JP6692230B2 - paint - Google Patents

Description

  The present invention relates to a coating material, and more particularly to a coating material in which decomposition of a haloacetylene compound is suppressed.

  It has been conventionally known to add haloacetylene compounds such as 3-iodo-2-propynylbutyl carbamate (IPBC) to paints for the purpose of antifungal properties.

  When such a coating material is an alkyd resin, the metal dryer contained together with the alkyd resin may accelerate the decomposition of the haloacetylene compound.

  Therefore, in order to suppress the decomposition of the haloacetylene compound, for example, it has been proposed to add a linseed oil epoxidized product to a composition containing IPBC (see, for example, Patent Document 1).

Japanese Patent Publication No. 2015-516381

  However, in the composition of Patent Document 1, suppression of decomposition of the haloacetylene compound may be insufficient.

  Then, the objective of this invention is providing the coating material which can further suppress decomposition | disassembly of a haloacetylene compound.

  The present invention (1) is a coating material containing an alkyd resin, an organic solvent, a metal drier, a haloacetylene compound, a polymer of a vinyl monomer containing an epoxy group, and an epoxidized unsaturated fatty acid ester.

  The present invention (2) includes the coating material according to (1) above, wherein the polymer of the epoxy group-containing vinyl monomer has a tetrahydrofuran-soluble content of 1.0% by mass or more.

  The present invention (3) further includes the coating material according to (1) or (2) above, which contains a color pigment.

  When the coating composition of the present invention contains an alkyd resin and a metal drier, it contains a polymer of an epoxy group-containing vinyl monomer and an epoxidized unsaturated fatty acid ester together with a haloacetylene compound.

  Therefore, according to the coating material of the present invention, the decomposition of the haloacetylene compound can be further suppressed.

  The coating material of the present invention contains an alkyd resin, an organic solvent, a metal drier, a haloacetylene compound, a polymer of an epoxy group-containing vinyl monomer, an epoxidized unsaturated fatty acid ester, and an organic solvent. ..

  In the present invention, the alkyd resin is an oxidative curing type alkyd resin that is cured by a metal drier, and is obtained, for example, by polycondensation and transesterification of polybasic acid and fatty acid (or fatty oil) with polyhydric alcohol. It is a synthetic resin.

  Examples of polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, maleic anhydride and the like.

  Examples of fatty acids include long-chain unsaturated fatty acids such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, and tall oil fatty acid.

  Examples of the fatty oil include soybean oil, linseed oil, castor oil, tung oil, dehydrated castor oil, safflower oil and the like. In the present invention, for example, a dry oil-modified alkyd using linseed oil, tung oil, dehydrated castor oil or the like, for example, soybean oil, safflower oil, or a semi-dry oil alkyd using tall oil fatty acid can be used. ..

  Examples of polyhydric alcohols include hydrogenated bisphenol A, glycerin, tris (2-hydroxyethyl) isocyanurate, and pentaerythritol.

  In addition, as the alkyd resin, a commercially available product can be used, and examples thereof include Haliftar series (specifically, Haliftar 764, Haliftar 816, and above Harima Kasei Group Co., Ltd.), Araquid series (Arakawa Chemical Industry Co., Ltd.). ), Beckosol series (manufactured by DIC) and the like.

  As alkyd resins, medium oil alkyd (oil content of alkyd excluding organic solvent (described later) is 45% or more and less than 55%), long oil alkyd (oil content of 55% or more and less than 65%), super long oil alkyd Any of (the same oil content is 65% or more) can be used, and long oil alkyd and ultralong oil alkyd are preferably used.

  These alkyd resins can be used alone or in combination of two or more kinds.

  The content ratio of the alkyd resin is, for example, 10 parts by mass or more, preferably 15 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less, relative to 100 parts by mass of the coating material. ..

  Such an alkyd resin is a solid or viscous liquid at room temperature, and is often used as a raw material for paints as an alkyd resin solution dissolved in an organic solvent (described later).

  The organic solvent is not particularly limited, and a known organic solvent can be used, and examples thereof include paraffin hydrocarbons, naphthene hydrocarbons, aromatic hydrocarbons, and the like.

  The paraffin hydrocarbon is a chain saturated hydrocarbon having a linear structure or a branched structure, and examples thereof include IP Solvent 1016 and IP Solvent 1620 (all manufactured by Idemitsu Kosan Co., Ltd.).

  The naphthene hydrocarbons are saturated hydrocarbons having a cyclic structure, and include, for example, Idemitsu Supersol CA25 (manufactured by Idemitsu Kosan Co., Ltd.), Exol D30 (manufactured by TonenGeneral Sekiyu KK), Exor D40 (manufactured by TonenGeneral Sekiyu KK), etc. Petroleum-based saturated hydrocarbons, such as cyclohexanes such as cyclohexane and methylcyclohexane.

  The aromatic hydrocarbons are hydrocarbons having an aromatic ring, and examples thereof include petroleum aromatic hydrocarbons such as Solvesso 150 (manufactured by ExxonMobil), for example, xylene.

  Further, examples of the organic solvent include industrial gasoline such as mineral spirit which is a mixture of petroleum hydrocarbons.

  Of these organic solvents, preferred are petroleum-based saturated hydrocarbons and petroleum-based aromatic hydrocarbons.

  These organic solvents can be used alone or in combination of two or more, and more preferably, a petroleum saturated hydrocarbon and a petroleum aromatic hydrocarbon are used in combination.

  The content ratio of the organic solvent is, for example, 50 parts by mass or more, preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and for example, 90 parts by mass or less with respect to 100 parts by mass of the coating material. It is preferably 80 parts by mass or less.

  The metal dryer is blended with the above-mentioned oxidation-curable alkyd resin. Then, the metal ions of the metal dryer are repeatedly oxidized and reduced to cure (oxidize) the alkyd resin.

  Examples of the metal dryer include metal salts of naphthenic acid, metal salts of octylic acid and the like.

  Examples of the metal include cobalt, barium, vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, cerium, nickel and tin.

  Of these, cobalt naphthenate and cobalt octylate are preferable.

  These metal dryers can be used alone or in combination of two or more kinds.

  The content ratio of the metal dryer is, for example, 0.05 parts by mass or more, preferably 0.25 parts by mass or more, and, for example, 5 parts by mass or less, preferably 2 parts with respect to 100 parts by mass of the alkyd resin. It is 0.5 parts by mass or less.

  The content ratio of the metal dryer is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and for example, 1 part by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the coating material. It is 0.5 parts by mass or less.

  When the content of the metal dryer is at least the above lower limit, curing of the alkyd resin can be promoted.

  Further, when the content ratio of the metal dryer is at most the above upper limit, it is possible to prevent the performance of the coating material from being impaired.

  The haloacetylene compound is represented by the following general formula (1).

(In the formula, R1 and R2 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent, X1 represents a halogen atom, and z represents an integer of 0 or 1.)
In the formula of the general formula (1), examples of the hydrocarbon group represented by R1 and R2 that may have a substituent include, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group and an aralkyl group. And so on.

  In formula (1), R1 is preferably a hydrogen atom or n-butyl.

  In formula (1), R2 is preferably a hydrogen atom or n-butyl.

  R1 and R2 are preferably different from each other, specifically, when R1 is a hydrogen atom, R2 is n-butyl, and when R1 is n-butyl, R2 is Is a hydrogen atom.

  In the formula (1), examples of the halogen atom represented by X1 include fluorine, chlorine, bromine and iodine. Preferred is iodine.

  In addition, z represents an integer of 0 or 1, and z is preferably 1.

  Of these haloacetylene compounds, preferably 3-iodo-2-propynylbutyl carbamate (IPBC) is used.

  These haloacetylene compounds can be used alone or in combination of two or more kinds.

  The content ratio of the haloacetylene compound is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and for example, 10 parts by mass with respect to 100 parts by mass in total of the alkyd resin and the organic solvent. Hereafter, it is preferably 5.0 parts by mass or less.

  The content ratio of the haloacetylene compound is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, and for example, 2000 parts by mass or less, relative to 100 parts by mass of the metal dryer.

  The content ratio of the haloacetylene compound is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 5.0 parts by mass or less, relative to 100 parts by mass of the coating material. It is preferably 3.0 parts by mass or less.

  When the content ratio of the haloacetylene compound is at least the above lower limit, it is possible to exhibit antifungal properties and other antibiotic activities.

  Further, when the content ratio of the haloacetylene compound is at most the above upper limit, it is possible to prevent the performance of the coating material from being impaired.

  The polymer of the epoxy group-containing vinyl monomer is obtained, for example, by polymerizing the epoxy group-containing vinyl monomer. The epoxy group-containing vinyl monomer polymer is preferably obtained as particles by polymerizing the epoxy group-containing vinyl monomer by various polymerization methods described below and, if necessary, drying. When the polymer of the epoxy group-containing vinyl monomer is obtained as particles, it can be dispersed in the paint.

  The epoxy group-containing vinyl monomer is selected from oil-soluble epoxy group-containing vinyl monomers, and examples thereof include epoxy group-containing (meth) acrylic acid ester monomers and epoxy group-containing ether monomers. Be done.

  The epoxy group-containing (meth) acrylic acid ester monomer is, for example, a methacrylic acid ester and / or an acrylic acid ester containing an epoxy group, and specifically, glycidyl acrylate (GA) and glycidyl methacrylate ( GMA), hydroxybutyl acrylate glycidyl ether and the like.

  Examples of the epoxy group-containing ether monomer include linear, branched or cyclic epoxy group-containing aliphatic ether monomers such as vinyl glycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether and 4-vinylcyclohexyl glycidyl ether. Examples include epoxy group-containing aromatic ether monomers such as 3-vinylbenzyl glycidyl ether and 4-vinylbenzyl glycidyl ether.

  Of these, an epoxy group-containing (meth) acrylic acid ester monomer is preferable, and glycidyl methacrylate (GMA) is more preferable.

  The method for polymerizing the epoxy group-containing vinyl monomer is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, miniemulsion polymerization, solution polymerization, and bulk polymerization.

  In emulsion polymerization, water, an epoxy group-containing vinyl monomer, an emulsifier, and a water-soluble polymerization initiator are mixed to polymerize the epoxy group-containing vinyl monomer.

  Examples of the emulsifier include anionic emulsifiers such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dodecyldiphenyl ether disulfonate, sodium nonyldiphenyl ether sulfonate, and naphthalenesulfonic acid formaldehyde condensate sodium salt, for example, poly Examples thereof include nonionic emulsifiers such as oxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers, polyoxyalkylene aralkyl aryl ethers, polyoxyalkylene block copolymers and polyoxyalkylene aryl ethers.

  Examples of the polyoxyalkylene alkyl ether include polyoxyethylene alkyl ether and the like.

  Examples of polyoxyalkylene alkylaryl ethers include polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether.

  Examples of the polyoxyalkylene aralkyl aryl ether include polyoxyethylene styrenated phenyl ether and the like.

  Examples of polyoxyalkylene block copolymers include polyoxyethylene-polyoxypropylene block copolymers.

  Examples of the polyoxyalkylene aryl ether include polyoxyethylene aryl ether and the like.

  Of these, anionic emulsifiers are preferable, and sodium lauryl sulfate is more preferable.

  The content ratio of the emulsifier is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 5.0 parts by mass with respect to 100 parts by mass of the epoxy group-containing vinyl monomer. Hereafter, it is preferably 3.0 parts by mass or less.

In emulsion polymerization, a dispersant may be used in addition to the emulsifier in order to obtain good polymerization stability.
As the dispersant, it is possible to use all of those mentioned in the suspension polymerization described below, the amount thereof is in accordance with the amount of the dispersant used in the suspension polymerization described later, and the method of its use is emulsification. The method of using the emulsifier in the polymerization is followed.

  Examples of the water-soluble polymerization initiator include 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis. (2-Amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis (N, N′-dimethylene) Isobutylamidine), 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis (1-imino-1-) Pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azo Sus [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate and other water-soluble azo compounds, for example, Persulfate compounds such as potassium sulfate, sodium persulfate, ammonium persulfate (APS), for example, water-soluble inorganic peroxides such as hydrogen peroxide, and water-soluble organic peroxides such as tert-butyl peroxide, cumene peroxide. Examples thereof include oxides. Furthermore, as the water-soluble polymerization initiator, for example, a water-soluble polymerization initiator excluding a water-soluble azo compound, ascorbic acid, a sulfite (a salt of a sulfite compound and an alkali metal) (for example, sodium hydrogen sulfite, sodium hyposulfite) , Sodium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, potassium hyposulfite, potassium sulfite, potassium hydrogen sulfite, etc.), sodium hydroxymethanesulfinate (Rongalit), thiourea dioxide, sodium thiosulfate, divalent iron salt, monovalent Redox water-soluble polymerization initiators in combination with water-soluble reducing agents such as copper salts and amines may also be mentioned.

  Of these, a redox water-soluble polymerization initiator is preferable, and a redox water-soluble polymerization initiator composed of a persulfate compound and a sulfite is preferable.

  If the water-soluble polymerization initiator contains a redox water-soluble polymerization initiator, the polymerization temperature described later can be lowered.

  These water-soluble polymerization initiators can be used alone or in combination of two or more kinds.

  The content ratio of the water-soluble polymerization initiator is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, and, for example, 5 parts by mass with respect to 100 parts by mass of the epoxy group-containing vinyl monomer. The amount is 0.0 parts by mass or less, preferably 3.0 parts by mass or less.

  When using a redox water-soluble polymerization initiator, the content ratio of the water-soluble reducing agent is, for example, 50 parts by mass or more, preferably 70 parts by mass or more, relative to 100 parts by mass of the water-soluble polymerization initiator, Moreover, for example, it is 150 parts by mass or less.

  As a method of emulsion polymerization, a known method is adopted, for example, a polymerization method in which an epoxy group-containing vinyl monomer, an emulsifier, and a water-soluble polymerization initiator are blended in water all at once and polymerized (all at once). Charging method), for example, a polymerization method (divided charging method) in which an epoxy group-containing vinyl monomer, an emulsifier, and a water-soluble polymerization initiator are divided into a plurality of parts and mixed in water to perform polymerization, for example, an epoxy group A part of the contained vinyl monomer, a part of the emulsifier, and a part of the water-soluble polymerization initiator are mixed in water to perform seed polymerization, and then the rest of each is continuously fed to carry out main polymerization. A legal method (continuous feed method) can be mentioned.

  In addition, in such emulsion polymerization, as a side reaction, a ring-opening reaction by addition of water to the epoxy group and a ring-opening reaction by addition of the generated hydroxyl group to the epoxy group occur. As a result, the concentration of epoxy groups decreases, and the crosslinking reaction of the reaction product is promoted.

  In order to control such a side reaction, it is desirable that the polymerization temperature is low and the polymerization time is short.

  Specifically, the polymerization temperature of the emulsion polymerization is, for example, 30 ° C. or higher, and for example, 70 ° C. or lower, preferably 65 ° C. or lower, and more preferably 60 ° C. or lower.

  The polymerization time of the emulsion polymerization is, for example, 3 hours or more, and for example, 8 hours or less, preferably 6 hours or less, more preferably 5 hours or less.

  Then, it is desirable to maintain the pH of the reaction liquid during the polymerization to be neutral.

  Specifically, the pH value of the reaction solution is, for example, 3 or more, preferably 5 or more, more preferably 6 or more, and for example, 9 or less, preferably 8 or less, more preferably 7. It is 5 or less.

  In particular, when the water-soluble polymerization initiator contains a persulfate compound, the pH is lowered during emulsion polymerization. Therefore, a pH adjuster is preferably added to the reaction solution, and the pH value of the reaction solution is set to the above value. Adjust to.

  Further, after the polymerization reaction, when the pH of the aqueous dispersion of the polymer of the epoxy group-containing vinyl monomer is low, thereafter, the particles (polymer) coexist with water as they are until they are taken out. A side reaction occurs. Therefore, it is preferable to add a pH adjuster to the reaction liquid after polymerization.

  Specifically, the pH adjuster is added to, for example, the reaction liquid during polymerization or the reaction liquid after polymerization, and preferably added to the reaction liquid during polymerization.

  For example, in the case of emulsion polymerization by the continuous feed method, the pH adjusting agent is added to the reaction solution of the seed polymerization and also added to the reaction solution of the main polymerization (feed) or added to the reaction solution after the polymerization. However, preferably, the pH adjuster is added to the reaction solution of the seed polymerization and also to the reaction solution of the main polymerization.

  By adding a pH adjuster to the reaction liquid during polymerization, the pH of the reaction liquid during polymerization can be maintained at a neutral level and the above-mentioned side reaction can be suppressed.

  Further, by adding a pH adjuster to the reaction liquid after polymerization, it is possible to suppress the above-mentioned side reaction that occurs until the particles (polymer) are taken out.

  Examples of the pH adjuster include alkaline pH adjusters such as ammonia and alkaline inorganic compounds.

  As the alkaline inorganic compound, for example, sodium hydroxide, potassium hydroxide, alkali metal hydroxides such as lithium hydroxide, for example, calcium hydroxide, magnesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, Examples thereof include alkali metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and lithium hydrogen carbonate.

  Of these, alkali metal carbonates are preferable, and sodium carbonate and sodium hydrogen carbonate are more preferable.

  The mixing ratio of the pH adjusting agent is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and for example, 100 parts by mass or less, preferably 80 parts by mass, relative to 100 parts by mass of the persulfate compound. Below the section.

  In suspension polymerization, a hydrophobic solution containing an epoxy group-containing vinyl monomer is prepared, the hydrophobic solution is dispersed in water, and the epoxy group-containing vinyl monomer is radically polymerized in the presence of an oil-soluble polymerization initiator. ..

  Specifically, first, an epoxy group-containing vinyl monomer is mixed with an oil-soluble polymerization initiator to prepare a hydrophobic solution (oil phase).

  Examples of the oil-soluble polymerization initiator include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate and diisopropyl. Oil-soluble organic peroxides such as peroxydicarbonate and benzoyl peroxide, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 Examples thereof include oil-soluble azo compounds such as'-azobis (2-methylbutyronitrile).

  Of these, oil-soluble organic peroxides are preferable.

  The content ratio of the oil-soluble polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and, for example, 5 parts by mass with respect to 100 parts by mass of the epoxy group-containing vinyl monomer. The amount is 0.0 parts by mass or less, preferably 3.0 parts by mass or less.

  Thereby, a hydrophobic solution is prepared.

  Next, the hydrophobic solution is dispersed (suspended) in water.

  To disperse (suspend) the hydrophobic solution in water, first, an aqueous dispersant solution (aqueous phase) is prepared.

  Specifically, a dispersant aqueous solution is prepared by mixing water and a dispersant and stirring them uniformly.

  Examples of the dispersant include water-soluble agents such as polyvinyl alcohol (PVA), polyvinylpyrrolidone, gelatin, gum arabic, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyacrylic acid and its sodium salt, styrene-maleic acid copolymer and its sodium salt. Polymers, for example, inorganic dispersants such as tribasic calcium phosphate, colloidal silica, montmorillonite, magnesium carbonate, aluminum hydroxide, zinc white, and the like, for example, sodium salt of a condensate of aromatic sulfonic acid and formaldehyde. ..

  Of these, polyvinyl alcohol (PVA) is preferable.

  The compounding ratio of the dispersant other than the sodium salt of the condensate of aromatic sulfonic acid and formaldehyde is, for example, 0.5 parts by mass or more, preferably 1 part by mass with respect to 100 parts by mass of the epoxy group-containing vinyl monomer. It is at least 20 parts by mass, preferably at most 10 parts by mass.

  Further, in order to obtain good polymerization stability, a sodium salt of a condensate of aromatic sulfonic acid and formaldehyde can be used together. The compounding ratio of the dispersant for the sodium salt of the condensate of aromatic sulfonic acid and formaldehyde is, for example, 0.01 part by mass or more, preferably 0.1 part by mass, relative to 100 parts by mass of the epoxy group-containing vinyl monomer. It is not less than 1.0 part by mass, and preferably not more than 1.0 part by mass, preferably not more than 0.5 part by mass.

  In addition, in order to ensure polymerization stability, a small amount of an emulsifier may be added to the aqueous dispersant solution.

  Examples of the emulsifier include those described above, and anionic emulsifiers and nonionic emulsifiers are preferable.

  These emulsifiers can be used alone or in combination of two or more kinds, and preferably an anionic emulsifier and a nonionic emulsifier are used together.

  The mixing ratio of the emulsifier is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and for example, 0.1 part by mass with respect to 100 parts by mass of the epoxy group-containing vinyl monomer. Hereafter, it is preferably 0.05 part by mass or less.

  Next, the hydrophobic solution is dispersed (suspended) in an aqueous dispersant solution.

  Specifically, an aqueous dispersant solution and a hydrophobic solution are mixed. As a result, the hydrophobic solution is dispersed (suspended) in an aqueous dispersant solution to obtain an aqueous dispersion.

  The mixing ratio of the hydrophobic solution is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass with respect to 100 parts by mass of the aqueous dispersion. It is below.

  In water dispersion (suspension) of the hydrophobic solution, for example, a homomixer (homomixer), an ultrasonic homogenizer, a pressure homogenizer, a milder, a porous membrane press-in disperser, or the like is used, and preferably a homomixer is used. Be done.

  The stirring conditions are appropriately set, and when a homomixer is used, the rotation speed thereof is set to, for example, 1000 rpm or more, preferably 1500 rpm or more, for example 5000 rpm or less.

  Next, the epoxy group-containing vinyl monomer in the hydrophobic solution dispersed in water is radically polymerized.

  In radical polymerization, for example, the reaction is started by heating an aqueous dispersion.

  As in the emulsion polymerization, a lower polymerization temperature is preferable and a shorter polymerization time is preferable.

  Specifically, the polymerization temperature of suspension polymerization is appropriately selected depending on the type of oil-soluble polymerization initiator, and is, for example, 30 ° C. or higher, and is, for example, 80 ° C. or lower, preferably 70 ° C. or lower.

  When the polymerization temperature of the suspension polymerization is not more than the above upper limit, the hydrolysis of the epoxy group of the epoxy group-containing vinyl monomer can be controlled.

  When the polymerization temperature of suspension polymerization is at least the above lower limit, the polymerization reaction can be stably carried out.

  The polymerization time of suspension polymerization is, for example, 3 hours or more, and for example, 8 hours or less, preferably 6 hours or less.

  When the polymerization time of suspension polymerization is not more than the above upper limit, the hydrolysis of the epoxy group of the epoxy group-containing vinyl monomer can be controlled.

  When the polymerization time of suspension polymerization is not less than the above lower limit, the conversion rate of the polymerization reaction can be sufficiently increased.

  In mini-emulsion polymerization, a hydrophobic solution containing an epoxy group-containing vinyl monomer and a hydrophobe is prepared, and the hydrophobic solution is emulsified in an aqueous emulsifier solution. In the presence of an oil-soluble polymerization initiator, the epoxy group-containing vinyl monomer is added. Polymerize the body.

  Specifically, first, an epoxy group-containing vinyl monomer, a hydrophobe, and an oil-soluble polymerization initiator are blended to prepare a hydrophobic solution (oil phase).

  The hydrophobe is a poorly water-soluble low molecular weight substance added to the epoxy group-containing vinyl monomer in order to maintain the epoxy group-containing vinyl monomer as stable oil droplets in the emulsion described later.

  As the hydrophob, for example, a long-chain alkyl compound such as hexadecane, for example, dodecyl methacrylate, stearyl methacrylate, or the like, an alkyl moiety having a long-chain alkyl methacrylate, for example, a higher alcohol such as cetyl alcohol, for example, olive oil. Such as oil.

  As the hydrophob, a long-chain alkyl compound is preferable, and hexadecane is more preferable.

  The mixing ratio of the hydrophob is, for example, 0.1 part by mass or more, preferably 1 part by mass or more, and for example, 10 parts by mass or less, relative to 100 parts by mass of the epoxy group-containing vinyl monomer. ..

  The type and blending ratio of the oil-soluble polymerization initiator are the same as those mentioned in the suspension polymerization.

  Thereby, a hydrophobic solution is prepared.

  Separately, water and an emulsifier are blended to prepare an emulsifier aqueous solution (aqueous phase).

  Specifically, an emulsifier aqueous solution is obtained by mixing water and an emulsifier and stirring them uniformly.

  Examples of the emulsifier include the emulsifiers described above.

  The mixing ratio of the emulsifier is, for example, 0.1 part by mass or more, preferably 1.0 part by mass or more, and for example, 20 parts by mass or less, relative to 100 parts by mass of the epoxy group-containing vinyl monomer. It is preferably 10 parts by mass or less.

  When the anionic emulsifier and the nonionic emulsifier are used in combination as the emulsifier, the mixing ratio of the anionic emulsifier is, for example, 10 parts by mass or more, and preferably 20 parts by mass or more, relative to 100 parts by mass of the nonionic emulsifier. And, for example, 80 parts by mass or less, preferably 60 parts by mass or less.

  In the mini-emulsion polymerization, a dispersant may be used in addition to the emulsifier in order to obtain good polymerization stability. As the dispersant, it is possible to use all those mentioned in the suspension polymerization, and the amount and method of use thereof are in accordance with the amount and method of use of the dispersant in suspension polymerization.

  As a result, an emulsifier aqueous solution is prepared.

  The hydrophobic solution is then emulsified in the aqueous emulsifier solution.

  Specifically, a hydrophobic solution is mixed with an emulsifier aqueous solution, and a high shearing force is applied to them to emulsify the hydrophobic solution into the emulsifier aqueous solution to prepare a mini-emulsion.

  The mixing ratio of the hydrophobic solution is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 150 parts by mass or less, preferably 90 parts by mass or less, relative to 100 parts by mass of the emulsifier aqueous solution. Is.

  For the emulsification of the hydrophobic solution, for example, a homomixer (homomixer), an ultrasonic homogenizer, a pressure homogenizer, a milder, a porous membrane press-fitting emulsifier, and the like are used, and preferably a homomixer is used.

  The stirring conditions are appropriately set, and when a homomixer is used, the rotation speed is set to, for example, 6000 rpm or more, preferably 8000 rpm or more, for example, 20000 rpm or less.

  The average particle size (median size) of the mini-emulsion particles is, for example, less than 1 μm, preferably 750 nm or less, more preferably 600 nm or less, further preferably less than 500 nm, and, for example, 100 nm or more, preferably 200 nm or more. Is.

  Next, the emulsified hydrophobic solution-containing epoxy group-containing vinyl monomer is radically polymerized.

  In radical polymerization, the aqueous dispersion is heated to initiate polymerization.

  As in the emulsion polymerization, a lower polymerization temperature is preferable and a shorter polymerization time is preferable.

  Specifically, the polymerization temperature of the mini-emulsion polymerization is appropriately selected depending on the type of the oil-soluble polymerization initiator, and is, for example, 30 ° C. or higher and, for example, 80 ° C. or lower, preferably 70 ° C. or lower.

  When the polymerization temperature of the miniemulsion polymerization is not more than the above upper limit, hydrolysis of the epoxy group of the epoxy group-containing vinyl monomer can be controlled.

  When the polymerization temperature of the miniemulsion polymerization is at least the above lower limit, the polymerization reaction can be stably carried out.

  The polymerization time of the miniemulsion polymerization is, for example, 3 hours or more, and for example, 8 hours or less, preferably 6 hours or less.

  When the polymerization time of the miniemulsion polymerization is not more than the above upper limit, the hydrolysis of the epoxy group of the epoxy group-containing vinyl monomer can be controlled.

  When the polymerization time of the miniemulsion polymerization is not less than the above lower limit, the conversion rate of the polymerization reaction can be sufficiently increased.

  Then, the aqueous dispersion of the polymer of the epoxy group-containing vinyl monomer obtained by the above various polymerization methods is dried by using, for example, a spray dryer to remove water.

  As a result, particles made of a polymer of epoxy group-containing vinyl monomer are obtained.

  In addition, in the polymerization of the epoxy group-containing vinyl monomer, copolymerizable with the epoxy group-containing vinyl monomer and copolymerizable with the epoxy group-containing vinyl monomer as long as the excellent effects of the present invention are not impaired. The monomers can be copolymerized.

Examples of the copolymerizable monomer include, for example, an epoxy group-free monomer and a polymerizable carbon-
Examples thereof include copolymerizable monomers having at least one carbon double bond in the molecule.

  Examples of the copolymerizable monomer include (meth) acrylic acid ester-based monomers, (meth) acrylic acid-based monomers, aromatic vinyl monomers, ether-based monomers, vinyl ester-based monomers. Examples thereof include a monomer, a maleic acid ester-based monomer, a vinyl halide monomer, and a nitrogen-containing vinyl monomer.

  The mixing ratio of the copolymerizable monomer is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the epoxy group-containing vinyl monomer. ..

  In the polymerization of the epoxy group-containing vinyl monomer, preferably, the copolymerizable monomer is not contained and only the epoxy group-containing vinyl monomer is polymerized. Therefore, the polymer of the epoxy group-containing vinyl monomer is preferably a polymer of only the epoxy group-containing vinyl monomer, more preferably a homopolymer of the epoxy group-containing vinyl monomer (that is, 1 It is a polymer of only a vinyl monomer containing an epoxy group).

  However, in emulsion polymerization, the epoxy group-containing vinyl monomer is dissolved in the aqueous phase from the oil droplets of the epoxy group-containing vinyl monomer, then the epoxy group-containing vinyl monomer moves to the polymer particles, and the polymerization Therefore, the epoxy group of the epoxy group-containing vinyl monomer is easily opened by hydrolysis. Therefore, when the epoxy group of the epoxy group-containing vinyl monomer is ring-opened and the generated hydroxyl group reacts with the epoxy group of the polymer of the epoxy group-containing vinyl monomer, a cross-linking reaction occurs, and the epoxy group-containing vinyl described below is obtained. Tetrahydrofuran soluble content of the monomer polymer is reduced.

  On the other hand, in suspension polymerization and mini-emulsion polymerization, the epoxy group-containing vinyl monomer undergoes in-situ polymerization. Therefore, since the epoxy group-containing vinyl monomer exists only in the hydrophobic phase (oil phase), ring opening of the epoxy group of the epoxy group-containing vinyl monomer due to hydrolysis is less likely to occur as compared with emulsion polymerization. Therefore, the tetrahydrofuran-soluble content of the polymer of the epoxy group-containing vinyl monomer described below increases. Thereby, the decomposition of the haloacetylene compound can be further suppressed.

  Then, the tetrahydrofuran-soluble content of the obtained polymer of the epoxy group-containing vinyl monomer is, for example, 0.5% by mass or more, preferably 1.0% by mass or more, and more preferably 3.0% by mass. As described above, the content is more preferably 7.0% by mass or more, particularly preferably 10% by mass or more, and for example, 30% by mass or less.

  When the tetrahydrofuran-soluble content of the polymer of the epoxy group-containing vinyl monomer is within the above range, the crosslinking reaction due to ring opening of the epoxy group of the epoxy group-containing vinyl monomer is suppressed. Therefore, the decomposition of the haloacetylene compound can be further suppressed by the epoxy group of the polymer of the epoxy group-containing vinyl monomer dissolved in the organic solvent.

  Further, the tetrahydrofuran-soluble component of the polymer of the epoxy group-containing vinyl monomer is obtained as follows.

  For example, first, a powder of a polymer of an epoxy group-containing vinyl monomer is precisely weighed in a predetermined amount (for example, 2.5 g), added to 25 ml of tetrahydrofuran, and then shaken, and then at room temperature, The powder of the polymer of the vinyl monomer containing an epoxy group is dissolved in tetrahydrofuran by dipping for 96 hours. Then, the content of the polymer of the epoxy group-containing vinyl monomer in the supernatant of the immersion liquid (for example, 5 ml) (supernatant) was measured. The content (total amount) of the polymer of the epoxy group-containing vinyl monomer in tetrahydrofuran is calculated from the obtained content (supernatant solution), and the tetrahydrofuran-soluble component (content (total amount) / predetermined amount) is calculated. ..

  The blending ratio of the polymer of the epoxy group-containing vinyl monomer in the paint is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, and, for example, 300 parts by mass with respect to 100 parts by mass of the haloacetylene compound. It is not more than 200 parts by mass, preferably not more than 200 parts by mass.

  The mixing ratio of the epoxy group-containing vinyl monomer polymer in the paint is, for example, 0.1 parts by mass or more, and preferably 0.5 parts by mass or more, relative to 100 parts by mass of the paint. For example, it is 5.0 parts by mass or less, preferably 3.0 parts by mass or less.

  When the blending ratio of the epoxy group-containing vinyl monomer polymer in the coating material is at least the above lower limit, the decomposition of the haloacetylene compound can be further suppressed.

  Further, when the blending ratio of the polymer of the epoxy group-containing vinyl monomer in the paint is not more than the above upper limit, it is possible to prevent the performance of the paint from being impaired.

  Examples of the epoxidized unsaturated fatty acid ester include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized rapeseed oil, and epoxidized sunflower oil.

  Of these, epoxidized linseed oil is preferable from the viewpoint of low epoxy equivalent (high oxirane oxygen content).

  These epoxidized unsaturated fatty acid esters can be used alone or in combination of two or more kinds.

  The oxirane oxygen content of the epoxidized unsaturated fatty acid ester is, for example, 4% or more, preferably 6% or more, more preferably 8% or more, and, for example, 10% or less.

  The blending ratio of the epoxidized unsaturated fatty acid ester in the coating material is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, and, for example, 300 parts by mass or less, with respect to 100 parts by mass of the haloacetylene compound. It is preferably 200 parts by mass or less.

  The blending ratio of the epoxidized unsaturated fatty acid ester in the coating material is, for example, 50 parts by mass or more, preferably 80 parts by mass or more, relative to 100 parts by mass of the epoxy group-containing vinyl monomer polymer. Further, for example, it is 150 parts by mass or less, preferably 130 parts by mass or less.

  The blending ratio of the epoxidized unsaturated fatty acid ester in the coating material is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and, for example, 5 parts by mass with respect to 100 parts by mass of the coating material. The amount is 0.0 parts by mass or less, preferably 3.0 parts by mass or less.

  When the compounding ratio of the polymer of the epoxidized unsaturated fatty acid ester in the coating material is at least the above lower limit, the decomposition of the haloacetylene compound can be further suppressed.

  Further, when the blending ratio of the polymer of the epoxidized unsaturated fatty acid ester in the coating material is not more than the above upper limit, it is possible to prevent the performance of the coating material from being impaired.

  The coating material of the present invention may further contain a coloring pigment.

  Examples of color pigments include inorganic pigments, organic pigments, and flake pigments.

  Examples of the inorganic pigments include metal oxides such as titanium oxide (titania), zinc oxide (zinc white), yellow iron oxide, red iron oxide (black iron), black iron oxide (iron black), and chromium oxide (III), For example, chromate salts such as chrome yellow (yellow lead) and chrome vermillion (molybdenum red), for example, sulfides such as lithobon, cadmium yellow, and cadmium red, such as deep blue (purshan blue), ultramarine blue (ultramarine blue). ) And the like, for example, carbon such as carbon black and the like.

  Examples of organic pigments include Fast Yellow G (CI Pig Yellow 1), Isoindolinone Yellow R (CI Pig Yellow 110), Pyrazolone Orange (CI Pig Orange 13), and Naphthol Carmine FB (C.I. CI Pig Red 5), quinacridone magenta (CI Pig Red 122), quinacridone red (CI Pig Violet 19), dioxazine violet (CI Pig Violet 23), phthalocyanine blue R (CI Pig Blue 15). ), Phthalocyanine green (CI Pig Green 7), indanthrone blue (CI Pig Blue 60), and the like.

  Examples of the flake pigment include aluminum flake, mica, colored mica, silica flake, glass flake and the like.

  Of these, inorganic pigments are preferable, and metal oxides are more preferable. Further, when the paint is a white paint, titanium oxide (titania) is preferable.

  These color pigments can be used alone or in combination of two or more kinds.

  The mixing ratio of the coloring pigment varies depending on the coloring ability of the pigment, but is, for example, 0.01 parts by mass or more and 100 parts by mass or less, for 100 parts by mass of the coating material.

  If the paint further contains a coloring pigment, the paint can be colored.

  Then, in order to prepare the coating material of the present invention, an alkyd resin, an organic solvent, a metal dryer, a haloacetylene compound, a polymer of an epoxy group-containing vinyl monomer, and an epoxidized unsaturated fatty acid ester are necessary. According to the above, the coloring pigment is mixed in the above-mentioned ratio, and they are stirred at room temperature. Thereby, the paint is prepared.

  The paint thus prepared contains an alkyd resin and a metal drier. Therefore, the decomposition of the haloacetylene compound is promoted.

  However, the coating material thus prepared contains a polymer of an epoxy group-containing vinyl monomer and an epoxidized unsaturated fatty acid ester together with a haloacetylene compound.

  Therefore, even if the paint contains a metal dryer, the decomposition of the haloacetylene compound can be suppressed.

  When the coating material contains a color pigment, the color pigment may further accelerate the decomposition of the haloacetylene compound.

  However, the coating material of the present invention contains a polymer of an epoxy group-containing vinyl monomer and an epoxidized unsaturated fatty acid ester together with a haloacetylene compound.

  Therefore, even when the paint contains a color pigment, the decomposition of the haloacetylene compound can be suppressed.

  In addition, for example, in Japanese Patent Publication No. 2014-31365, it is proposed to include a haloacetylene compound such as 3-iodo-2-propynylbutylcarbamate (IPBC) in a polymer particle containing an epoxy group.

  However, when such particles are blended with a coating material containing an organic solvent, the haloacetylene compound in the particles may be dissolved in the organic solvent, which may reduce the stability of the haloacetylene compound.

  However, the coating material of the present invention contains a polymer of an epoxy group-containing vinyl monomer and an epoxidized unsaturated fatty acid ester together with a haloacetylene compound.

  Therefore, the haloacetylene compound can exist stably even in an organic solvent.

  The coating material of the present invention is not particularly limited, and includes, for example, coating material for exterior building materials of wooden buildings, paint for wooden exterior materials such as playground equipment, decks, bridges, guardrails, fences, floors, walls, pillars, doors, and ceilings. It can be used as a paint for wood interiors, and a paint for wood furniture, and can be preferably used as a paint for exterior building materials of wood buildings, a paint for wood exteriors, and the like.

  The method for applying the prepared coating material is not particularly limited, and examples thereof include brush coating, roller coating, and spray coating.

  Then, the coating material applied by the above method is dried and oxidatively cured to form a coating film.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to the examples and comparative examples. Further, specific numerical values such as a mixing ratio (content ratio), a physical property value, and a parameter used in the following description are described in the above-mentioned "Description of Embodiments", and a corresponding mixing ratio ( Substitute the upper limit value (value defined as "below" or "less than") or the lower limit value (value defined as "greater than or equal to" "exceeding") such as content ratio), physical property value, parameter etc. be able to.

  The trade names or abbreviations of the active ingredients used in the following Examples and Comparative Examples are shown below.

IPBC: 3-iodo-2-propynylbutyl carbamate, manufactured by Troy GMA: glycidyl methacrylate, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. Emal 2FG: trade name, sodium lauryl sulfate, anionic emulsifier, manufactured by Kao Neocor SW-C: trade name , 70% by mass solution of sodium dioctylsulfosuccinate in isopropanol, anionic emulsifier, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Pronone 208: trade name, polyoxyethylene polyoxypropylene block copolymer, nonionic emulsifier, NOF CORPORATION Neugen EA-177: Trade name, polyoxyethylene styrenated phenyl ether, nonionic emulsifier, Dai-ichi Kogyo Seiyaku Co., Ltd. PVA217: trade name, polyvinyl alcohol, Kuraray Demol NL: trade name, β-naphthalenesulfonic acid formalin condensate sodium , Dispersant, manufactured by Kao APS: ammonium persulfate, water-soluble polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd. SBS: sodium bisulfite, water-soluble reducing agent, manufactured by Wako Pure Chemical Industries, perloyl L: trade name, dilauroyl peroxide, Japanese Adeka Sizer O-180A (trade name): trade name, epoxidized linseed oil (oxirane oxygen content: 9.1%), ADEKA Co., Ltd. Haliftal 764: trade name, alkyd resin (semi-drying oil alkyd, long oil alkyd, oil length) 63%, non-volatile content 70%, mineral spirit 30%), manufactured by Harima Kasei Group Co., Ltd. Cobalt dryer: Co-OCTOATE 8% (Co content 8%, mineral spirit solution), manufactured by DIC Idemitsu Super Sol CA25: trade name, petroleum -Based saturated hydrocarbons, Solvesso 150 manufactured by Idemitsu Kosan Co., Ltd .: trade name, petroleum-based aromatic hydrocarbons, Kusonmobiru Co., Ltd. 1. Preparation of Polyglycidyl Methacrylate (PGMA) Preparation Example 1 (Emulsion Polymerization)
a) Seed polymerization To a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 132.0 g of ion-exchanged water and 0.2 g of Emal 2FG were added and dissolved, whereby an emulsifier was obtained. An aqueous solution was prepared. Then, after substituting with nitrogen and adding 20.0 g of GMA as an epoxy group-containing vinyl monomer, dipping it in a water bath and rotating with a stirring blade of 6 cm diameter at a rotation speed of 200 rpm (peripheral speed 37.7 cm / min). The temperature was raised with stirring. This prepared the emulsion.

  At an inner temperature of 55 ° C., an aqueous solution (water-soluble polymerization initiator) in which APS 0.03 g was dissolved in ion-exchanged water 1.5 g, and an aqueous solution in which SBS 0.024 g was dissolved in ion-exchanged water 1.2 g (water-soluble reduction) Agent) was added.

The light blue color of the emulsion confirmed that the initiation of the polymerization reaction of the emulsion polymerization, and then the reaction was continued for 30 minutes. As a result, a reaction liquid was obtained.
b) Main Polymerization In a 500 mL container, 70.0 g of ion-exchanged water and 1.8 g of Emal 2FG were added and dissolved. This prepared the feed emulsifier aqueous solution.

  Next, 180.0 g of GMA was added to the obtained aqueous solution and stirred to prepare a GMA emulsion (feed emulsion).

  The prepared GMA emulsion (feed emulsion) was continuously fed to the reaction solution by a tubing pump over 3 hours.

  At the same time, an aqueous solution of 0.57 g of APS dissolved in 28.5 g of ion-exchanged water (feed water-soluble polymerization initiator), and an aqueous solution of 0.456 g of SBS dissolved in 22.8 g of ion-exchanged water (feed water-soluble reducing agent) Was continuously fed over 3.5 hours to control the liquid temperature at 60 to 65 ° C.

  After the completion of feeding the GMA emulsion, the inside of the container and the tube was washed with 12.0 g of ion-exchanged water, the washing solution was fed into the reaction solution, and the reaction was aged at 60 to 65 ° C for 1.5 hours, and then 40 The reaction was completed by cooling below ℃.

  Thereby, an emulsion of PGMA was obtained.

The resulting PGMA emulsion was allowed to stand at room temperature for 5 days, and then a spray dryer L-8 type (manufactured by Okawara Kakoki Co., Ltd.) was used to feed 2.1 kg / Hr of liquid, atomizer speed 24000 rpm, and inlet temperature. Spray-drying was performed at 100 ° C. and an outlet temperature of 50 to 55 ° C. to obtain PGMA powder.
c) Measurement of Tetrahydrofuran Soluble Content 2.5 g of the obtained PGMA powder was precisely weighed and added to, for example, 25 ml of tetrahydrofuran, then shaken, and then immersed at room temperature for 96 hours to obtain the PGMA powder. It was dissolved in tetrahydrofuran. Then, the content of the PGMA powder in 5 ml of the supernatant of the immersion liquid (supernatant) was measured. Next, the content (total amount) of PGMA powder in tetrahydrofuran was calculated from the obtained content (supernatant liquid), and the tetrahydrofuran-soluble component (content (total amount) / predetermined amount) was calculated. The tetrahydrofuran-soluble component was 0.5% by mass.

  The compounding recipe of each component is shown in Table 1.

Preparation Example 2 (emulsion polymerization)
When the reaction was completed by cooling, PGMA powder was obtained by spray drying in the same manner as in Preparation Example 1 except that 1.3 g of a 2% aqueous sodium carbonate solution was added to the reaction solution as a pH adjusting agent.

  The tetrahydrofuran-soluble content was 2.9% by mass.

Preparation Example 3 (emulsion polymerization)
The formulation of each component was changed according to the description in Table 1, except that 0.04 g of sodium hydrogen carbonate was added to the emulsifier aqueous solution and 0.32 g of sodium hydrogen carbonate was added to the feed emulsifier aqueous solution as a pH adjuster. Spray drying was performed in the same manner as in Preparation Example 1 to obtain PGMA powder.

  The tetrahydrofuran-soluble component was 6.4% by mass.

  The compounding recipe of each component is shown in Table 1.

Preparation Example 4 (suspension polymerization)
A hydrophobic solution (oil phase) was prepared by adding 112.6 g of GMA and 0.6 g of perloyl L to a 200 mL beaker and uniformly stirring at room temperature.

  Separately, in a 1000 mL beaker, 240.0 g of ion-exchanged water, 45.0 g of a 10 mass% PVA-217 aqueous solution, 1.1 g of a 1 mass% aqueous solution of pronone 208, and 0.5 g of demole NL were added and stirred uniformly at room temperature. A dispersant aqueous solution (aqueous phase) was prepared by.

  Then, the dispersant aqueous solution and the hydrophobic solution are blended, and T.I. K. A hydrophobic solution was uniformly suspended by stirring with a homomixer MARK 2.5 type (manufactured by Primix Co., Ltd.) at a rotation speed of 2500 rpm for 5 minutes to prepare a suspension.

  Then, the obtained suspension was added to a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introducing tube, and heated under stirring under a nitrogen stream to polymerize the suspension.

  Polymerization was started when the temperature of the suspension reached 55 ° C. while heating the suspension. Then, the temperature was maintained at 70 ° C. for 6 hours and then cooled to room temperature.

  As a result, a suspension of PGMA particles having an average particle diameter of 17.5 μm was obtained.

  The obtained PGMA suspension was spray-dried in the same manner as in Preparation Example 1 to obtain PGMA powder.

  The tetrahydrofuran-soluble content was 10.8% by mass.

  Table 2 shows the formulation of each component.

Preparation Example 5 (miniemulsion polymerization)
A hydrophobic solution (oil phase) was prepared by adding 114.0 g of GMA, 6.0 g of hexadecane (hydrophobe) and 1.2 g of perloyl L to a 200 mL beaker and uniformly stirring at room temperature.

  Separately, 254.8 g of ion-exchanged water, 4.0 g of Neocor SW-C, and 20.0 g of 25 mass% aqueous solution of Neugen EA-177 were added to a 1000 mL beaker, and the mixture was uniformly stirred at room temperature to give an emulsifier aqueous solution (aqueous phase). ) Was prepared.

  Then, an emulsifier aqueous solution and a hydrophobic solution are mixed, and T. K. A mini-emulsion was prepared by homogenizing a hydrophobic solution uniformly with water using a homomixer MARK 2.5 type (manufactured by PRIMIX) for 5 minutes at a rotation speed of 10,000 rpm.

  Then, the obtained mini-emulsion was added to a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and the temperature was raised with stirring under a nitrogen stream to polymerize the mini-emulsion.

  Polymerization was started when the temperature of the miniemulsion reached 55 ° C while the temperature of the miniemulsion was being raised. Then, it was maintained at 70 ° C. for 2 hours, and then cooled to room temperature.

As a result, a suspension of PGMA particles having an average particle diameter of 441 nm was obtained.
The obtained PGMA suspension was spray-dried in the same manner as in Preparation Example 1 to obtain PGMA powder.

  The tetrahydrofuran-soluble component was 12.1% by mass.

  Table 2 shows the formulation of each component.

2. Preparation of paint Example 1
In a 2000 ml container, Idemitsu Supersol CA25 524.0 g, Solvesso 150 50.0 g, titanium oxide (R-980, Ishihara Sangyo Co., Ltd.) 200.0 g, Haliftal 764 200.0 g, cobalt dryer 1.0 g, IPBC 10.0 g, ADEKA. 10.0 g of Sizer O-180A and 10.0 g of PGMA powder of Preparation Example 1 were added, and the mixture was stirred with a stirring blade having a diameter of 6 cm at a rotation speed of 1000 rpm (peripheral speed 188.5 cm / min).

  Thereby, the paint was obtained.

Example 2
In a 2000 ml container, Idemitsu Supersol CA25 691.8 g, Solvesso 150 60.0 g, yellow iron oxide (TSY-1, manufactured by Toda Kogyo Co., Ltd.) 20.0 g, red iron oxide (120 ED, manufactured by Toda Kogyo Co., Ltd.) 2.0 g, carbon black. (MA230, manufactured by Mitsubishi Chemical Co., Ltd.) 0.2 g, Haliftal 764 200.0 g, cobalt dryer 1.0 g, IPBC 10.0 g, ADEKA CIZER O-180A 10.0 g, and PGMA powder 10.0 g of Preparation Example 1. In addition, stirring was carried out at a rotation speed of 1000 rpm (peripheral speed 188.5 cm / min) with a 6 cm diameter stirring blade.

  Thereby, the paint was obtained.

Example 3
In a 2000 ml container, Idemitsu Supersol CA25 683.5 g, Solvesso 150 60.0 g, yellow iron oxide (TSY-1, manufactured by Toda Kogyo Co., Ltd.) 15.0 g, red iron oxide (120 ED, manufactured by Toda Kogyo Co., Ltd.) 15.0 g, carbon black. (MA230, manufactured by Mitsubishi Chemical Co., Ltd.) 0.5 g, halyphtal 764 200.0 g, cobalt dryer 1.0 g, IPBC 10.0 g, ADEKA CIZER O-180A 10.0 g, and PGMA powder 10.0 g of Preparation Example 1 were added, Stirring was performed at a rotation speed of 1000 rpm (peripheral speed 188.5 cm / min) with a stirring blade having a diameter of 6 cm.

  Thereby, the paint was obtained.

Example 4
In a 2000 ml container, Idemitsu Supersol CA25 689.0 g, Solvesso 150 60.0 g, yellow iron oxide (TSY-1, manufactured by Toda Kogyo Co., Ltd.) 8.0 g, red iron oxide (120 ED, manufactured by Toda Kogyo Co., Ltd.) 12.0 g, carbon black. (MA230, manufactured by Mitsubishi Chemical Co., Ltd.) 5.0 g, Haliftal 764 200.0 g, cobalt dryer 1.0 g, IPBC 10.0 g, ADEKA CIZER O-180A 10.0 g, and PGMA powder 10.0 g of Preparation Example 1 were added, Stirring was performed at a rotation speed of 1000 rpm (peripheral speed 188.5 cm / min) with a stirring blade having a diameter of 6 cm.

  Thereby, the paint was obtained.

Examples 5-20, Comparative Examples 1-8
A coating material was obtained in the same manner as in Example 1 except that the formulation of each component was changed according to Tables 3 to 6.

Comparative Examples 9-12
A coating material was obtained in the same manner as in Example 1 except that GMA was added instead of PGMA powder.

3. Evaluation The paints of Examples 1 to 20 and Comparative Examples 1 to 12 were added to a glass container, sealed, and left at 50 ° C for 8 weeks.

  Then, the content of IPBC was measured by high performance liquid chromatography (HPLC).

  The residual rate of IPBC (content of IPBC after standing / content of IPBC before standing) was calculated, and suppression of decomposition of IPBC was evaluated.

  The results are shown in Tables 3-6.

Claims (3)

Alkyd resin,
An organic solvent,
A metal dryer,
A haloacetylene compound,
A polymer of epoxy group-containing vinyl monomer,
A coating material comprising an epoxidized unsaturated fatty acid ester.   The coating material according to claim 1, wherein the polymer of the epoxy group-containing vinyl monomer has a tetrahydrofuran-soluble content of 1.0% by mass or more.   The coating composition according to claim 1 or 2, further comprising a coloring pigment.