JP2008007688A - Thermosetting fine particle and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide thermosetting resin fine particles applicable to optical uses, capable of controlling a particle diameter, having a uniform particle diameter and substantially containing no dispersion stabilizer. <P>SOLUTION: The thermosetting resin fine particle is obtained by polymerizing monofunctional and polyfunctional ethylenically unsaturated monomers with use of a radical polymerization initiator in water and/or an alcoholic solvent in the absence of a dispersion stabilizer. The particle contains the monofunctional and/or polyfunctional ethylenically unsaturated monomers having a functional group expressed by structural formula (1) (in the formula R<SB>1</SB>is a hydrogen atom or a 1-6C alkyl group). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to thermosetting resin fine particles that are cured by heat, and more particularly to thermosetting monodispersed resin fine particles that are micron-sized and have a narrow particle size distribution. The thermosetting resin fine particles obtained in the present invention can be used by adding to a thermosetting resin binder or a thermosetting monomer, and are used as an antiblocking agent, a light diffusing agent, a light scattering agent, a spacer, or a film. It is useful as a reinforcing agent, a resin modifier for modifying mechanical strength, a matting agent, and a lubricant.

  Conventionally, studies have been made to disperse reactive resin fine particles in a matrix resin and to apply this as a reinforcing agent. For example, Patent Document 1 discloses resin fine particles in which resin fine particles are produced by emulsion polymerization, and the resulting fine particles are used as seeds for further seed emulsion polymerization to leave vinyl groups on the surface. Patent Document 2 discloses a method in which an ethylenically unsaturated bond is present at the end of a carbon chain extending outward from resin fine particles through a reaction between an active hydrogen group and an isocyanate group. However, these are methods in which unsaturated groups remain as reactive groups, and can be applied to uses that are cured by ultraviolet rays or electron beams. However, in applications that are cured by heat, warping, cracking, etc. It can cause problems and is not very effective.

  On the other hand, a cyclic ether group is mentioned as a thermosetting functional group. Among them, a trimethyleneoxy group is a 4-membered cyclic ether, and compared with an epoxy group known as a thermosetting functional group, It is a stable functional group with a high thermal decomposition temperature and heat resistance. In addition, since thermosetting proceeds slowly, problems such as warpage that occur in the case of unsaturated groups are also eliminated. So far, inventions related to dispersed resin compositions containing trimethyleneoxy groups have been disclosed. For example, in Patent Document 3, a block copolymer containing trimethyleneoxy groups, carboxyl groups, and sulfonic acid compounds is used as a suspension stabilizer. By producing the thermosetting water-based paint composition as described above, the VOC (Volatile Organic Compounds) of the paint has been reduced. Patent Document 4 discloses an invention relating to an original plate for lithographic printing, in which developability on a printing press is improved by using polymer fine particles having a thermally reactive group such as a trimethyleneoxy group.

However, the thermosetting group-containing resin fine particles obtained in Patent Document 3 are not crosslinked and have a problem in versatility to non-aqueous systems. Further, since the polymer fine particles of Patent Document 4 are fine particles synthesized to solve the problems on the lithographic printing original plate, they do not take into consideration advantageous characteristics in optical design, and in recent years, the light diffusing agent has been particularly demanded. It is not suitable for application to light scattering agents and spacers. Patent Documents 3 and 4 both use a large amount of a dispersion stabilizer and a surfactant for the purpose of maintaining the dispersion stability of the particles. For this reason, there is a possibility of causing a harmful effect when the compatibility with the coating film is lowered or various physical properties are controlled.
Japanese Patent No. 2722661 Japanese Patent Publication No.7-86125 Japanese Patent Laid-Open No. 2002-179990 JP 2003-291552 A

  An object of the present invention is to provide optically designed thermosetting resin fine particles that can be used for optical applications such as a light diffusing agent, a light scattering agent, and a spacer. That is, an object of the present invention is to provide thermosetting resin fine particles having a controllable particle size and having a uniform particle size, and further substantially free of a dispersion stabilizer.

  Furthermore, the object of the present invention is to provide thermosetting resin fine particles that can improve heat resistance, solvent resistance, and pencil hardness by thermosetting, and to improve the adhesion and pencil hardness in a state where the amount of warpage is suppressed. An object of the present invention is to provide a thermosetting composition containing the resin fine particles that can be produced.

  In the present invention, a monofunctional ethylenically unsaturated monomer and a polyfunctional ethylenically unsaturated monomer are radically polymerized with a radical polymerizable initiator in water and / or an alcohol solvent in the absence of a dispersion stabilizer. A resin fine particle comprising a monofunctional ethylenically unsaturated monomer and / or a polyfunctional ethylenically unsaturated monomer having at least a functional group of the following structural formula (1): It relates to the thermosetting resin fine particles to be contained.

(ただし、Ｒ₁は水素原子または炭素数１〜６のアルキル基である。)

(Wherein, R ₁ is hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

  Furthermore, the present invention relates to the above thermosetting resin fine particles having an average particle size of 0.5 to 3.0 μm and a coefficient of variation of 10% or less.

  Furthermore, the present invention relates to a thermosetting composition comprising the thermosetting resin fine particles, a thermosetting resin binder and / or a thermosetting monomer.

  Furthermore, the present invention provides a dispersion-stabilized monofunctional ethylenically unsaturated monomer and polyfunctional ethylenically unsaturated monomer containing at least an ethylenically unsaturated monomer having a functional group represented by the following structural formula (1). The present invention relates to a method for producing thermosetting resin fine particles characterized by radical polymerization with a radical polymerizable initiator in water and / or alcohol solvent in the absence of an agent.

(ただし、Ｒ₁は水素原子または炭素数１〜６のアルキル基である)

(Wherein, R ₁ is hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

  According to the present invention, thermosetting resin fine particles having a functional group that reacts by heat and having a uniform particle diameter can be provided. More specifically, it is a thermosetting resin fine particle that can be dispersed even in a non-aqueous solvent, and when added to a thermosetting coating agent, it improves adhesion and pencil hardness while suppressing the amount of warpage, and further heat resistance. Thermosetting resin fine particles capable of improving the property and solvent resistance can be provided. When the thermosetting resin fine particles obtained by the present invention are added to the thermosetting resin, they are uniformly dispersed in the film or coating film to prevent blocking, light diffusing agent, light scattering agent, spacer, film reinforcing agent. It can be used as a resin modifier, matting agent, and lubricant for mechanical strength modification.

  The thermosetting resin fine particles referred to in the present invention contain at least an ethylenically unsaturated monomer having a trimethyleneoxy group having the following structure (1) as a constituent material in the fine particles. It is.

(ただし、Ｒ₁は水素原子または炭素数１〜６のアルキル基である)

(Wherein, R ₁ is hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

  Examples of the ethylenically unsaturated monomer having a trimethyleneoxy group of the structural formula (1) include (3-ethyl-3-oxetanyl) methoxy methacrylate, (3-methyl-3-oxetanyl) methoxy methacrylate, ( 3-butyl-3-oxetanyl) methoxy methacrylate and the like.

  The trimethyleneoxy group is a 4-membered cyclic ether group, and is a functional group having a large basicity, although the ring distortion is smaller than that of an epoxy group generally known as a cyclic ether group. It has thermosetting and UV cationic curing properties.

  The trimethyleneoxy group possessed by the thermosetting resin fine particles of the present invention is present on the surface or inside of the resin fine particles, and by heat, the functional groups and functional groups such as carboxyl groups, acid anhydride groups, epoxy groups, phenolic hydroxyl groups, and the like. Can be reacted. This reaction can be used for the reaction between the resin fine particles and the resin fine particles containing the functional group, the thermosetting resin binder, and the thermosetting monomer. As a result, the hardness of the resin fine particles is enhanced, and the hardness and adhesion of the coating are further enhanced.

The trimethyleneoxy group contained in the resin fine particles is preferably 5.0 × 10 ^{−5 to} 2.0 × 10 ⁻³ mol / g in the resin constituting the fine particles, and more preferably 2.0 ×. More preferably, it is 10 ^{−4 to} 1.7 × 10 ⁻³ mol / g. If the addition amount is less than this range, the hardness may not increase. If the addition amount is more than this range, aggregation may occur during fine particle synthesis, and resin fine particles may not be produced.

The presence of trimethyleneoxy groups in the resin fine particles is performed by infrared spectroscopy. In infrared spectroscopy, the presence of a trimethyleneoxy ring can be observed by a spectral peak appearing near 980 cm ⁻¹ .

  Examples of the ethylenically unsaturated monomer that can be used in the present invention include (meth) acrylic acid residues, crotonic acid residues, maleic acid residues, itaconic acid residues and other unsaturated carboxylic acid residues, ethenyl groups, Examples include compounds containing structures such as vinyl groups such as 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 2-pentenyl group, styryl group, cinnamyl group, tetrahydrofurfuryl group and the like. .

For example, as a monofunctional ethylenically unsaturated monomer,
Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid t -Butyl, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acryl Acrylic esters such as decyl acid, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate ;
Styrene monomers such as styrene, vinyl toluene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 1-butyl styrene, chlorostyrene;
Fluorine group-containing monomers such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc. Can be mentioned.

In addition, as the polyfunctional ethylenically unsaturated monomer,
(Meth) acrylic acid allyl, (meth) acrylic acid 1-methylallyl, (meth) acrylic acid 2-methylallyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3- Butenyl, 1,3-methyl-3-butenyl (meth) acrylate, 2-chloroallyl (meth) acrylate, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, (meth) acrylic acid 2- (allyloxy) ethyl, allyl lactyl (meth) acrylate, citronellyl (meth) acrylate, geranyl (meth) acrylate, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallyl itaconic acid, (Meth) vinyl acrylate, crotonate, vinyl oleate, vinyl linolenate, (meth) acrylic Acid 2- (2'-vinyloxyethoxy) unsaturated group-containing (meth) acrylic acid esters such as ethyl;
Di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid triethylene glycol, di (meth) acrylic acid tetraethylene glycol, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid pentaerythritol, diacrylic acid Polyfunctional (meth) acrylic acid esters such as 1,1,1-trishydroxymethylethane, triacrylic acid 1,1,1-trishydroxymethylethane, 1,1,1-trishydroxymethylpropane triacrylic acid;
Divinyls such as divinylbenzene and divinyl adipate;
Examples include diallyls such as diallyl isophthalate, diallyl phthalate, and diallyl maleate.

Furthermore, heterocyclic-containing (meth) acrylic esters such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate;
Hydroxy (alkoxy) -containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, etc. Kind;
Unsaturation such as (meth) acrylic acid, itaconic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid Carboxylic acids;
Unsaturated carboxylic acid anhydrides such as itaconic anhydride and maleic anhydride;
3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxy And alkoxysilyl group-containing monomers such as silane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane.

  These ethylenically unsaturated monomers are not limited to the exemplified compounds, and two or more types can be used in combination. Moreover, it is preferable to use so that the quantity of a polyfunctional ethylenically unsaturated monomer may be 5-30 weight% among all the monomers.

  In the present invention, a radical polymerizable initiator is used when the resin fine particles are synthesized. The radical polymerizable initiator is a compound that promotes the cleavage of unsaturated groups in the ethylenically unsaturated monomer and generates a radical chain reaction by generating radicals by heat or a catalyst. Examples of the radical polymerizable initiator include ionic / nonionic initiators. In the present invention, these can be used alone or in combination.

For example, as an ionic initiator, 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries), 2,2′-azobis {2- [N- ( 4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries), 2,2′-azobis {2- [N- (4-droxyphenyl) amidino] propane} dihydrochloride (VA-548) 2,2'-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, manufactured by Wako Purechemical), 2,2'-azobis [2- (N-allyl) Amidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries), 2,2′-azobis {2 -[N- (4-Hydroxyethyl) amidino] propane} dihydrochloride (VA-558, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (5- Tyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044) 2,2-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, Wako Pure Chemical) 2,2-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (5-Hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries), 2,2-azobis {2- [1- (2-hydroxy Ethyl) -2-imidazolin-2-yl] propane} dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (2-imidazolin-2-yl) propane ] Cationic initiators such as (VA-061, Wako Pure Chemical Industries)
And anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries) and ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries).

As a nonionic initiator, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2,4- Dimethylvaleronitrile) (V-65, Wako Pure Chemical Industries) 2,2'-azobisisobutyronitrile (V-60, Wako Pure Chemical Industries), 2,2'-azobis (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries), 1,1'-azobis (cyclohexane-1-carbonitrile) (V-40, manufactured by Wako Pure Chemical Industries), 1-[(1-cyano-1-methylethyl) azo Azonitrile compounds such as formamide (V-30, manufactured by Wako Pure Chemical Industries), 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile (V-19, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [2-Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] (VA-080, manufactured by Wako Pure Chemical Industries), 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxy Methyl) ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries), 2,2′-azobis [2-methyl-N- [2- (1-hydroxybutyl)]-propionamide] (VA-085, Wako Pure Chemical), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] (VA-086, Wako Pure Chemical), 2,2'-azobis (2-methyl) Propionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, manufactured by Wako Pure Chemical Industries), 2, 2 '-Azobis (N-butyl-2-methylpropionamide) (VAm-110, manufactured by Wako Pure Chemical Industries), 2,2'-Azobis (N-cyclohexyl-2-methylpropionamide) (Vam-111, Wako Pure Chemical Industries, Ltd.) 2,2′-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2-methylpropane) (VR-160) , Nonionic azo polymerization initiators such as alkylazo compounds such as Wako Pure Chemicals)
Methyl ethyl ketone peroxide (Permec H, manufactured by NOF Corporation), cyclohexanone peroxide (Perhexa H, manufactured by NOF Corporation), methylcyclohexanone peroxide (Perhexa Q, manufactured by NOF Corporation), methyl acetoacetate peroxide (Percure SA, manufactured by NOF Corporation) ), Ketone peroxides such as acetylacetone peroxide (Percure A, manufactured by NOF Corporation), 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation), 1 1,1-bis (t-hexylperoxy) cyclohexane (Perhexa HC, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (Perhexa 3M, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclohexane (Perhexa C, manufactured by NOF Corporation), 1,1-bis (t-butylpero) Xyl) cyclododecane (Perhexa CD-R, manufactured by Nippon Oil & Fats), 2,2-bis (t-butylperoxy) butane (Perhexa 22, manufactured by Nippon Oil & Fats), n-butyl 4,4-bis (t-butylper Peroxyketals such as oxy) valerate (Perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (Pertetra A, manufactured by NOF Corporation), t-butyl Hydroperoxide (Perbutyl H-69, manufactured by NOF Corporation), p-Mentane hydroperoxide (Permenta H, manufactured by NOF Corporation), Diisopropylbenzene hydroperoxide (Park Mill P, manufactured by NOF Corporation), 1, 1, 3, 3 -Hydrides such as tetramethylbutyl hydroperoxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Perkmill H-80, manufactured by NOF Corporation), t-hexyl hydroperoxide (Perhexyl H, manufactured by NOF Corporation) Peroxides, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (Perhexin 25B, manufactured by NOF Corporation), di-t-butyl peroxide (Perbutyl DR, manufactured by NOF Corporation), t-Butyl cumyl peroxy species (Perbutyl C, manufactured by Nippon Oil & Fats), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by Nippon Oil & Fats), Dicumyl Peroxy species (Perk Mill DR, (Nippon Yushi), dialkyl peroxides such as α, α'-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, Nippon Oil & Fats), octanoyl peroxy species (Perroyl O, NIPPON YOS), Lauroyl Peroxy species (Parroyl L, manufactured by Nippon Oil & Fats), Stearoyl Peroxy species (Perroyl S, manufactured by Nippon Oil & Fats), Succinic Acid Peroxy species (Perroyl SA, manufactured by Nippon Oil & Fats), Benzoyl peroxide (Nyper BW) Nippon Oil & Fats), Isobutyryl peroxide (Perroyl IB, Nippon Oil & Fats), 2,4-dichlorobenzoyl peroxy species (Nyper CS, Nippon Oil & Fats), 3,5,5-trimethylhexanoyl peroxy species (paroyl) 355, manufactured by NOF Corporation), di-n-propyl peroxydicarbonate (Perroyl NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (Perloyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perroyl TCP, manufactured by NOF Corporation), di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by NOF Corporation), di-2-ethoxyhexyl peroxydicarbonate (Parroyl OPP, manufactured by Nippon Oil & Fats), di-2-methoxybutyl peroxydicarbonate (Perroyl MBP, manufactured by Nippon Oil & Fats), Di (3- Peroxydicarbonates such as chill-3-methoxybutyl) peroxydicarbonate (Perroyl SOP, manufactured by Nippon Oil & Fats), α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Daiper ND-R, Nippon Oil & Fats) ), Cumyl peroxyneodecanoate (Park Mill ND-R, manufactured by Nippon Oil & Fats), 1,1,3,3-tetramethylbutylperoxyneodecanoate (Perocta ND-R, manufactured by Nippon Oil & Fats), 1 -Cyclohexyl-1-methylethylperoxyneodecanoate (Percyclo ND-R, manufactured by Nippon Oil & Fats), t-Hexylperoxyneodecanoate (Perhexyl ND-R, manufactured by Nippon Oil & Fats), t-Butylperoxyneo Decanoate (Perbutyl ND-R, manufactured by NOF), t-hexyl peroxypivalate (Perhexyl PV, manufactured by NOF), t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF) 1,1, , 3, -Tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation) 2,5-Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, Japan 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by Nippon Oil & Fats), t-hexylperoxy 2-ethylhexanoate (Perhexyl O, manufactured by Nippon Oil & Fats), t-Butylperoxy 2-ethylhexanoate (Perbutyl O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, Japan) Oil), t-butyl peroxymaleic acid (perbutyl MA, manufactured by Nippon Oil), t-butylperoxy 3,5,5-trimethylhexanoate (perbutyl 3) 5, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane (Perhexa 25MT, manufactured by NOF Corporation) , T-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF), t-butylperoxy 2-ethylhexyl monocarbonate (Perbutyl E, manufactured by NOF), t-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF) ) 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF Corporation), t-butyl peroxyacetate (Perbutyl A, manufactured by NOF Corporation), t-butylperoxy-m -Toluoyl benzoate (Perbutyl ZT, manufactured by NOF), t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF), bis (t-butylperoxy) isophthalate (Perbuth Peroxyesters such as Le IF, manufactured by NOF Corporation), t-butyl peroxyallyl monocarbonate (Peromer AC, manufactured by NOF Corporation), t-butyltrimethylsilyl peroxide (Perbutyl SM, manufactured by NOF Corporation), 3, 3 ' , 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB-50, manufactured by NOF Corporation), 2,3-dimethyl-2,3-diphenylbutane (Nofmer BC, manufactured by NOF Corporation), etc. Organic peroxides and the like.

  In particular, it is not limited to these, It is also possible to use 2 or more types together. The initiator is preferably used in an amount of 0.10 to 10% by weight based on the total amount of the monomers.

  The present invention is also characterized in that when the resin fine particles are synthesized, the polymerization is carried out in water and / or an alcohol solvent. By adjusting the mixing ratio of water and alcohol, the polymerization stability and particle diameter of the particles can be controlled. The higher the ratio of water in the solvent, the easier it is to synthesize particles with a smaller particle diameter, and conversely, the higher the ratio of solvent, the larger the particle diameter can be made.

  Specific examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol and the like. However, it is possible to add and synthesize organic solvents other than alcohol solvents as necessary. Examples of organic solvents other than alcohol solvents include ethers such as diethyl ether, isopropyl ether, butyl ether, methyl cellosolve, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, and diethyl ketone. These organic solvents can be used in combination of two or more.

  The water and / or solvent used in the resin fine particle synthesis is preferably 70 to 90% by weight of the total weight in the system, and the amount of water in the solvent is preferably 0 to 70% by weight.

  The thermosetting resin fine particles of the present invention are characterized by having an average particle diameter of 0.5 to 3.0 μm and a coefficient of variation of 10% or less. Monodispersed fine particles having a particle size in this range are particularly expected to be used in optical applications such as a light diffusing agent, a light scattering agent, and a spacer, and the fact that the particle size is uniform is an important factor. Therefore, the present invention is characterized by the thermosetting resin fine particles having a particle size range and distribution that can be used for optical applications, for which demand is increasing in recent years.

  The average particle diameter referred to in the present invention is the number average of 100 particles measured with an optical microscope, and the coefficient of variation is a numerical value obtained by statistically calculating the 100 particle diameters and calculating the following equation.

  Coefficient of variation (%) = (standard deviation / average particle size) × 100

  Furthermore, the thermosetting resin fine particles of the present invention are characterized by containing substantially no dispersion stabilizer.

The dispersion stabilizer refers to a surfactant capable of forming micelles or a high molecular weight substance that serves as a dispersion stabilizer. For example, surfactants include anionic surfactants such as alkyl sulfonates such as sodium dodecyl sulfonate, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate,
Alkylamine salts like coconut amine acetate, stearylamine acetate, quaternary like lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzenedimethylammonium chloride Cationic surfactants such as ammonium salts,
In addition, amphoteric surfactants such as lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl dimethylamine oxide, or even polyethylene glycols such as polyethylene glycol nonylphenyl ether Nonionic surfactants such as alkyl ethers can be mentioned. Furthermore, those having a functional group copolymerizable with an ethylenically unsaturated monomer bonded to these surfactants can be said to be surfactants.

  Examples of the high molecular weight dispersion stabilizer include polyvinyl alcohol, polyacrylic acid, copolymers thereof and neutralized products thereof, and polymethacrylic acid, copolymers thereof and neutralized products thereof, polyvinylpyrrolidone, hydroxypropyl. A cellulose (HPC) etc. are mentioned.

  In the present invention, in order to provide resin fine particles effective for controlling the physical properties of the coating film, the resin fine particles were produced by a synthesis technique not using these dispersion stabilizers. As a method for producing particles, there are generally various methods such as an emulsion polymerization method, a dispersion polymerization method, a suspension polymerization method, and a soap-free emulsion polymerization method. In the present invention, a micron-sized particle is used in the absence of a dispersion stabilizer. This is achieved by using a dispersion polymerization method capable of producing monodispersed fine particles, particularly a method developed by the present inventors. Details are disclosed in Japanese Patent Laid-Open No. 2001-278907. In this synthesis method, by performing polymerization using a specific ionic initiator, particles can be formed in the absence of a dispersion stabilizer. Moreover, it becomes possible to obtain particles having a relatively large particle diameter by adding a nonionic initiator.

  The fine particle production method of the present invention can also obtain monodisperse thermosetting resin fine particles by the synthesis method. That is, an ethylenically unsaturated monomer having a trimethyleneoxy group and other monofunctional / polyfunctional ethylenically unsaturated monomers are uniformly dissolved in a solvent to remove dissolved oxygen, and then the reaction system is changed to 60 Heat to ~ 80 ° C. Then, what melt | dissolved the radically polymerizable initiator in the solvent is added, and it obtains by heating and stirring for 3 to 10 hours.

  However, if there is a need to use a dispersion stabilizer due to adjustment of physical properties or the like, it is also possible to synthesize fine particles by adding a dispersion stabilizer. When a dispersion stabilizer is used, it is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the monomer.

  The thermosetting resin fine particles of the present invention can be used as a thermosetting coating agent by being added to a thermosetting resin binder or a thermosetting monomer. When used as a thermosetting coating agent, thermosetting resin fine particles are added to a mixture of a thermosetting resin binder, a thermosetting monomer, a catalyst, and the like.

  Examples of the thermosetting resin binder include a polyurethane resin, a polyurea resin, a polyurethane urea resin, a polyester resin, an unsaturated polyester resin, a polyether resin, a polycarbonate resin, an epoxy resin, an amino resin, and styrene having a thermosetting functional group. Resin, acrylic resin, methacrylic resin, melamine resin, polyamide resin, phenol resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate acidic group-containing urethane resin, petroleum resin, casein, shellac, rosin-modified maleic acid resin, rosin-modified phenol Resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, alkyd resin, silicone resin, fluororesin, drying oil, synthetic drying oil, chlorinated polypropylene, butyral resin, chlorinated Such as vinylidene resin and the like. The thermosetting composition of this invention can use together the said resin binder which does not have a thermosetting functional group in order to adjust the physical property of a cured coating film.

  The thermosetting functional group here is not particularly limited as long as it is a functional group capable of reacting with heat. A functional group capable of reacting with the trimethyleneoxy group in the thermosetting resin fine particles of the present invention by heat is preferable. The thermosetting resin binder needs to have two or more thermosetting functional groups in the molecule. Examples of the functional group capable of reacting with the trimethyleneoxy group include a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group. In addition, a functional group showing a known curing reaction can be used in combination. For example, functional groups that can react with carboxyl groups include epoxy groups, vinyl groups, carbodiimide groups, isocyanate groups, sultone groups, aziridine groups, and tetrahydrofuran derivative groups, and functional groups that can react with hydroxyl groups include epoxy groups. Groups, acid anhydride groups, tetrahydrofuran derivative groups, vinyl ether groups, carboxyl groups, isocyanate groups, aziridine groups, caprolactone groups, phenol groups and the like, but are not particularly limited thereto.

  Next, the thermosetting monomer is a low molecular compound having two or more thermosetting functional groups described above in the molecule. Specific examples of thermosetting monomers are given below.

  Thermosetting monomers having two or more carboxyl groups include benzoic acid, terephthalic acid, isophthalic acid, orthophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, citric acid, maleic acid, Dicarboxylic acids such as methyl nadic acid, dodecenyl succinic acid, sebacic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, pyromellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid, cyclohexanedicarboxylic acid, diphenolic acid, etc. Is mentioned. Moreover, the monomer which formed the acid anhydride ring in the said monomer can be used similarly.

Examples of the thermosetting monomer having two or more acid anhydride groups include 1,2,3,4-butanetetracarboxylic acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3, 5,6-tricarboxynorbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene- Aliphatic tetracarboxylic anhydrides such as 1,2-dicarboxylic anhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic anhydride;
Pyromellitic anhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3, 3 ', 4,4'-biphenyl ether tetracarboxylic acid anhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid Acid anhydride, 1,2,3,4-furantetracarboxylic acid anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diph Nyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (tri Phenylphthalic acid anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4 ′ -Diphenylmethane anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic anhydride, 9,9-bis [4- (3,4-dicarbo) Shifenokishi) phenyl] aromatic fluorene anhydride tetracarboxylic anhydride;
3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinate And polycyclic tetracarboxylic acid anhydrides such as acid anhydrides.

  Examples of the thermosetting monomer having two or more phenolic hydroxyl groups include hydroquinone, catechol, resorcinol, 1,4-dihydroxynaphthalene, bisphenol A, bisphenol F, and phloroglicinol.

  Furthermore, the monomer which combined the said thermosetting functional group can also be used. For example, salicylic acid, p-hydroxybenzoic acid, β-oxynaphthoic acid, 5-hydroxyisophthalic acid, 6-hydroxy-2-naphthoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, protocatecic acid, etc. Can do. In some cases, a compound having a phenolic amino group can also be used. Examples thereof include p-aminobenzoic acid, anthranilic acid, o-aminophenol, m-aminophenol, and p-aminophenol.

  In addition, compounds having a functional group such as an epoxy group, a vinyl group, a carbodiimide group, an isocyanate group, a sultone group, an aziridine group, a tetrahydrofuran derivative group, an alkoxysilyl group, a vinyl ether group, a caprolactone group, and a phenol group can also be used.

  For the purpose of adjusting the physical properties of the cured coating film, a monofunctional monomer can also be used in combination with the thermosetting monomer.

  In the present invention, the above-mentioned thermosetting resin binder and thermosetting monomer may be used alone or in combination. However, when it is necessary to store in a mixed state for a long time, it is preferable to select a combination of thermosetting compounds in which the curable compositions hardly react with each other at the storage temperature.

  Moreover, when making the thermosetting resin and thermosetting composition of this invention thermoset, it is preferable to thermoset at 50-400 degreeC, More preferably, it is preferable to thermoset at 100-300 degreeC. If the curing temperature is less than 50 ° C., the curing does not proceed sufficiently and the desired heat resistance may not be obtained. In addition, when the curing temperature is higher than 400 ° C., particularly when it is overheated for a long time, the curable material of the present invention may cause thermal degradation.

  The catalyst is a compound for accelerating the thermosetting reaction. In the case of a trimethyleneoxy group, it is preferable to use benzyldimethylamine, toluenesulfonic acid, or alkoxytitanium as the catalyst. In the case of other reactive functional groups, it is appropriately selected depending on the combination of functional groups. For example, it is preferable to use an amine catalyst for the addition reaction between a carboxyl group and an epoxy group.

  The catalyst is preferably added in an amount of 0 to 10%, more preferably 0 to 5%, based on the thermosetting compound.

  The thermosetting composition using the thermosetting resin fine particles of the present invention can be used as a curable composition containing no organic solvent or as a curable composition containing an organic solvent. When an organic solvent is included, it may be applied to various substrates, and after the organic solvent is volatilized, heat energy necessary for curing may be applied. A well-known thing can be used as an organic solvent. Specific examples include cyclohexanone, methyl ethyl ketone, toluene, methyl propylene glycol acetate and the like.

  In addition, as an optional component as long as the purpose is not impaired, a solvent, a dye, a pigment, an antioxidant, a polymerization inhibitor, a leveling agent, a moisturizer, a viscosity modifier, an antiseptic, an antibacterial agent, an antistatic agent, and an antiblocking agent. An agent, an ultraviolet absorber, an infrared absorber, an electromagnetic shielding agent, a filler, and the like can be added.

  The thermosetting resin fine particles of the present invention are fine particles that exhibit reactivity by heat. The fine particles have a particle size of 0.5 to 3.0 μm and a coefficient of variation of 10% or less. The thermosetting resin fine particles of the present invention can be used by adding to a thermosetting coating agent, for example, an anti-blocking agent, a light diffusing agent, a light scattering agent, a spacer, a film reinforcing agent, and a mechanical strength modifier. It can be used in a wide range of applications from fine to general applications such as resin modifiers, matting agents, and lubricants.

Next, the present invention will be described specifically by way of examples. In the examples, “parts” and “%” are all based on weight unless otherwise specified.
(Example 1)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 70 parts of methanol, 13 parts of water, 13.5 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 part, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) 0.8 part was charged, and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 6 hours. A resin fine particle dispersion having a diameter of 1.33 μm and a coefficient of variation of 3.09% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%.

The trimethyleneoxy group in the fine particles was confirmed by infrared spectroscopy (apparatus: Thermo electron corporation). That is, it was confirmed that the decomposition of the trimethyleneoxy group did not proceed before and after the fine particle synthesis by the presence or absence of the infrared absorption spectrum wavelength of 980 cm ⁻¹ .

(Example 2)
In a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 70 parts of methanol, 13 parts of water, 12.8 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 parts, 1.5 parts of (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) were added, and dissolved oxygen was removed by flowing nitrogen gas. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 6 hours. A resin fine particle dispersion having a diameter of 1.25 μm and a coefficient of variation of 2.85% was obtained. Thereafter, the solvent in the dispersion was replaced with toluene by heating / pressurizing operation to obtain a non-aqueous dispersion having a solid content of 30%. In addition, the presence of a trimethyleneoxy group was confirmed by infrared spectroscopy as in Example 1.

(Example 3)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 70 parts of methanol, 13 parts of water, 12.0 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 parts, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, Ube Industries) 1.5 parts, 2-methacryloyloxyethyl hexahydrophthalic acid (HO-HH, Wako Pure Chemical Industries) 0.8 parts was charged, and nitrogen gas was flowed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 6 hours. A resin fine particle dispersion having a diameter of 1.42 μm and a coefficient of variation of 3.77% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%. In addition, the presence of a trimethyleneoxy group was confirmed by infrared spectroscopy as in Example 1.

Example 4
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 76 parts of methanol, 9 parts of water, 13.5 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 part, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) 0.8 part was charged, and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, 2.20 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 1 part of methanol are added simultaneously and heated with stirring for 6 hours. A resin fine particle dispersion having a diameter of 2.60 μm and a coefficient of variation of 2.59% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%. In addition, the presence of a trimethyleneoxy group was confirmed by infrared spectroscopy as in Example 1.

(Example 5)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 76 parts of methanol, 9 parts of water, 13.5 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 part, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) 0.8 part was charged, and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, 2.20 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 1 part of methanol are added simultaneously and heated with stirring for 6 hours. A resin fine particle dispersion having a diameter of 3.33 μm and a coefficient of variation of 6.27% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%. In addition, the presence of a trimethyleneoxy group was confirmed by infrared spectroscopy as in Example 1.

(Example 6)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, methanol 60 parts, water 25 parts, styrene (St, manufactured by Wako Pure Chemical Industries) 13.5 parts, divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 part, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) 0.8 part was charged, and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 6 hours. A fine resin particle dispersion having a diameter of 0.41 μm and a coefficient of variation of 3.89% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%. In addition, the presence of a trimethyleneoxy group was confirmed by infrared spectroscopy as in Example 1.

(Example 7)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 70 parts of methanol, 13 parts of water, 13.5 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 part, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) 0.8 part was charged, and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.45 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol is heated at the same time with stirring for 6 hours. A fine resin particle dispersion having a diameter of 2.45 μm and a coefficient of variation of 15.2% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%. In addition, the presence of a trimethyleneoxy group was confirmed by infrared spectroscopy as in Example 1.

(Comparative Example 1)
In a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 70 parts of methanol, 13 parts of water, 14.3 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 parts was charged and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 7 hours. A resin fine particle dispersion having a diameter of 1.03 μm and a coefficient of variation of 2.96% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%.

(Comparative Example 2)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 70 parts of methanol, 13 parts of water, 13.5 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 parts, (3-ethyl-3-oxetanyl) methoxymethyl methacrylate (OXMA, manufactured by Ube Industries) 0.8 part, sodium lauryl sulfate (SDS, manufactured by Wako Pure Chemical Industries) 0.15 part, nitrogen gas To remove dissolved oxygen. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 7 hours. A fine resin particle dispersion having a diameter of 0.88 μm and a variation coefficient of 7.23% was obtained. Thereafter, the obtained resin fine particles were washed with 3000 parts of water three times, and then dried to completely remove moisture, and the resin fine particle powder was dispersed in methyl ethyl ketone to obtain a non-aqueous dispersion having a solid content of 30%. It was.

(Comparative Example 3)
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 70 parts of methanol, 13 parts of water, 13.5 parts of styrene (St, manufactured by Wako Pure Chemical Industries), divinylbenzene (DVB, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.8 part and 0.8 part of glycidyl methacrylate (GMA, manufactured by Ube Industries) were charged, and dissolved oxygen was removed by flowing nitrogen gas. After heating the reactor to 60 ° C., 0.07 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries) was dissolved in 0.5 part of ion-exchanged water, A solution prepared by dissolving 0.15 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 part of methanol was added at the same time and heated with stirring for 6 hours. A resin fine particle dispersion having a diameter of 1.52 μm and a coefficient of variation of 5.01% was obtained. Thereafter, the solvent in the dispersion was replaced with methyl ethyl ketone by heating and pressurizing operations to obtain a non-aqueous dispersion having a solid content of 30%.

<Evaluation of resin fine particle composition>
10 parts of each resin fine particle obtained above, 1 part of bisphenol A type epoxy resin Epicoat 828 (epoxy equivalent 190, manufactured by Japan Epoxy Resin Co., Ltd.), 1.2 parts of pyromellitic anhydride, benzyldimethylamine 0.006 The coating was applied to a glass plate with an applicator so that the film thickness was 10 μm, and cured in an oven at 200 ° C. for 1 hour. The resin fine particle composition thus produced was used for the following evaluation.

  The pencil hardness was tested according to JIS K5400 8.4.2. Note that “2H” or higher was judged to be a practical level.

  To fix, the coating film was reciprocated 10 times with # 1000 steel wool while applying a load of 200 g, and the powder on the coating film was visually observed. In addition, "○" or more was judged to be a practical level.

  The results of each example and comparative example are summarized in Table 1.

  As is clear from Table 1, Examples 1 to 7 of the present invention were excellent in both pencil hardness and adhesion as compared with Comparative Examples 1 to 3.

The thermosetting resin fine particles of the present invention are generally used for anti-blocking agents, light diffusing agents, light scattering agents, spacers, film reinforcing agents, resin modifiers for improving mechanical strength, matting agents, lubricants, etc. Can be used in a wide range of applications from precision to precision.

Claims (4)

Resin fine particles obtained by radical polymerization of a monofunctional ethylenically unsaturated monomer and a polyfunctional ethylenically unsaturated monomer with a radically polymerizable initiator in water and / or alcohol solvent in the absence of a dispersion stabilizer. There,
Thermosetting resin fine particles, wherein the monofunctional ethylenically unsaturated monomer and / or the polyfunctional ethylenically unsaturated monomer contains at least an ethylenically unsaturated monomer having a functional group represented by the following structural formula (1).

(Wherein, R ₁ is hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)   The thermosetting resin fine particles according to claim 1, having an average particle size of 0.5 to 3.0 µm and a coefficient of variation of 10% or less.   A thermosetting composition comprising the thermosetting resin fine particles according to claim 1, and a thermosetting resin binder and / or a thermosetting monomer. In the absence of a dispersion stabilizer, a monofunctional ethylenically unsaturated monomer and a polyfunctional ethylenically unsaturated monomer containing at least an ethylenically unsaturated monomer having a functional group represented by the following structural formula (1): A method for producing thermosetting resin fine particles, wherein radical polymerization is performed with a radical polymerizable initiator in water and / or an alcohol solvent.

(Wherein, R ₁ is hydrogen atom or an alkyl group having 1 to 6 carbon atoms)