alkyd resins are particularly desirable.

Such polyester and/or alkyd resins are obtained according to conventional methods, and typical polybasic acid components used on the spot include ester acid, terephthalic acid, orthophthalic acid, 2,6-7tale dicarboxylic acid, 4,4'-diphenylcarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid Acids, methylendomethylenetetrahydrophthalic acid, maleic acid, hepmalic acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid or dimeric fatty acids; male or cycloben Mentetracarboxylic acid, trimellitic acid, pyromellitic acid, and trimesine also include various reactive derivatives thereof, such as various alkyl esters and anhydrides.

These polysalts M (representative examples of alcohol components used with component i are ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1.3-7"tanediol, 1.5" - Aliphatic glycols such as bentanediol, 1,6-hexanediol, neopentyl glycol; cycloaliphatic glycols such as 1s4-cyclohexane dimetatool, hydrogenated bisphenol A; bishydroxyethyl terephthalate, alkylene of bisphenol A; It goes without saying that aromatic glycols such as oxide adducts can be used in combination with known and commonly used monoepoxy compounds. Glycerici and trimethylo.

- Polyester compounds obtained by adding ε-caprolactone to the various alcohol components listed above can also be used. Of course.

Further, typical fatty acids used to obtain the above-mentioned alkyd resin include octylic acid, palmitic acid, stearic acid, persatic acid, oleic acid, linoleic acid, lylunic acid, and palmitic acid. Oil fatty acids, hydrogenated coconut oil fatty acids, tall oil fatty acids 1 castor oil fatty acids, dehydrated castor oil fatty acids, rice bran oil fatty acids, necessarily oil fatty acids, soybean oil fatty acids' or? Examples include long-chain monobasic acids of Ca or more, such as flower oil fatty acids.

Polyester and/or alkyd resins can be obtained by conventional methods using various polyester-forming components, but in addition to these resins, compounds such as 12-hydroxystearin or its self-condensate can also be used to form polyesters. Of course, it can also be used as a sexual component.

The polycarbonate compound obtained in this way has a number average molecular ffi (Mn) of 20
Between 0 and 3,000? Those having an acid value within the range of 40 to 600 are preferred.

Of course, a polycarboxylic compound such as those mentioned above and a polycarboxylic acid anhydride may be used in combination.

In addition, in preparing the above-mentioned fine particles 1 coalesced t- for carrying out the method of the present invention, the above-mentioned methods may be used.
It is particularly desirable to introduce a functional group (polar group) such as a hydroxyl group into both the dispersion stabilizer and the anchoring polymer.

This means that when the fine particle polymer obtained by carrying out the method of the present invention is blended into, for example, a melamine curable paint to form a cured coating, the dispersion stabilizer portion also This is because the core portion of the non-aqueous dispersion polymer also reacts with the curing agent component, resulting in a uniform and highly transparent coating film.

In order to prepare the target fine particle polymer by the method of the present invention, in the presence of each of the above-mentioned independent solvents, the above-mentioned dispersion stabilizer, and the above-mentioned polycarboxylic acid compound and/or polycarboxylic acid anhydride, the above-mentioned A cutting mold containing an epoxy group-containing monomer is combined by a conventional method, or a cutting mold containing the above-described dispersion stabilizer and an epoxy group-containing monomer is combined in the presence of the various solvents listed above. After polymerizing the above-mentioned polycarboxylic acid compound and/or polycarboxylic acid anhydride by a conventional method, the above-mentioned polycarboxylic acid compound and/or polycarboxylic acid anhydride may be added to the reaction system to cause the reaction. A crosslinked particulate polymer is obtained.

Here, the intraparticle crosslinking of the non-aqueous dispersion polymer, that is, the epoxy group derived from the epoxy vinyl group-containing monomer,
On the other hand, the esterification reaction between the polycarboxylic acid compound and/or the carboxyl group based on the polycarboxylic acid anhydride is allowed to proceed simultaneously with the non-aqueous dispersion polymerization, or is carried out upon completion of this non-aqueous dispersion polymerization reaction. The esterification reaction can be allowed to proceed by raising the temperature of the system, or by using a known and commonly used reaction catalyst (reaction accelerator) such as a basic catalyst such as 2-methylimidazole or dimethylamine ethanol. It may be possible to advance the process by allowing both to coexist.

In addition, the non-aqueous dispersion polymerization reaction carried out to prepare the target fine particle polymer (by the method of the present invention) may also be carried out using any of the known and commonly used polymerization initiators such as azo or peroxide initiators. Furthermore, various known and commonly used chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, or α-methylstyrene dimer may be used for such non-aqueous dispersion polymerization. You can also do it.

In this way, the desired fine particle polymer is obtained, but the fine particle polymer can be used even if a non-aqueous polymer dispersion liquid or a dispersion liquid of a non-aqueous dispersion polymer with no inter-particle cross-linking is used. It goes without saying that Rurui may be used in the form of a powder from which the solvent has been removed and, if necessary, further subjected to a pulverization step.

[Applications of the present invention]

As described above, the fine particle polymer obtained according to the method of the present invention can be used as an organic pigment or an organic filler, and can also be used as a paint, especially for metallic bases such as automobiles or for top clear coatings. It can also be used as a so-called flow regulator by adding it to high solids content type paints such as those for commercial use.

〔Example〕

Next, the present invention will be explained in more detail with reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, all parts and % are based on the amount of M unless otherwise specified. shall be taken as a thing.

Example 1 (Preparation example of a hydroxyl group-containing polymer as a main vehicle component for paints) 160 parts of xylene and 160 parts of n-butanol were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reflux condenser. 120 parts of styrene, 180 parts of n-butyl acrylate, 120 parts of n-butyl methacrylate,
108 parts of β-hydroxypropyl acrylate, β-
66 parts of hydroxypropyl methacrylate and 06 parts of acrylic and 80 parts of n-butanol, ter
48 parts of t-butyl peroxyoctate, ter
3 parts of t-butyl peroxide and azobis-1a
A mixture consisting of 12 parts of o-butyronitrile was added dropwise over a period of 8 hours, and after the addition was completed, the same temperature was maintained for 15 hours to allow the reaction to proceed completely. The non-volatile content (NY) was 60%.
Gardner color (G, C,) Z>E 1 Below,
Gardner viscosity (G, Vis,) at 25°C is E, and Mn! A solution of the desired polymer having a TIi of 1.000 and a TIi of 0° C. was obtained, but the OHV of this solution based on the solid content was 109. Hereinafter, these NFC polymers (
It is abbreviated as the solution of a-1).

Reference Example 2 (same as above) The monomer composition was 120 parts of styrene, 90 parts of methyl methacrylate, 120 parts of n-butyl methacrylate,
The desired polymer was prepared in the same manner as in Reference Example 1, except that 114 parts of n-butyl acrylate, 90 parts of β-didroxypropyl acrylate, 60 parts of β-hydroxypropyl methacrylate, and 6 parts of acrylic acid were used. Obtained solution gold. NY of this is 60%, G, C, is less than 1, G,
Vi+i is H, Mn is 3.000, and T
I9 was 20°C. Moreover, the OHV (based on solid content) of this product was 94. Hereinafter, this will be referred to as polymers C&-2.
) solution.

Reference Example 3 (same as above) In a reactor equipped with a stirrer, a thermometer, a crab inlet tube, and a reaction product water distillation tube, 215 parts of adipic acid and hexahydro corresponding to 63.8 mol% of the total polybasic acid components were added. 400 parts of 7-mer acid anhydride and 44.6 parts of trimethylolpropane
50 parts of ethylene glycol and 3 parts of neopentyl glycol representing 76.7 mol% of the total alcohol content.
The temperature was gradually raised to 230°C over 5 hours in a nitrogen stream and maintained at the same temperature until the acid value reached 10. 010
An oil-free alkyd resin was obtained.

Next, this resin was cooled to below 250°C.
of xylene was added to obtain a solution of oil 7-ary alkyd resin with an NV of 80%. Hereinafter, this nt-polymer (a
-3) Abbreviated as solution.

Reference Example 4 (same as above) In a polyester reactor similar to Reference Example 3, 83.2 parts of adipic acid and 400 parts of hexahydro-7-meric anhydride, which corresponds to 82 mole% of the total polybasic acid components, and trimethylolpropane were added. 61.1 parts of and 90 parts of total alcohol content
423 parts of neopentyl glycol corresponding to mol% of I got free alkyd resin Sagi.

Next, this resin was cooled to below fi-100°C and heated to 250°C.
1 part of xylene and 0.1 part of diptyltin dilaurate were added, the temperature was raised to 65°C, and while maintaining the same temperature, 100 parts of hexamethylene diinocyanate was added for 2 hours while being careful not to generate heat. He gradually became a subordinate.

After the dropwise addition was completed, the mixture was kept at the same temperature for 2 hours and then at 80°C for 1 hour to obtain a partially urethanized oil-free alkyd resin with a NY content of 80%. 1iJt-obtained. This thing's OH
M was 118 and Mn was 1,070. Hereinafter, and n will be abbreviated as a solution of polymer Hu (a-4).

Reference Example 5 (same as above) In a polyester reactor similar to Reference Example 3, 15 parts and 4 parts of adipic acid, 300 parts of hexahydrophthalic anhydride corresponding to 64.4 mol% of the total polybasic acid components, and trimethylolpropane were added. and 230 parts of neopentyl glycol, which corresponds to 59 mol% of the total alcohol component, and 200 parts of coconut oil fatty acid were added, and the temperature was gradually raised to 230°C over 5 hours in a nitrogen atmosphere. and the acid value is 1
An alkyd resin was obtained by keeping the temperature at the same temperature until the temperature reached 0. Next, this resin was cooled to below t-100°C, and 250 parts of xylene was added to make an alkyd resin with a NY content of 80%. It was made into a solution.

The OHV of this solid lunch box is 125, and the Mn is 1.
: It happened at 14 degrees. Hereinafter, this nt-polymer HC&-5)
It is abbreviated as a solution of

, 1 Reference Example 6 (same as above) In a reactor similar to Reference Example 1, 134 parts (i mol) of trimethylolpropane and 684 parts (i mol) of ε-caprolactone were added.
6 mol) and α04 parts of tetrabutyl titanate.

The temperature was raised to 180°C and maintained at the same temperature for 10 hours to obtain a lactone-added polyester resin.

This product had NY of 100%, G via of X, OHv of 206, and 1Mn of 820. Below is this
It is abbreviated as t-polymers (a-6).

Reference Example 7 (Example of Preparation of Polycarboxylic Acid Compound for Preparing Fine Particle Polymer) 1,800 parts of 12-hydroxystearic acid was placed in a reactor equipped with a stirring device, a thermometer, a cooling tube 2, and a nitrogen introduction tube. was charged and the temperature was raised to 220°C to perform esterification.

During this temperature rise, melting of 12- and trostearic acid begins when the temperature reaches 72°C or higher, so stir at the same time as melting.
f: Start.

Water began to distill out at about 190°C, and esterification proceeded until the acid value reached about 38. After reacting for about 7 hours, it was cooled and taken out.

The self-condensed polyester of 12- and droxystearic acid obtained here has NY of ioo%, G, Vis, and z.
2, and G, C, were 16. Hereinafter, it will be abbreviated as n and all intermediates (b-1).

Next, 1. of the thus obtained intermediate (b-1). O
0 parts of O and 115 parts of hexahydrophthalic anhydride were charged into the same reactor as in Reference Example 1, and heated at 140°C in a nitrogen atmosphere.
The mixture is heated to 100% and then kept at the same temperature for 4 hours to add cyhexahydrophthalic anhydride to the intermediate to obtain a polycarboxylic acid compound. Thereafter, the temperature was lowered to below 100°C, and 478 parts of Isopar EJ (an aliphatic hydrocarbon crystal metal manufactured by Exxon, USA) was added to form a solution with a nitrogen content of 70% and an acid value of 52.5. Obtained.

The dirt is abbreviated as intermediate (b-2).

Example 1 In a reaction apparatus similar to Reference Example 1, 450 parts of the intermediate (b-1) obtained in Reference Example 7 and 33Q of n-butyl acetate were added.
, 46 parts of glycidyl methacrylate equivalent to the carboxyl group in intermediate (b-1), 1 part of 2-methylimidazole, and 1 part of hydroquinone were charged and the temperature was raised to 130°C. Glycidyl methacrylate is added to intermediate (b-1) by subsequently reacting at the same temperature for 6 hours, but this reaction can be carried out by monitoring the acid value.

The thus obtained n-terminal unsaturated bond-containing polyester is N
The solution had Y of 60%, G, Mis, A1, G, C, 16, and an acid value of 1 or less. Hereinafter, this will be abbreviated as a dispersion stabilizer (e-1).

Separately, "Isopar E" was added to the same reactor as in Reference Example 1.
The temperature was raised to 100°C, and at the same temperature 168 parts of methyl methacrylate, 105 parts of ethyl acrylate, and 70 parts of β-hydroxyethyl methacrylate were charged.
3.2 parts of glycidyl methacrylate and 12.1 parts of the above intermediate (b-2), 3.4 parts of azobisisobutyronitrile, 411 parts of the above dispersion stabilizer, 2
- A mixture of 3 parts of Cl of methylimidazole and 356.3 parts of Isopar E is added dropwise over 8 hours, followed by reaction at the same temperature for 10 hours to disperse the desired fine particle polymer. (1-obtained.

This object had an NV of 40% and G, Vis, and A, making it a milky white Venus. Hereinafter, this will be abbreviated as fine particle polymer (D-1).

Example 2 In the same reaction apparatus as in Reference Example 1, 20
0.2 parts and 2 parts of 3-methylhexahydrophthalic anhydride were charged in total, and the temperature was raised to 100° C. in a nitrogen stream.

Next, the other raw materials were mixed with -168 parts of methyl methacrylate, 105 parts of ethyl acrylate, 70 parts of β-hydroxyethyl methacrylate, 3.2 parts of glycidyl methacrylate, and the intermediate (b) obtained in Reference Example 7. −
: 6.2 parts of 2), the dispersion stabilizer obtained in Example 1 (
41.1 parts of a-IJ, 0.1 parts of 2-methylimidazole.
A dispersion of the desired fine particle polymer was obtained in the same manner as in Example 1, except that 7 parts, 35 parts of Isopar EJ, and 5.4 parts of azobisisobutyronitrile were used.

This product had a milky white color with 40% NY and As in G, Vis, and As. Hereinafter, it will be abbreviated as 2'Lt-fine particle polymer (DL2).

Example 3 200.2 parts of "Isopar E" and 4.1 parts of 3-methylhexahydrophthalanhydride were charged into the same reaction apparatus as in Reference Example 1, and the temperature was raised to 100°C in a nitrogen stream. , and then the other raw material compositions were changed to - 168 parts of methyl methacrylate, 105 parts of ethyl acrylate, 70 parts of β-hydroxyethyl methacrylate, 3.2 parts of glycidyl methacrylate, 2'Lfc dispersion stabilization obtained in Reference Example 7. Except for changing to 41.1 parts of agent (a-1), 0.7 parts of 2-methylimidazole, 35 parts 6 parts of "Isopar E" and 3.4 parts of azobisisobutyronitrile. In the same manner as in Example 2, a dispersion of the desired fine particle polymer was obtained.

This was a milky white Venus with 40% NY and As in G and Via. Hereinafter, this will be abbreviated as fine particle polymer (D-3).

Comparative Example 1 As a control, the same procedure as in Example 1 was used, except that the sound used for intermediate (b-2) of Reference Example 7 was omitted, and 14 parts of methacrylic acid was used instead. A dispersion of a fine particle polymer was obtained.

This product had a milky white color with an NV of 40% and G and Vis of A. Hereinafter, and 2''L will be abbreviated as fine particle polymer (DL-1).

ntaso3(':jL) obtained in each of the above Examples and Comparative Examples
The degree of gelation of the fine particle polymer is as shown in Table 1.

Table 1 As described above, it is known that the fine particle polymer obtained according to the method of the present invention has a low degree of gelation.

Note that this "degree of gelation" was measured as follows.

That is, the resulting fine particle polymer dispersion.

Add 3 parts separately to 3 parts, stir for 30 minutes with a high speed stirrer, and then centrifuge 3. OOO
After separating for 2 hours at rpm, the supernatant was discarded. After that, 3 parts of acetone gold was added to the formula,
After performing the series of operations of stirring and centrifugation three times in total, the residue is dried, and the dry residue N content is expressed as a weight percentage of the initial solid content, and this "degree of gelation" is The higher the value, the higher the degree of gelling of the fine particle polymer.

Application Examples 1 to 9 Fine particle polymers (D-1) to (D
-3) and the hydroxyl group-containing heavy bodies (a-1) to (a-6) as main vehicle components for paints obtained in Reference Examples 1 to 6.
``Sumimar M-100CJ (
Hexamethoxymethylmelamine manufactured by Sumitomo Chemical ■;
Aminoplast with NV=100%] and, if necessary, a pigment are mixed in the proportions listed in Table 2, and then "Solbetun 1ook" (an aromatic hydrocarbon mixture manufactured by Ecun Corporation in the United States) is mixed. )/n-butanol=70/
Each paint was diluted to a spray viscosity using a mixed solvent total dilution thinner of 30 (volume ratio) to prepare each paint t''.

However, when it came to one-part color paints that also used pigments,
・Spray paint on a mild steel plate with α8 thickness to a dry film thickness of 40 mμ, and after setting for 30 minutes,
For clear paints that do not contain pigments, use metallic paste paints with the following formulation to a dry film thickness of 1.
Apply to a thickness of 2 μm or more, set for 5 minutes,
Next, this clear paint was applied to a dry film thickness of 40 mm, and after setting for 30 minutes,
J:n Baked at 140°C for 30 minutes.

The results of the evaluation of the gasoline resistance of the cured coating films thus obtained are summarized in Table 3.

'The formulation of the metallic base paint is as follows.

That is, 80 parts of hydroxyl group-containing polymers (a-2) 247 parts of fine particle polymer (D-1)
Sumimaru H-100CJ 60 parts "Alpaste 1109MAJ (Toyo Al 4 parts 2 parts aluminum base made of aluminum; NV = 65%)" Dilution thinner [Toluene/xylene/at acetic acid ethyl/seron lupacete - -] = 40/20/ 20/20 (capacity ratio) “Neighborhood 5225J (King α6, USA)
Comparative Application Examples 1 to 4 Comparative Application Examples 1 to 4 Paints were prepared in the same manner as Application Examples 1 to 9, film formation was performed, and gasoline resistance was evaluated, except that D'-1i was used as the fine particle polymer. .

In addition, in preparing the metallic paste paint used at that time, fine particle polymer (D'-1)'I
r was used.

As shown in Table 3, it is known that the coating film formed using the fine particle polymer obtained according to the method of the present invention has excellent gasoline resistance.

:4 Yaku [Effects of the present invention] The fine particle polymer obtained by the method of the present invention has a high degree of gelation as shown in Table 1, and therefore:
As shown in Table 6, the coating material to which the fine particle polymer obtained by the method of the present invention is added provides a coating film with excellent gasoline resistance, for example.

Claims (1)

[Scope of Claims] 1. Production of vinyl monomer The vinyl monomer described above is polymerized in a non-aqueous dispersion in the presence of a dispersion stabilizer in an organic solvent that does not dissolve the polymer; In a method for producing a microparticle polymer, which is a non-aqueous dispersion polymer crosslinked by intraparticle crosslinking, non-aqueous dispersion polymerization is carried out using an epoxy group-containing vinyl monomer as an essential vinyl monomer; A method for producing a particulate polymer, characterized in that intraparticle crosslinking is performed using a compound having two or more carboxyl groups in the molecule and/or a polycarboxylic acid anhydride. 2. The method according to claim 1, wherein the compound having two or more carboxyl groups in one molecule is a polyester resin. 3. The method according to claim 1, wherein the compound having two or more carboxyl groups in one molecule is an alkyd resin. 4. The method according to claim 1, characterized in that a polyester resin and an alkyd resin are used together as the compound having two or more carboxyl groups in one molecule. 5. The method according to claim 1, wherein the polycarboxylic anhydride is 3-methyl-tetrahydrophthalic anhydride. 6. The method according to claim 1, wherein the polycarboxylic anhydride is 3-methyl-hexahydrophthalic anhydride. 7. The method described in claim 1, characterized in that 3-methyl-tetrahydrophthalic anhydride and 6-methyl-hexahydrophthalic anhydride are used together as the polycarboxylic anhydride. .