JP2007191562A - Reactive monodisperse resin micro-particle and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive monodisperse resin micro-particle having an affinity for a matrix resin and to provide a micro-particle improving fixing properties or pencil hardness of a film in the presence of a photo-curable resin binder or a photo-curable monomer. <P>SOLUTION: The reactive monodisperse resin micro-particle is a resin micro-particle having at least one reactive functional group selected from a hydroxy group, an epoxy group, a carboxy group and an alkoxysilyl group and ethylenically unsaturated groups. The resin micro-particle has 8.0×10<SP>-5</SP>to 1.0×10<SP>-3</SP>mol/g ethylenically unsaturated groups and 95-100 mol% of the whole reactive functional groups and the ethylenically unsaturated groups is present on the resin micro-particle surface. The resin micro-particle has 0.1-10 μm particle diameter and ≤10% coefficient of variation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

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 a method in which resin fine particles are prepared by an emulsion polymerization method, and seed emulsion polymerization is further performed using the obtained fine particles as a seed. This method is a method in which the vinyl group remains on the surface by increasing the proportion of the crosslinkable monomer added later in the seed emulsion polymerization. However, in this method, there are many vinyl groups used for crosslinking, and the particle surface localized amount of the remaining vinyl groups is uncertain, so that the efficiency of the matrix resin as a reinforcing agent is poor. Moreover, only a particle diameter range of 10-100 nm is obtained.
On the other hand, Patent Document 2 discloses a method in which an ethylenically unsaturated bond is present at the end of a carbon chain extending outward from a resin fine particle through a reaction between an active hydrogen group and an isocyanate group. The fine particles produced by this method are polydispersed, and are not suitable for fields requiring monodispersity such as light diffusing agents, light scattering agents, and spacers, which have been particularly demanding in recent years. In addition, since a large amount of emulsifier is used, there is a possibility of causing adverse effects such as a decrease in water resistance. Patent Document 3 also discloses a method of introducing a polymerizable unsaturated compound onto a polymer dispersion stabilizer produced in the presence of a polymer dispersion stabilizer. Therefore, a method that does not include these contaminants is desired.
Furthermore, although the fine particles of these inventions have a functional group that is cured by ultraviolet rays or electron beams, the affinity with the matrix resin may decrease, resulting in a problem in dispersibility. Moreover, although it can apply to the use hardened with an ultraviolet-ray or an electron beam, it is not so effective for the use hardened with a heat | fever. Therefore, it is desired to develop a fine particle material that is monodispersed and does not impair the affinity with the matrix resin and is versatile for thermosetting.
Japanese Patent No.2722661 Japanese Patent Publication No.7-86125 JP 2000-230007

Therefore, an object of the present invention is to provide fine particles that are monodispersed and have an affinity for a matrix resin.
It is another object of the present invention to provide fine particles capable of improving the adhesion of a film and the pencil hardness in the presence of a photocurable resin binder and a photocurable monomer.

  In order to solve this problem, the present inventors have conceived reactive resin fine particles in which a reactive functional group containing an ethylenically unsaturated group is localized on the surface. As a result, it is possible to provide reactive monodispersed resin fine particles having a particle diameter of 0.1 to 10 μm and a coefficient of variation of 10% or less, without a dispersion stabilizer.

The present invention is a resin fine particle having at least one reactive functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, and an ethylenically unsaturated group,
The ethylenically unsaturated group of the resin fine particles is 8.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / g, and
The present invention relates to reactive monodisperse resin fine particles in which 95 to 100 mol% of the total reactive functional groups and ethylenically unsaturated groups are present on the surface of resin fine particles and have a particle size of 0.1 to 10 μm and a coefficient of variation of 10% or less.

Furthermore, the present invention relates to an ethylenically unsaturated monomer (a) having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, and other ethylenically unsaturated monomers ( b) and resin fine particles (c) obtained by radical polymerization,
Reaction of a compound (d) having an ethylenically unsaturated group with a functional group capable of reacting with at least one functional group selected from the hydroxyl group, epoxy group, carboxyl group and alkoxysilyl group possessed by the resin fine particles (c) Reactive monodisperse resin fine particles,
The difference between the solubility parameter (σa) of the monomer (a) and the solubility parameter (σb) of the monomer (b) relates to the reactive monodisperse resin fine particles represented by the following formula.
0.2 ≦ σa−σb ≦ 2.5
(However, σa: solubility parameter of monomer (a) having at least one reactive functional group selected from hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group and ethylenically unsaturated group σb: other Solubility parameter of ethylenically unsaturated monomer (b))

 Furthermore, this invention relates to the reactive monodisperse resin fine particle whose ratio of the ethylenically unsaturated group with respect to the reactive functional group whole quantity is 50-99.9 mol%.

 The present invention further relates to reactive monodisperse resin fine particles in which the ethylenically unsaturated group is a polymerizable unsaturated carboxylic acid residue.

  Furthermore, the present invention relates to reactive monodispersed resin fine particles obtained by polymerizing resin fine particles in the absence of a dispersion stabilizer.

  The present invention further relates to a photocurable composition comprising the reactive monodispersed resin fine particles obtained above and a photocurable resin binder and / or monomer.

Furthermore, the present invention relates to an ethylenically unsaturated monomer (a) having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, and other ethylenically unsaturated monomers ( b) and resin fine particles (c) obtained by radical polymerization,
Reaction of a compound (d) having an ethylenically unsaturated group with a functional group capable of reacting with at least one functional group selected from the hydroxyl group, epoxy group, carboxyl group and alkoxysilyl group possessed by the resin fine particles (c) A method for producing reactive resin fine particles, characterized by comprising:
The difference between the solubility parameter (σa) of the monomer (a) and the solubility parameter (σb) of the monomer (b) is represented by the following formula, and relates to a method for producing reactive monodisperse resin fine particles: .
0.2 ≦ σa−σb ≦ 2.5
(However, σa: solubility parameter of monomer (a) having at least one reactive functional group selected from hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group and ethylenically unsaturated group σb: other Solubility parameter of ethylenically unsaturated monomer (b))

 Further, the present invention provides a reactive monodisperse characterized by polymerizing an ethylenically unsaturated monomer (a) and another ethylenically unsaturated monomer (b) in the absence of a dispersion stabilizer. The present invention relates to a method for producing resin fine particles.

 According to the present invention, it was possible to provide reactive monodisperse resin fine particles having a functional group that reacts with ultraviolet rays or electron beams localized on the surface and having a uniform particle size. More specifically, reactive monodisperse resin fine particles capable of preventing falling off from the coating film when used by adding to a photocurable coating agent can be provided. The reactive monodisperse resin fine particles obtained by the present invention are uniformly dispersed in a film or a coating film when added to a photocurable resin, and an antiblocking agent, a light diffusing agent, a light scattering agent, a spacer, and film reinforcement. It can be used as an agent, a resin modifier for modifying mechanical strength, a matting agent, and a lubricant.

 The reactive monodispersed resin fine particles referred to in the present invention are monodispersed resin fine particles having at least one reactive functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group and an ethylenically unsaturated group. Say.

 Examples of the hydroxy group include hydroxyalkylene groups such as a hydroxy group, a hydroxymethylene group, and a hydroxyethylene group. The epoxy group includes a glycidyl group, the carboxyl group includes a carboxyalkyl group and a carboxyphenyl group, and the alkoxysilyl group includes an alkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group. It is not limited to these.

 Examples of ethylenically unsaturated groups include (meth) acrylic acid residues, crotonic acid residues, maleic acid residues, itaconic acid residues and other unsaturated carboxylic acid residues, ethenyl groups, 1-propenyl groups, and allyl groups. , Vinyl groups such as isopropenyl group, 1-butenyl group, 2-butenyl group, 2-pentenyl group, styryl group, cinnamyl group, tetrahydrofurfuryl group, and the like, but are not limited thereto. In particular, it is preferable to use an unsaturated carboxylic acid residue that is highly reactive, has many types, and is versatile even in view of cost.

 At least one reactive functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group contained in the resin fine particles of the present invention is used for a reaction when an ethylenically unsaturated group is localized on the surface. In other words, it remains on the particle surface and contributes to the improvement of physical properties by improving the dispersibility of the particles, improving the compatibility with the matrix resin, and further thermosetting.

 The ethylenically unsaturated group finally present in the particles is used as a reactive group that is cured by irradiation with ultraviolet rays or electron beams. It is important that this ethylenically unsaturated group is localized on the surface of the resin fine particles. By localizing the ethylenically unsaturated functional group on the particle surface, the reaction with the matrix resin is promoted in the subsequent curing reaction, which effectively works to improve the strength of the cured film.

The reactive monodispersed resin fine particles of the present invention are characterized in that the concentration of ethylenically unsaturated groups contained in the resin fine particles is 8.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / g.

 Furthermore, in the reactive monodispersed resin fine particles of the present invention, 95 to 100 mol% of all reactive functional groups and ethylenically unsaturated groups contained in the resin fine particles are localized on the particle surface. By these things, hardening reaction with matrix resin is fully performed, and while it can express the outstanding physical property, the dispersibility to matrix resin also becomes favorable. Furthermore, resin fine particles having high curability can be obtained efficiently by using a small amount of a raw material for introducing these reactive functional groups.

Examples of the method for measuring reactive functional groups and ethylenically unsaturated groups present on the particle surface include infrared spectroscopy, conductivity titration, potentiometric titration, and X-ray photoelectron spectroscopy. Infrared spectroscopy can measure spectra of various functional groups, conductivity titration and potentiometric titration can determine the various functional groups on the particle surface, and X-ray photoelectron spectroscopy can measure the chemical state of particle surface compounds. In the present invention, the amount of functional groups was quantified by a known titration method. That is, the hydroxyl value was determined by the hydroxyl value, the epoxy group was determined by the epoxy value, and the carboxyl group was determined by the acid value. The alkoxysilyl group was quantified for Si atoms by surface analysis using ESCA (monochromic X-ray source, 15 kV-10 mA). In addition, the functional group quantified by these quantitative methods was defined as the functional group present on the particle surface. The amount of the ethylenically unsaturated group was calculated by quantifying the functional groups (hydroxyl group, epoxy group, carboxyl group, alkoxysilyl group) present on the particle surface before and after modification, and calculating the disappearance amount.

 Further, since the resin fine particles of the present invention are finally intended to be cured by irradiation with ultraviolet rays or electron beams, the ethylenically unsaturated groups contained therein are the reactive functional groups and ethylenically unsaturated groups in the resin fine particles. The total content is preferably 50 to 99.9 mol%, more preferably 70 to 99.9 mol%.

 Furthermore, the reactive monodispersed resin fine particles of the present invention are reactive monodispersed resin fine particles having an average particle diameter of 0.1 to 10 μm and a coefficient of variation of 10% or less.

 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

Next, the manufacturing method of the reactive monodispersed resin fine particles of the present invention will be described. The reactive monodispersed resin fine particles of the present invention are produced, for example, by the following two steps.
Step (A): an ethylenically unsaturated monomer (a) having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, and another ethylenically unsaturated monomer ( a step of producing resin fine particles (c) by radical polymerization of b).
However, the difference between the solubility parameter (σa) of the monomer (a) and the solubility parameter (σb) of the monomer (b) is expressed by the following equation.
0.2 ≦ σa−σb ≦ 2.5
(However, σa: solubility parameter of monomer (a) having at least one reactive functional group selected from hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group and ethylenically unsaturated group σb: other Solubility parameter of ethylenically unsaturated monomer (b))
Step (B): Compound having functional group capable of reacting with at least one functional group selected from hydroxyl group, epoxy group, carboxyl group and alkoxysilyl group possessed by resin fine particles (c) and ethylenically unsaturated group ( A step of producing reactive monodisperse resin fine particles by reacting d).

 In the step (A), the resin fine particles (c) are synthesized with a monomer, an initiator, and a solvent. 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. A dispersion polymerization method capable of producing monodispersed fine particles is used.

 A method of obtaining micron-sized monodispersed fine particles in the absence of a dispersion stabilizer by dispersion polymerization is achieved by using a method developed by the present inventors. Details are disclosed in JP-A-2001-278907. This synthesis method enables the formation of particles in the absence of a dispersion stabilizer by performing polymerization using a specific ionic initiator in a mixed solution of water / organic solvent. Furthermore, micron-sized particles can be obtained by adding a nonionic initiator.

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} dihydro Chloride (VA-546, manufactured by Wako Pure Chemical Industries), 2,2'-azobis {2- [N- (4-droxyphenyl) amidino] propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries), 2, 2'-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [2- (N-allylamidino) propane] dihydrochloride (VA- 553, manufactured by Wako Pure Chemical), 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical), 2,2'-azobis {2- [N- (4-hydroxyethyl ) Amidino] propane} dihydrochloride (VA-558, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, Wako Pure) 2,2-azobis [2- (2-imidazoline) -2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl ) Propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (VA-058, sum) Manufactured by Kojun Pharmaceutical Co., Ltd.), 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-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (2- Cationic initiators such as imidazolin-2-yl) propane] (VA-061, Wako Pure Chemical Industries, Ltd.)
Anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries), ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries),
Is mentioned.

In addition, 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, sum 2,2'-Azobisisobutyronitrile (V-60, Wako Purechemical), 2,2'-azobis (2-methylbutyronitrile) (V-59, Wako Purechemical) 1,1'-azobis (cyclohexane-1-carbonitrile) (V-40, manufactured by Wako Pure Chemical Industries), 1-[(1-cyano-1-methylethyl) azo] formamide (V-30, Wako Pure Chemical Industries, Ltd.) Azonitrile compounds such as 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 (hydroxymethyl) Ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [2-methyl-N- [2- (1-hydroxybutyl)]-propi Namide] (VA-085, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] (VA-086, manufactured by Wako Pure Chemical Industries), 2,2 '-Azobis (2-methylpropionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, Wako Pure) 2,2'-azobis (N-butyl-2-methylpropionamide) (VAm-110, manufactured by Wako Pure Chemical Industries), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) ( Vam-111 (manufactured by Wako Pure Chemical), etc., 2,2'-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical), 2,2'-azobis (2- Nonionic azo polymerization initiators such as alkylazo compounds such as (methylpropane) (VR-160, manufactured by Wako Pure Chemical Industries, Ltd.)
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-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-butylperoxy) cyclododecane Hexa 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-butylperoxy) valerate (perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (Pertetra A, manufactured by NOF Corporation) and other peroxyketals, t-butyl hydroperoxide (perbutyl) H-69, manufactured by NOF Corporation), p-menthane hydroperoxide (Permenta H, manufactured by NOF Corporation), diisopropylbenzene hydroperoxide (Park Mill P, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylhydro Hydroperoxides such as peroxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Perkmill H-80, manufactured by NOF Corporation), t-hexyl hydroperoxide (Perhexyl H, manufactured by NOF Corporation), 2,5 -Dimethyl-2,5-bis (t-butyl -Oxy) hexyne-3 (perhexine 25B, manufactured by NOF Corporation), di-t-butyl peroxide (perbutyl DR, manufactured by NOF Corporation), t-butylcumyl peroxy species (perbutyl C, manufactured by NOF Corporation), 2,5- Dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation), Dicumyl peroxy species (Parkmill DR, manufactured by NOF Corporation), α, α'-bis (t-butylperoxy) diisopropylbenzene Dialkyl peroxides such as (Perbutyl P, manufactured by Nippon Oil & Fats), Octanoyl Peroxy species (Perroyl O, manufactured by Nippon Oil & Fats), Lauroyl Peroxy species (Perroyl L, manufactured by Nippon Oil & Fats), Stearoyl Peroxy species (Parroyl S, Nippon Oil & Fats, Succinic Acid Peroxy (Perroyl SA, manufactured by Nippon Oil & Fats), Benzoyl peroxide (Nyper BW, manufactured by Nippon Oil & Fats), Isobutyryl peroxide (Perroyl IB, manufactured by Nippon Oil & Fats) ), 2,4-dichlorobenzoyl peroxy species (Nyper CS, manufactured by NOF Corporation), 3,5,5-trimethylhexanoyl peroxy species (Perroyl 355, manufactured by NOF Corporation), diacyl peroxides, 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, Nippon Oil & Fats), di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by Nippon Oil & Fats), di-2-ethoxyhexyl peroxydicarbonate (Perroyl OPP, manufactured by Nippon Oil & Fats), di-2-methoxybutyl per Peroxydicarbonates such as oxydicarbonate (Perroyl MBP, manufactured by NOF), di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perroyl SOP, manufactured by NOF) Carbonates, α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Dyper ND-R, manufactured by NOF Corporation), cumylperoxyneodecanoate (Parkmill ND-R, manufactured by NOF Corporation), 1,1 , 3,3-tetramethylbutyl peroxyneodecanoate (Perocta ND-R, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxyneodecanoate (Percyclo ND-R, manufactured by NOF Corporation), t-Hexylperoxyneodecanoate (Perhexyl ND-R, manufactured by NOF), t-Butylperoxyneodecanoate (Perbutyl ND-R, manufactured by NOF), t-Hexylperoxypivalate (Perhexyl PV) , Manufactured by NOF Corporation), t-butyl peroxypivalate (perbutyl PV, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation) ) 2,5-Dimethyl-2,5-bis (2-ethyl) Ruhexanoyl peroxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corporation), t-hexylperoxy 2-ethyl Hexanoate (Perhexyl O, manufactured by NOF), t-butyl peroxy 2-ethylhexanoate (Perbutyl O, manufactured by NOF), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF), t -Hexylperoxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF), t-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF), t-butylperoxy 3,5,5-trimethylhexanoate (Perbutyl) 355, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane (peroxyethylene) 25MT, manufactured by NOF Corporation), t-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation), t-butyl peroxy 2-ethylhexyl monocarbonate (Perbutyl E, manufactured by NOF Corporation), t-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF), t-butyl peroxyacetate (Perbutyl A, manufactured by NOF), t-Butyl peroxy-m-toluoyl benzoate (Perbutyl ZT, manufactured by NOF), t-Butyl peroxybenzoate (Perbutyl Z, manufactured by NOF), Bis (t-butylperoxy) isophthalate (Perbutyl IF, Japan) Peroxyesters such as oil and fat), t-butylperoxyallyl monocarbonate (Peromer AC, manufactured by Nippon Oil & Fats), t-butyltrimethylsilyl peroxide ( -Butyl 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 Nonionic organic peroxides such as (Nofmer BC, manufactured by NOF Corporation) can be used.
It is not particularly limited to these, and two or more types can be used in combination. The initiator is preferably used in an amount of 0.10 to 10% by weight based on the total amount of the monomers.

 The monomer includes an ethylenically unsaturated monomer (a) having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, and other ethylenically unsaturated monomers ( Use b).

As the monomer (a),
Heterocycle-containing (meth) acrylic acid esters such as (meth) acrylic acid glycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid tetrahydrofurfuryl;
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 Alkoxysilyl group-containing monomers such as silane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane;
However, it is not limited to these.

Monomer (b) includes monofunctional and polyfunctional ethylenically unsaturated compounds. 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;
Examples thereof include fluorine group-containing monomers such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and the like.

In addition, as a polyfunctional ethylenically unsaturated monomer,
Allyl (meth) acrylate, 1-methylallyl (meth) acrylate, 2-methylallyl (meth) acrylate, 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, (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, Vinyl (meth) acrylate, vinyl crotonate, vinyl oleate, vinyl linolenate, 2- (2'-vinyloxy) (meth) acrylate (Meth) acrylic acid esters containing unsaturated groups such as ciethoxy) 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, but are not limited thereto. Two or more types can be used in combination.
The amount of the polyfunctional monomer in the monomer (b) is preferably used so as to be 5 to 20% by weight of the total monomers.

In particular, in the reactive monodispersed resin fine particles of the present invention, it is important that the difference in solubility parameter σ between the monomers (a) and (b) satisfies the following formula.
0.2 ≦ σa-σb ≦ 2.5
(However, σa: solubility parameter of monomer (a) having at least one reactive functional group selected from hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group and ethylenically unsaturated group σb: other Solubility parameter of ethylenically unsaturated monomer (b))

 The solubility parameter is a value defined by the square root of the cohesive energy density, and is a value serving as an index representing the affinity between molecules. The value increases as the attractive force between the molecules increases, and the affinity between substances having similar solubility parameters is considered good.

 In the present invention, attention is paid to this solubility parameter. As long as the difference in solubility parameter between the monomers (a) and (b) satisfies the above formula, the reactive functional group is selectively localized on the surface. It has been found that fine monodisperse resin fine particles can be produced. That is, in the particle preparation process by dispersion polymerization, the difference in the respective affinities of the monomers (a) and (b) with respect to the solvent is used to give a difference in the precipitation rate as a multimer.

 Table 1 shows some examples of solubility parameters of the monomers (a) and (b). The solubility parameter values in the table were calculated based on the data described in literature: POLYMER HANDBOOK second edition (J. BRANDRUP, E.H. IMMERGUT), IV339 Table B2.

At this time, if the solubility parameter difference between the monomers (a) and (b) is less than 0.2, the difference in affinity for the solvent is reduced, there is no difference in the polymerization precipitation rate, and the reactive functional group is applied to the particle surface. Difficult to localize. Further, if the difference in solubility parameter is larger than 2.5, the particles are aggregated or deformed, which is not appropriate. Even when particles are formed, oligomers and polymers containing a large amount of monomer (a) are not taken into the particles, and the amount remaining in the solvent increases, which is not efficient in localizing functional groups.
The difference in solubility parameter is more preferably in the range of 0.2 ≦ σa−σb ≦ 2.3, and the monomers (a) and (b) may be combined.

 In the synthesis method of step (A), the monomer (a) and the monomer (b) are uniformly dissolved in the solvent, dissolved oxygen is removed, and after heating to 60 ° C., the initiator is ionized. A method of adding water dissolved in exchange water or a solvent and heating and stirring for 3 to 10 hours can be mentioned.

 The fine particles synthesized in this way are monodisperse particles having a particle diameter of 0.1 to 10 μm and a coefficient of variation of 10% or less, in which reactive functional groups are localized on the particle surface. Further, since no dispersion stabilizer is used and no metal ions are present, it can be used in the next step without the need for washing or the like.

 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.

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-hydroxyethyl imidazolinium betaine, lauryl dimethylamine oxide, or even polyethylene glycols such as polyethylene glycol nonyl phenyl 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 also be used as the surfactant.

 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. These can also be used in combination.

  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.

Next, step (B) will be described. Step (B) is a compound having a functional group capable of reacting with at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, which the resin fine particles (c) have, and an ethylenically unsaturated group This is a step of producing reactive monodisperse resin fine particles by reacting (d). Moreover, it synthesize | combines using a catalyst as needed.
After completion of the reaction, the obtained dispersion is repeatedly washed with a solvent three times or more, and finally the functional group derived from the monomer (a) and the ethylenic unsaturated derived from the monomer (d) remaining on the particle surface. Measure the group.

 The functional group capable of reacting with at least one functional group selected from the hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group possessed by the resin fine particles (c) is, for example, the functional group possessed by the resin fine particles (c) is a hydroxyl group. In this case, an isocyanate group, an acid anhydride group, an alkoxysilyl group and the like can be mentioned. Further, when the functional group of the resin fine particles (c) is an epoxy group, examples thereof include a carboxyl group, an acid anhydride group, and an amino group. Further, when the functional group of the resin fine particles (c) is a carboxyl group, examples thereof include a vinyl group, an epoxy group, an oxazoline group, and a carbodiimide group. In addition, when the functional group of the resin fine particles (c) is an alkoxysilyl group, examples thereof include an alkoxysilyl group and a hydroxyl group. Among these, a combination of a carboxyl group and an epoxy group is most preferable from the viewpoint of being able to react stably.

The monomer (d) having a functional group capable of reacting with at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, which the resin fine particles (c) have, and an ethylenically unsaturated group, For example, the monomers exemplified as the monomer (a) or the monomers exemplified as the monomer (b) can be used in appropriate combination.
The ethylenically unsaturated group is preferably a polymerizable unsaturated carboxylic acid residue from the viewpoint of curability. The monomer (d) is preferably added in an amount of 0.5 to 100 times, more preferably 1 to 10 times the reactive functional groups localized on the surface of the resin fine particles (c).

 The catalyst is appropriately selected according to the combination of reactive 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 solvent used in the step (B) may be the same as the solvent used in the step (A). However, when a solvent different from that used in the step (A) is used, the solvent substitution of the resin fine particles may be performed in advance.

 The synthesis method in step (B) will be described. The resin fine particles (c) obtained in the step (A) and the monomer (d) are charged, the reaction temperature is adjusted to 70 to 150 ° C. according to the boiling point of the solvent used, and the catalyst is heated to the target temperature. To start the reaction. The progress of the reaction is confirmed by quantifying the decrease in the functional group contained in the monomer (a) or monomer (d) over time according to the type of the functional group present.

The reactive monodispersed resin fine particles of the present invention can be added to a photocurable resin binder or a photocurable monomer and used as a photocurable coating agent. When used as a photocurable coating agent, it is added to a mixture of a binder resin, an ethylenically unsaturated compound, a photopolymerization initiator, and the like.
Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, vinyl resin. Etc. These resins may be photocurable resin binders into which ethylenically unsaturated bonds are introduced. Any method for introducing an ethylenically unsaturated bond may be used. For example, a resin binder having a vinyl group in a side chain obtained by polymerizing a monomer containing a monomer having a photocurable functional group of at least two kinds (for example, a vinyl group and an acrylic group) having different reactivities can be given. Further, there is a photocurable resin binder obtained by polymerizing a monomer having a reactive functional group to obtain a resin having a reactive functional group and then modifying the reactive functional group. These resins may be added alone, or a plurality of resins including other resins may be mixed and added.
As the photocurable monomer, a known monofunctional or polyfunctional acrylic monomer or vinyl monomer can be used. Below, it illustrates about a photocurable monomer.

  Examples of the ethylenically unsaturated compound include alkyl (meth) acrylates and alkylene glycol (meth) acrylates as (meth) acrylate compounds.

  More specifically, as the alkyl-based (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadeci (Meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkyl (meth) acrylates having 1 to 22 carbon atoms such as docosyl (meth) acrylate.

Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol. Mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, etc.
A monoacrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain or a corresponding monomethacrylate,
Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate , N-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy Tetrapropylene glycol (meth) acrylate, ethoxytetrapropyleneglycol (Meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetra Methylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, monoacrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain, or a corresponding monomethacrylate,
Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Examples thereof include polyoxyalkylene acrylates having a phenoxy or aryloxy group at the terminal, such as phenoxytetrapropylene glycol (meth) acrylate, or corresponding methacrylates.

  Examples of the carboxyl group-containing unsaturated compound include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meta ) Acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like.

  Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. It is done.

Examples of the nitrogen-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- (meth) acrylamide. , N-butoxymethyl- (meth) acrylamide, monoalkylol (meth) acrylamide such as N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl ( (Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, Acrylamide-type unsaturated compounds such as N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dialalkylol (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate methylethylaminoethyl (meth) acrylate, unsaturated compounds having a dialkylamino group such as dimethylaminostyrene and diethylaminostyrene, and halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ as counter ions. Examples thereof include quaternary ammonium salts of dialkylamino group-containing unsaturated compounds having ON or QSO ^3- (Q: alkyl group having 1 to 12 carbon atoms), acryloylmorpholine, and the like.

  Further, other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2 -Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) ) Acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkylalkyl (meth) acrylates having a kill group; perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyls such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene, and alkylenes , Vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and other alkoxysilyl group-containing vinyl compounds and derivatives thereof, glycidyl acrylate, 3,4-epoxycyclohexyl Examples thereof include glycidyl group-containing acrylates such as acrylates.

Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.
Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.
Examples of the vinyl compound include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, and the like. Can be mentioned.
Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like.

  Furthermore, the compound having at least one ethylenically unsaturated bond, and specific examples of polyfunctional compounds include the following.

  First, non-halogen aliphatic compounds are exemplified. Specifically, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayrad R-167, hydroxypivalate neopentyl glycol di (Meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: Nippon Kayaku Kayrad HX series alkyl type (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified proleng Cold di (meth) acrylate: alkylene glycol type (meth) acrylate such as Nagase Sangyo Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) acrylate: Sartomer SR-454, propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA- 310, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type (meth) acrylate such as Nagase Sangyo DA (M) -321, pentae Rithritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate: Toagosei Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylates, alkyl-modified dipentaerythritol poly (meth) acrylates: Kaprorad-modified dipentaerythritol poly (meth) acrylates such as Nippon Kayaku Kayrad D-310, 320, 330, etc .: Nippon Kayaku Kayrad DPCA-20 , 30, 60, 120, etc. Pentaerythritol type (meth) acrylate, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate Nagase Sangyo Denacol DA (M) -314, glycerol type (meth) acrylate such as triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl Di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toa Gosei Aronix M-315, Tris (methacrylic) Isocyanurate type (meth) acrylates such as (Roxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate, etc. It is.

  Moreover, the compound which further contains a sulfur atom in a molecule | numerator among the compounds which have a polymerizable ethylenically unsaturated group comprised only from an aliphatic group is illustrated. 1,3-propanediol dithio (meth) acrylate, 1,4-butanediol dithio (meth) acrylate, 1,6-hexanediol dithio (meth) acrylate, neopentyl glycol dithio (meth) acrylate, bis (thioacryloxy) Neopentyl glycol) adipate, bis (thiomethacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol dithio (meth) acrylate, hydroxypivalate neopentyl glycol dithio (meth) acrylate, caprolactone modified hydroxypivalate neopentyl Alkyl thio (meth) acrylate such as glycol dithio (meth) acrylate, ethylene glycol dithio (meth) acrylate, diethylene glycol dithio (Meth) acrylate, triethylene glycol dithio (meth) acrylate, tetraethylene glycol dithio (meth) acrylate, polyethylene glycol dithio (meth) acrylate, epichlorohydrin modified ethylene glycol dithio (meth) acrylate, epichlorohydrin modified diethylene glycol dithio (meth) acrylate, propylene Glycol dithio (meth) acrylate, dipropylene glycol dithio (meth) acrylate, tripropylene glycol dithio (meth) acrylate, tetrapropylene glycol dithio (meth) acrylate, polypropylene glycol dithio (meth) acrylate, epichlorohydrin modified prolene glycol dithio (meth) ) Alkylene glycol type thio such as acrylate (Meth) acrylate, trimethylolpropane trithio (meth) acrylate, ditrimethylolpropane trithio (meth) acrylate, neopentyl glycol modified trimethylolpropane dithio (meth) acrylate, ethylene oxide modified trimethylolpropane trithio (meth) acrylate, Trimethylolpropane type thio (meth) acrylate such as propylene oxide modified trimethylolpropane trithio (meth) acrylate, epichlorohydrin modified trimethylolpropane trithio (meth) acrylate, pentaerythritol trithio (meth) acrylate, pentaerythritol tetrathio ( (Meth) acrylate, stearic acid-modified pentaerythritol dithio (meth) acrylate, dipentaerythritol Pentaerythritol-type thio (meth) such as hexahexa (meth) acrylate, dipentaerythritol monohydroxypentathio (meth) acrylate, alkyl-modified dipentaerythritol polythio (meth) acrylate, caprolactone-modified dipentaerythritol polythio (meth) acrylates Glycerol-type thio (meth) acrylate such as acrylate, glycerol dithio (meth) acrylate, epichlorohydrin modified glycerol trithio (meth) acrylate, triglycerol dithio (meth) acrylate, dicyclopentanyl dithio (meth) acrylate, tricyclopentanyl Dithio (meth) acrylate, cyclohexyldithio (meth) acrylate, methoxylated cyclohexyldithio (meth) acrylate Any cycloaliphatic thio (meth) acrylate, tris (thioacryloxyethyl) isocyanurate, tris (thiomethacryloxyethyl) isocyanurate, caprolactone-modified tris (thioacryloxyethyl) isocyanurate, caprolactone-modified tris (thiomethacryloxyethyl) ) Isocyanurate type thio (meth) acrylate such as isocyanurate.

  Examples of the aromatic polyhydroxy compound include di- or poly (meth) acrylate compounds such as hydroquinone, resorcin, catechol, pyrogallol, bisphenol A di (meth) acrylate, and ethyl (propi) ylene oxide modified bisphenol A di (meth) acrylate. , Bisphenol F di (meth) acrylate, Ethi (propi) lene oxide modified bisphenol F di (meth) acrylate, Bisphenol S di (meth) acrylate, Ethi (propi) lene oxide modified bisphenol S di (meth) acrylate, Epichlorohydrin modified phthalate (Meth) acrylate compounds having an aromatic group such as acid di (meth) acrylate, tetrachlorobisphenol S ethyl (propylene) oxide modified di (meth) acrylate, tetra Romo and bisphenol S ethylene (prop) Ren'okishido modified di (meth) styrenes having an aromatic group substituted by a halogen atom with chlorine or atomic weight, such as acrylates and (meth) acrylate compounds.

  Examples of the urethane acrylate include phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer: Kyoeisha Chemical AH-600, phenylglycidyl ether acrylate tolylene diisocyanate urethane prepolymer: Kyoeisha Chemical AT-600, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer. Polymer: Kyoeisha Chemical UA-306H, phenylglycidyl ether acrylate isophorone diisocyanate urethane prepolymer: Kyoeisha Chemical AI-600, glycerol dimethacrylate tolylene diisocyanate urethane prepolymer: Kyoeisha Chemical UA-101T, glycerol dimethacrylate isophorone diisocyanate urethane prepolymer: Kyoeisha Chemistry A-101I, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer Kyoeisha Chemical UA-306T, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer and the like Kyoeisha Chemical UA-306I and the like.

The photopolymerization initiator is added when the photosensitive composition is cured by ultraviolet rays. In addition, an initiator is not particularly necessary when curing with an electron beam.
The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

Specific examples of monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-enetanone. 3,3′-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3′4,4′-tetra ( t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2- ( -Oxo-2-propenyloxyethyl)] metaammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2 -Hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy))-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2 -D) thiazoline and the like.
Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -9-butylcarbazole and the like.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.

  These are not limited to the above compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited. Moreover, a well-known organic amine can also be added as a sensitizer.

The photocurable coating agent using the reactive monodispersed resin fine particles of the present invention can be used as a curable composition containing no organic solvent or a curable composition containing an organic solvent.
In the case of containing an organic solvent, it may be applied to various substrates, and after the organic solvent is volatilized, active energy rays such as ultraviolet rays and electron beams necessary for curing may be irradiated. 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.

<Photosensitivity>
The reactive monodispersed resin fine particles of the present invention or the photocurable coating agent using the reactive monodispersed resin fine particles can be cured by a known radiation curing method to obtain a cured product. Electron beams, ultraviolet rays, and visible light of 400 to 500 nm can be used.
A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these ultraviolet rays or electron beams can be used in combination with heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  The reactive monodisperse resin fine particles of the present invention are fine particles that exhibit reactivity by ultraviolet rays or electron beams. The fine particles have a particle diameter of 0.1 to 10 μm and a coefficient of variation of 10% or less. The reactive monodisperse resin fine particles of the present invention can be used by adding to a photocurable coating agent, for example, for antiblocking agent, light diffusing agent, light scattering agent, spacer, film reinforcing agent, mechanical strength modification. It can be used in a wide range of applications from fine particles such as resin modifiers, matting agents and lubricants to general applications.

  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
Step (A): In a reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, methanol 60 parts, water 23 parts, methyl methacrylate (MMA (σ = 7.86), Wako Pure Chemical Industries, Ltd.) 12 parts, Benzyl methacrylate (BzMA (σ = 8.78), Wako Pure Chemical Industries, Ltd.) 1.5 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical Industries, Ltd.) 0.8 parts, 2-methacryloyloxyethyl hexahydrophthalic acid (HO-HH 0.8 parts (σ = 9.68), manufactured by Wako Pure Chemical Industries, Ltd.) were added, and dissolved oxygen was removed by flowing nitrogen gas. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 0.005 part dissolved in 1 part of methanol was added simultaneously and heated with stirring for 7 hours, particle size 1.52 A resin fine particle dispersion having a μm and a coefficient of variation of 2.36% 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 amount of carboxyl groups on the particle surface was confirmed by measuring the acid value by potentiometric titration (apparatus: AUTO TITRATOR COM-1500, HIRANUMA). That is, a few drops of a phenolphthalein solution was added to a sample obtained by mixing 10 parts of the resin fine particle dispersion obtained in step (A), 22.5 parts of methyl ethyl ketone, and 2.5 parts of water, and a 0.1N ethanolic potassium hydroxide solution (Wako Pure Chemical Industries, Ltd.). The acid value of the dispersion liquid was determined by dropping (product details are described in JIS Handbook Reagents, Japanese Standards Association, p53). The amount of carboxyl groups inside the particles was calculated by subtracting the acid value of the dispersion from the theoretical acid value.
Further, the resin fine particle dispersion obtained in step (A) is centrifuged, and the acid value in the supernatant after separation is determined, and the acid value in the supernatant is subtracted from the acid value of the dispersion previously determined. The amount of carboxyl groups present on the particle surface was calculated. As a result, it was confirmed that the introduced carboxyl group was present on either the particle surface or the supernatant, and the abundance ratio was particle surface / particle interior / supernatant = 73/0/27.

Step (B): Next, the reactor was charged with 28 parts of the resin fine particle dispersion obtained in Step (A) and 4.0 parts of glycidyl methacrylate (GMA, manufactured by Wako Pure Chemical Industries, Ltd., 5 times mol of carboxyl groups), After heating to 70 ° C., 1.4 parts of N, N′-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heating and stirring were continued for 8 hours.
The progress of the reaction was confirmed by following the amount of decrease in the acid value on the particle surface. The ratio of ethylenically unsaturated groups to all functional groups at this time was 99.8%.

(Example 2)
Step (A): A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, methanol 60 parts, water 23 parts, methyl methacrylate (MMA (σ = 7.86), Wako Pure Chemical Industries, Ltd.) 12 parts, benzyl Methacrylate (BzMA (σ = 8.78), Wako Pure Chemical) 1.5 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical) 0.8 parts, Methacrylic acid (MAA (σ = 9.99), Wako Pure Chemical) 0.8 parts was charged, and nitrogen gas was flowed to remove dissolved oxygen. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 0.005 part dissolved in 1 part of methanol was added simultaneously and heated with stirring for 7 hours, particle size 1.63 A resin fine particle dispersion having a μm and a coefficient of variation of 3.29% 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%.

  When the amount of carboxyl groups on the particle surface was determined in the same manner as in Example 1, the abundance ratio was particle surface / particle interior / supernatant = 68/0/32.

Step (B): Next, the reactor was charged with 28 parts of the resin fine particle dispersion obtained in Step (A) and 4.0 parts of glycidyl methacrylate (GMA, manufactured by Wako Pure Chemical Industries, Ltd., 5 times mol of carboxyl groups), After heating to 70 ° C., 1.4 parts of N, N′-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heating and stirring were continued for 8 hours.
At this time, the ratio of ethylenically unsaturated groups to all functional groups was 99.7%.

(Example 3)
To 28 parts of the resin fine particle dispersion obtained in the step (A) of Example 1, 11 parts of 2- (2′-vinyloxyethoxy) ethyl acrylate (VEEA, manufactured by Wako Pure Chemical Industries, Ltd.) [10-fold mol of carboxyl group] After heating to 70 ° C., stirring was continued for 4 hours. The ratio of ethylenically unsaturated groups to all functional groups at this time was 63.8%.

Example 4
Step (A): 44 parts of methanol, 39 parts of water, 12 parts of methyl methacrylate (MMA (σ = 7.86), manufactured by Wako Pure Chemical Industries), benzyl in a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube Methacrylate (BzMA (σ = 8.78), Wako Pure Chemical Industries, Ltd.) 0.8 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical Industries, Ltd.) 0.8 parts, 2-hydroxyethyl methacrylate (HEMA (σ = 9.68), Wako Pure) (Product made from Yakuhin) 1.5 parts were charged, and nitrogen gas was flowed to remove dissolved oxygen. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 0.01 parts dissolved in 1 part of methanol was added simultaneously and heated with stirring for 7 hours, particle size 2.35 A fine resin particle dispersion having a μm and a coefficient of variation of 1.81% 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 amount of hydroxyl groups on the particle surface was confirmed by measuring the hydroxyl value (details are described in JIS Handbook Reagents, Japanese Standards Association, p56). The hydroxyl group value of the resin fine particle dispersion obtained in the step (A) was determined, and the hydroxyl group amount inside the particle was calculated by subtracting the hydroxyl value of the dispersion from the theoretical hydroxyl group.
Further, the resin fine particles obtained in the step (A) are centrifuged, the hydroxyl value in the supernatant after separation is obtained, and the particles are obtained by subtracting the hydroxyl value in the supernatant from the hydroxyl value of the dispersion obtained previously. The amount of hydroxyl groups present on the surface was calculated. As a result, the hydroxyl group in the dispersion is either on the particle surface or dissolved in the dispersion, and the abundance ratio is particle surface / inside particle / supernatant = 66/0/34 It was confirmed.

Step (B): Next, in the reactor, 30 parts of the resin fine particle dispersion obtained in Step (A), 1.9 parts of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Wako Pure Chemical Industries, Ltd.) Mole] was added, heated to 70 ° C., 1.5 parts of dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and heating and stirring were continued for 4 hours.
The progress of the reaction was confirmed by following the decrease of the added isocyanate group by infrared spectroscopy (IR method). When the IR spectrum of the dispersion was measured 4 hours after the reaction, the spectrum peak (2270 cm-1) of the isocyanate group that had been observed before the reaction was completely reduced, confirming the completion of the reaction. At this time, the ratio of ethylenically unsaturated groups to all functional groups was 99.0%.

(Example 5)
Step (A): A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, methanol 60 parts, water 23 parts, methyl methacrylate (MMA (σ = 7.86), Wako Pure Chemical Industries, Ltd.) 12 parts, benzyl Methacrylate (BzMA (σ = 8.78), Wako Pure Chemical) 1.5 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical) 0.8 parts, 2-methacryloyloxyethyl hexahydrophthalic acid (HO-HH ( (σ = 9.68), Wako Pure Chemical Co., Ltd.) 0.8 parts, sodium lauryl sulfate (SDS, Wako Pure Chemical Industries, Ltd.) 0.15 parts were charged, and nitrogen gas was passed to remove dissolved oxygen. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 0.005 part dissolved in 1 part of methanol was added simultaneously and heated with stirring for 7 hours, particle size 1.73 A resin fine particle dispersion having a μm and a coefficient of variation of 5.24% 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%.

  When the amount of carboxyl groups on the particle surface was determined in the same manner as in Example 1, the abundance ratio was particle surface / particle interior / supernatant = 70/0/30.

Step (B): Next, the reactor was charged with 28 parts of the obtained fine resin particle dispersion and 4.0 parts of glycidyl methacrylate (GMA, Wako Pure Chemical Industries) [5-fold mol of carboxyl group], and heated to 70 ° C. Then, 1.4 parts of N, N′-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heating and stirring were continued for 8 hours.
The progress of the reaction was confirmed by following the amount of decrease in the acid value on the particle surface. At this time, the ratio of ethylenically unsaturated groups to all functional groups was 97.0%.

(Example 6)
Step (A): 44 parts of methanol, 39 parts of water, 12 parts of methyl methacrylate (MMA (σ = 7.86), manufactured by Wako Pure Chemical Industries), benzyl in a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube Methacrylate (BzMA (σ = 8.78), Wako Pure Chemical Industries, Ltd.) 0.8 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical Industries, Ltd.) 0.8 parts, 2-hydroxyethyl methacrylate (HEMA (σ = 9.68), Wako Pure) 1.5 parts by chemical) and 0.15 parts by sodium lauryl sulfate (SDS, manufactured by Wako Pure Chemical Industries, Ltd.) were added, and dissolved oxygen was removed by flowing nitrogen gas. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 0.01 parts dissolved in 1 part of methanol was added simultaneously and heated with stirring for 7 hours, particle size 2.11 A resin fine particle dispersion having a μm and a coefficient of variation of 4.85% 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 amount of hydroxyl groups on the particle surface was determined in the same manner as in Example 4. As a result, it was confirmed that the abundance ratio was particle surface / inside particle / supernatant = 65/0/35.

Step (B): Next, the reactor was charged with 30 parts of the obtained resin fine particle dispersion, 1.9 parts of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Wako Pure Chemical Industries, Ltd., 0.99-fold mol of hydroxyl group), and 70 After heating to 0 ° C., 1.5 parts of dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heating and stirring were continued for 4 hours.
The progress of the reaction was confirmed by following the decrease of the added isocyanate group by infrared spectroscopy (IR method). When the IR spectrum of the dispersion was measured 4 hours after the reaction, the spectrum peak (2270 cm-1) of the isocyanate group that had been observed before the reaction was completely reduced, confirming the completion of the reaction. At this time, the ratio of ethylenically unsaturated groups to all functional groups was 99.0%.

(Comparative Example 1)
Step (A): A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, methanol 60 parts, water 23 parts, methyl methacrylate (MMA (σ = 7.86), Wako Pure Chemical Industries, Ltd.) 12 parts, benzyl Methacrylate (BzMA (σ = 8.78), Wako Pure Chemical Industries, Ltd.) 1.5 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical Industries, Ltd.) 0.8 parts, 2-methacryloyloxyethylphthalic acid (PA (σ = 10.84) (Manufactured by Wako Pure Chemical Industries, Ltd.) was charged with 0.8 parts, and dissolved oxygen was removed by flowing nitrogen gas. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 0.001 part of methanol was added at the same time, and heating was continued while stirring for 7 hours. After several hours of reaction, the sticking began to adhere to the reaction kettle and agglomerates were formed.

(Comparative Example 2)
Step (A): A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, methanol 60 parts, water 23 parts, methyl methacrylate (MMA (σ = 7.86), Wako Pure Chemical Industries, Ltd.) 12 parts, benzyl Methacrylate (BzMA (σ = 8.78), Wako Pure Chemical) 1.5 parts, Allyl methacrylate (AMA (σ = 7.88), Wako Pure Chemical) 0.8 parts, Acrylic acid (AA (σ = 10.84), Wako Pure Chemical) 0.8 parts was charged, and nitrogen gas was flowed to remove dissolved oxygen. After heating the reactor to 60 ° C, 0.02 part of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, Wako Pure Chemical Industries) dissolved in 0.5 part of ion-exchanged water and 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.005 part dissolved in 1 part of methanol was added simultaneously and heated with stirring for 7 hours, particle size 1.44 A resin fine particle dispersion having a μm and a coefficient of variation of 3.25% 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%.

  When the amount of carboxylic acid on the particle surface was measured in the same manner as in Example 1, the abundance ratio was particle surface / inside particle / supernatant = 30/0/70, and the particle surface was coated with respect to the amount of charged carboxyl groups. The efficiency of introducing introduced carboxyl groups was poor.

Step (B): Next, the reactor was charged with 28 parts of the obtained fine resin particle dispersion and 4.0 parts of glycidyl methacrylate (GMA, Wako Pure Chemical Industries) [5-fold mol of carboxyl group], and heated to 70 ° C. Then, 1.4 parts of N, N′-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heating and stirring were continued for 8 hours.
The progress of the reaction was confirmed by following the amount of decrease in the acid value on the particle surface. At this time, the ratio of ethylenically unsaturated groups to all functional groups was 99.4%.

(Comparative Example 3)
Step (B): 29 parts of the resin fine particle dispersion prepared in Example 1, 1.2 parts of glycidyl methacrylate (GMA, manufactured by Wako Pure Chemical Industries, Ltd.) [with respect to carboxyl group 1.5 times mol], heated to 70 ° C., N, N 1.5 parts of '-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries) was added and heating and stirring were continued for 8 hours.
At this time, the ratio of ethylenically unsaturated groups to all functional groups was 31.8%.

(Comparative Example 4)
Step (B): 29 parts of the resin fine particle dispersion prepared in Example 5 and 1.2 parts of glycidyl methacrylate (GMA, manufactured by Wako Pure Chemical Industries, Ltd., 1.5 times moles of carboxyl groups) were charged to 70 ° C., and then N, N 1.5 parts of '-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries) was added and heating and stirring were continued for 8 hours.
At this time, the ratio of ethylenically unsaturated groups to all functional groups was 24.1%.

(Comparative Example 5)
Step (B): 29 parts of the resin fine particle dispersion prepared in Example 4 and 1.2 parts of glycidyl methacrylate (GMA, manufactured by Wako Pure Chemical Industries, Ltd., 1.5 times moles of carboxyl groups) were charged to 70 ° C., and then N, N 1.5 parts of '-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries) was added and heating and stirring were continued for 8 hours.
At this time, the ratio of ethylenically unsaturated groups to all functional groups was 12.4%.

  The resin fine particles obtained in Examples 1 to 6 and Comparative Examples 2 to 5 were washed with purified water and further dried.

(Quantification of reactive functional groups)
The resin fine particles obtained by washing and drying were subjected to acid value or hydroxyl value measurement according to the type of functional group contained, and the amount of carboxyl groups or hydroxyl groups was calculated. Furthermore, in the examples or comparative examples, the amount of ethylenically unsaturated groups present on the surface of the resin particles is calculated by subtracting the calculated amount from the amount of carboxyl groups or hydroxyl groups on the surface of the resin fine particles obtained in step (A). did.

(Evaluation)
2 parts of the particles obtained above were added as a binder to a mixture of 55 parts of pentaerythritol triacrylate and 38 parts of acryloylmorpholine, and the mixture was stirred and mixed. Further, 5 parts of ircagua 184 was added as a photoinitiator, applied to a PET film with an applicator so that the film thickness was 10 μm, and irradiated with ultraviolet light of 400 mJ / cm ² with a metal halide lamp to prepare a coated product. What passed 1 week at room temperature was used for the following evaluation.
The pencil hardness was tested according to JIS K5400 8.4.2 and the results shown in Table 1 were obtained.
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. The results are shown in Table 2.

（表２）

(Table 2)

  As is clear from Table 1, Examples 1 to 6 of the present invention were superior in fixing properties as compared with Comparative Examples 1 to 5. Also, the pencil hardness of the coating film was high.

The reactive fine particles of the present invention are precise from general use of fine particles such as anti-blocking agents, light diffusing agents, light scattering agents, spacers, film reinforcing agents, resin modifiers for modifying mechanical strength, matting agents, lubricants, etc. Can be used for a wide range of purposes.

Claims (8)

Resin fine particles having at least one reactive functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group, and an ethylenically unsaturated group,
The ethylenically unsaturated group of the resin fine particles is 8.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / g, and
Reactive monodisperse resin fine particles in which 95 to 100 mol% of all of the reactive functional groups and ethylenically unsaturated groups are present on the surface of the resin fine particles with a particle size of 0.1 to 10 μm and a coefficient of variation of 10% or less. Radicals of an ethylenically unsaturated monomer (a) having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group and another ethylenically unsaturated monomer (b) In the resin fine particles (c) obtained by polymerization,
Reaction of a compound (d) having an ethylenically unsaturated group with a functional group capable of reacting with at least one functional group selected from the hydroxyl group, epoxy group, carboxyl group and alkoxysilyl group possessed by the resin fine particles (c) Reactive monodisperse resin fine particles,
The reactive monodisperse resin fine particles according to claim 1, wherein the difference between the solubility parameter (σa) of the monomer (a) and the solubility parameter (σb) of the monomer (b) is represented by the following formula.
0.2 ≦ σa−σb ≦ 2.5
(However, σa: solubility parameter of monomer (a) having at least one reactive functional group selected from hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group and ethylenically unsaturated group σb: other Solubility parameter of ethylenically unsaturated monomer (b))  The reactive monodisperse resin fine particles according to claim 1 or 2, wherein the ratio of the ethylenically unsaturated group to the total amount of the reactive functional groups is 50 to 99.9 mol%.  The reactive monodisperse resin fine particles according to any one of claims 1 to 3, wherein the ethylenically unsaturated group is a polymerizable unsaturated carboxylic acid residue.   The reactive monodispersed resin fine particles according to any one of claims 1 to 4, wherein the resin fine particles are polymerized in the absence of a dispersion stabilizer.   A photocurable composition comprising the reactive monodispersed resin fine particles according to claim 1 and a photocurable resin binder and / or monomer. Radicals of an ethylenically unsaturated monomer (a) having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group and another ethylenically unsaturated monomer (b) In the resin fine particles (c) obtained by polymerization,
Reaction of a compound (d) having an ethylenically unsaturated group with a functional group capable of reacting with at least one functional group selected from the hydroxyl group, epoxy group, carboxyl group and alkoxysilyl group possessed by the resin fine particles (c) A method for producing reactive resin fine particles, characterized by comprising:
A method for producing reactive monodisperse resin fine particles, wherein the difference between the solubility parameter (σa) of the monomer (a) and the solubility parameter (σb) of the monomer (b) is represented by the following formula:
0.2 ≦ σa−σb ≦ 2.5
(However, σa: solubility parameter of monomer (a) having at least one reactive functional group selected from hydroxyl group, epoxy group, carboxyl group, and alkoxysilyl group and ethylenically unsaturated group σb: other Solubility parameter of ethylenically unsaturated monomer (b)) The reactive monodisperse according to claim 7, wherein the ethylenically unsaturated monomer (a) and the other ethylenically unsaturated monomer (b) are polymerized in the absence of a dispersion stabilizer. Production method of resin fine particles.