JP2008156610A - Elastic resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resin particles having high compressive deformation recovery property, as retaining its high flexibility. <P>SOLUTION: The elastic resin particles characteristically include a crosslinked copolymer of: a urethane resin (A) essentially including at least one of a urethane prepolymer (c) composed essentially of at least one kind of high molecular polyol (a) selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol and polycarbonate polyol, and (a) di-isocyanate (b), and (a) di-isocyanate trimer (h), and having a C-C double bond; and a compound (B) that has no urethane bond, has a number average molecular weight of 100 to 1,000 and has two or more C-C double bonds. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to highly elastic resin particles having high resilience after release of a compressive load on the particles. More specifically, it is effective for use in LCD (Liquid Crystal Display) gap members, touch panel gap members, conductive gap members, spacers for electronic parts such as light diffusion members, and light diffusion materials for various optical materials. It relates to elastic resin particles.

  Conventionally, monodispersed resin particles are known to be useful as spacers for display devices such as LCDs and touch panels, conductive adhesives for mounting, and anisotropic conductive adhesives. In particular, in recent years, there is a demand for flexible particles that have good contact with the opposing substrate or panel surface and do not damage elements such as alignment films, color filters, and ITO (Indium Tin Oxide) conductive films on the substrate. (For example, refer to Patent Document 1).

However, although these soft particles have high flexibility, they have low recoverability after the compression load is released, and the compression deformation recovery rate from 10% deformation is all as small as about 70% or less. (For example, see Patent Documents 1 to 3).
JP 2000-319309 A Japanese Patent Application Laid-Open No. 08-225625 JP 2002-033022 A

  The present invention has been made in view of the above situation, and has been made for the purpose of providing resin particles having high flexibility and high compression deformation recovery property.

As a result of intensive studies, the present inventors have completed the present invention.
That is, the present invention comprises at least one polymer polyol (a) and diisocyanate (b) selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol, and polycarbonate polyol as essential components, and carbon- Crosslinked copolymer of urethane resin (A1) having a carbon double bond and compound (B) having no urethane bond and a number average molecular weight of 100 to 1000 and having two or more carbon-carbon double bonds Containing elastic resin particles;
And a diisocyanate trimer (h) as an essential component, a urethane resin (A2) having a carbon-carbon double bond, and a number-average molecular weight of 100 to 1000 without a urethane bond, and a carbon-carbon double An elastic resin particle comprising a cross-linked copolymer with a compound (B) having two or more bonds;
A bead spacer for a display device made of the elastic resin particles, and a bead spacer for a print image receiving layer made of the elastic resin particles.

The resin particles of the present invention are characterized by having high compressive deformation recovery properties while having high flexibility.

Examples of the polymer polyol (a) include at least one selected from the group consisting of a polyester polyol (a1), a polyether polyol (a2), a polyetherester polyol (a3), and a polycarbonate polyol (a4).
The number of functional groups in (a) is preferably 2.
200-8000 are preferable, as for the number average molecular weight (henceforth Mn) of (a), 500-8000 are more preferable, and 1000-6000 are more preferable.

The number average molecular weight Mn in (a) is a value obtained from a hydroxyl value (mg number of potassium hydroxide necessary for neutralizing acetic acid bound to an acetylated product obtained from 1 g of a sample).

Examples of the polyester polyol (a1) include: (1) by condensation polymerization of a low molecular diol and a dicarboxylic acid or an ester-forming derivative thereof [an acid anhydride, a lower alkyl (C1 to C4) ester, an acid halide, etc.]. (2) those obtained by ring-opening polymerization of a lactone monomer using a low molecular diol as an initiator; and mixtures of two or more of these.

Specific examples of the low molecular diol include aliphatic diols having 4 to 12 or more carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, etc., branched diol (propylene glycol, neopentyl glycol, 3-methyl 1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2 -, 1,3- or 2,3-butanediol and the like]; a diol having a cyclic group [for example, those described in JP-B No. 45-1474; 1,4-bis (hydroxymethyl) cyclohexane, m- or p-Xylylene glycol, ethylene oxide adduct of bisphenol A (molecular weight 500 Mitsuru), etc.] and mixtures of two or more thereof. Among these, preferred are aliphatic diols having a branched chain.

Specific examples of the dicarboxylic acid or ester-forming derivative thereof (1) include aliphatic dicarboxylic acids having 4 to 15 carbon atoms [succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid. Etc.], aromatic dicarboxylic acids having 8 to 12 carbon atoms [terephthalic acid, isophthalic acid, etc.], ester-forming derivatives thereof [acid anhydrides, lower alkyl esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides) And the like, and mixtures of two or more thereof.

Examples of the lactone monomer (2) include γ-butyrolactone, ε-caprolactone, γ-barrel lactone, and mixtures of two or more thereof.

Examples of the polyether polyol (a2) include compounds having a structure in which an alkylene oxide is added to two hydroxyl group-containing compounds (for example, the low molecular diol, divalent phenols, and the like).
Examples of the divalent phenols include bisphenols [bisphenol A, bisphenol F, bisphenol S, etc.], monocyclic phenols [catechol, hydroquinone, etc.], and the like.

Examples of the alkylene oxide include ethylene oxide (EO), propylene oxide (PO), 1,2-, 1,3-, 1,4 or 2,3-butylene oxide, styrene oxide, 5 to 10 or more carbon atoms. Α-olefin oxide, epichlorohydrin and mixtures of two or more thereof (block or random addition).

Among these, preferred are those in which alkylene oxide is added to a low-molecular diol, and more preferred are those in which PO is added to an aliphatic diol.

The polyether ester polyol (a3) is obtained by polycondensation of one or more of the above polyether polyols and one or more of the dicarboxylic acids exemplified as the raw material of the above polyester polyols or their ester-forming derivatives. Things.

Examples of the polycarbonate polyol (a4) include polyols represented by the following general formula (1).
_{HO - [- (CH 2)} 6 -OCOO] n- (CH 2) 6 -OH (1)

Of these polymer polyols (a), preferred are polyester diols, and more preferred are condensed polyester diols derived from one or more aliphatic diols having a branched chain and one or more dicarboxylic acids. Particularly preferred are condensed polyester diols derived from one or more aliphatic diols having a branched chain and one or more aliphatic dicarboxylic acids.

As polyisocyanate (b), (1) aliphatic diisocyanate having 2 to 18 carbon atoms (excluding carbon in NCO group, the same shall apply hereinafter) [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanato Ethyl-2,6-diisocyanatohexanoate and the like]; (2) C 4-15 alicyclic diisocyate [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) Cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene, etc.]; (3) araliphatic diisocyanate having 8 to 15 carbon atoms [m-and / Or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc.]; (4) aromatic diisocyanate [2,4-toluene diisocyanate (TDI), diphenylmethane- 4,4′-diisocyanate (TDI), etc.]; (5) Modified products of these diisocyanates (diisocyanates having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.); and mixtures of two or more thereof .
Of these, alicyclic diisocyanates and araliphatic diisocyanates are preferred, and IPDI, XDI, TMXDI and hydrogenated MDI are particularly preferred.

The urethane resin (A1) contains the polymer polyol (a) and the diisocyanate (b) as essential components, has a carbon-carbon double bond, and further has one or more carbon-carbon double bonds. preferable. Further, (A1) is a mixture of the urethane prepolymer (c) and the diisocyanate trimer (h) having the high molecular polyol (a) and the diisocyanate (b) as essential components. Also good.
In the case of a mixture of urethane prepolymer (c) and diisocyanate trimer (h), the weight ratio of (c) :( h) is preferably 20:80 to 50:50.

The urethane resin (A2) preferably contains the diisocyanate trimer (h) as an essential component, has a carbon-carbon double bond, and preferably has one or more carbon-carbon double bonds. The polyol component (A2) is not particularly limited.
Here, having one or more carbon-carbon double bonds is also referred to as urethane resin (A1) and / or urethane resin (A2) [hereinafter referred to as urethane resin (A). ] Has one or more carbon-carbon double bonds per molecule.

The carbon-carbon double bond of the urethane resin (A1) is obtained by the addition reaction of the urethane prepolymer (c) and the compound (f) having both an active hydrogen group capable of reacting with the carbon-carbon double bond and the isocyanate group. I can do it.
Examples of (f) include 2-hydroxyethyl acrylate (hereinafter referred to as HEA) and 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA).
The number of moles of (f) added is preferably 0.2 to 1.8 moles, more preferably 0.2 to 1 moles per mole of the bifunctional urethane prepolymer (c).

The carbon-carbon double bond of the urethane resin (A2) can be obtained by an addition reaction of the diisocyanate trimer (h) and (f).
The number of added moles of (f) is preferably (f) 0.2 to 2.8 moles, more preferably 0.5 to 2.5 moles, relative to 1 mole of the trifunctional diisocyanate trimer (h). More preferably, it is 0.5-1.5 mol.
Examples of (f) include 2-hydroxyethyl acrylate (hereinafter referred to as HEA) and 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA).

Here, as a carbon-carbon double bond which urethane resin (A) has, a (meth) acryloyl group is mentioned. Here, the (meth) acryloyl group refers to a methacryloyl group and an acryloyl group.

The urethane prepolymer (c) is an isocyanate group-terminated urethane prepolymer derived from an excess of a polyisocyanate (b), a high-molecular polyol (a) and optionally a low-molecular polyol (m). Examples of the low molecular polyol (m) include the above low molecular diols.
When forming the urethane prepolymer (c), the molar ratio of (a), (b) and (m) is preferably 0.1 to 0.9 mol per mol of (b) (a). Preferably it is 0.3-0.8 mol, (m) becomes like this. Preferably it is 0-0.9 mol, More preferably, it is 0.05-0.8 mol. The content of free isocyanate groups in the urethane prepolymer (c) is preferably 0.5 to 45% by weight, more preferably 1 to 35% by weight.

The diisocyanate trimer (h) is a trimer of the above diisocyanate, a compound having an isocyanurate ring and three isocyanate groups, preferably an aliphatic diisocyanate trimer, an alicyclic diisocyanate. Is a trimer of a fatty aromatic diisocyanate. Preferred examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcapro. And aliphatic diisocyanates such as bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate. Preferable examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) and the like. Preferable examples of the aliphatic aromatic diisocyanate include xylylene diisocyanate and tetramethyl xylylene diisocyanate. Of these, hexamethylene diisocyanate (HDI) trimer and isophorone diisocyanate (IPDI) trimer are particularly preferable.

The urethane resin (A) preferably further comprises a chain extender (e) as a constituent component.
Examples of the chain extender (e) include diamine and low molecular diol.
Examples of the diamine include alicyclic diamines [4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexyl, diaminocyclohexane, isophoronediamine, etc.]; aliphatic Diamine [ethylenediamine, hexamethylenediamine, etc.]; aromatic aliphatic diamine [xylylenediamine, α, α, α ′, α′-tetramethylxylylenediamine, etc.]; aromatic diamine [methylenedianiline, m-phenylenediamine, etc. ]. Of these, alicyclic diamines are preferred, and isophorone diamine is particularly preferred.
The chain extender (e) is preferably used as a blocked chain extender (e1). Examples of (e1) include diamine diketimine. Methyl ethyl ketone of the above diamine or diketimine of methyl isobutyl ketone is preferred.
Examples of the low molecular diol include the low molecular diols listed above.
Of the above, diamine is preferred.
When the chain extender (e) is used, the linear molecular weight is presumed to be large. Compared with the case where the chain extender (e) is not used, the compression elastic modulus at 10% displacement does not change much and the compression deformation recovery rate tends to increase. It is preferable.

The number of carbon-carbon double bonds in one molecule of the compound (B) having no urethane bond and a number average molecular weight of 100-1000 and having two or more carbon-carbon double bonds is 2-8. Preferably, 5-7 are more preferable from a viewpoint of having high compressive deformation recovery property.
If the number average molecular weight of the compound (B) is smaller than 100, curing shrinkage during the crosslinking reaction is increased, and if it is larger than 1000, the viscosity is increased, and handling such as miscibility with other materials becomes difficult.
The number average molecular weight of the compound (B) is preferably 170 to 1000, more preferably 170 to 700.

Specific examples of (B) include esters of (meth) acrylic acid and polyhydric alcohols [for example, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diester Pentaerythritol penta (meth) acrylate etc.]; esters of (meth) allyl alcohol and polyvalent carboxylic acids [eg diallyl phthalate, trimellitic acid triallyl ester etc.]; poly (meth) allyl ethers of polyhydric alcohols [eg Pentaerythritol tri (meth) allyl ether etc.]; Polyvinyl ethers of polyhydric alcohols [eg ethylene glycol divinyl ether etc.]; Polypropenyl ethers of polyhydric alcohols [eg ethylene glycol dipropenyl ether] ]; Esters of maleic acid and diols [such as ethylene di maleate]; esters of itaconic acid and a diol [for example, ethylene di-itaconate] and the like. Of these, preferred are esters of (meth) acrylic acid and polyhydric alcohols, and particularly preferred is dipentaerythritol penta (meth) acrylate. In the present invention, the description of (meth) acrylate means methacrylate and acrylate. The same applies to other similar descriptions.

The elastic resin particles (F) of the present invention comprise a cross-linked copolymer of a urethane resin (A) having a carbon-carbon double bond and a compound (B) having two or more carbon-carbon double bonds. The weight ratio of (A) :( B) is preferably 100: 5 to 100: 95.

The volume average particle diameter of the elastic resin particles (F) is preferably 1 to 20 μm. The volume average particle diameter is measured by a dynamic light scattering method.
The elastic resin particles of the present invention have high flexibility and recovery from high compression deformation while having high flexibility.
For example, by measuring the compression modulus at 10% displacement, it can be seen that the film has high flexibility. When the elastic resin particles of the present invention are measured with a Fischer scope H100C (manufactured by Fischer Instrument) (compressive modulus at 10% displacement measurement method 1), the compressive modulus at 10% displacement (MPa) is preferably 100 to 2500. More preferably, it is 240-2450.
In addition, when measured with a micro compression tester PCT-200 (manufactured by Shimadzu Corporation) (10% displacement compression elastic modulus measurement method 2), the 10% displacement compression elastic modulus (MPa) is preferably 100 to 2700. More preferably, it is 350-2600.
Moreover, it can be seen that the compression deformation recovery rate is high by measuring the compression deformation recovery rate. When the elastic resin particles of the present invention are measured with a Fischer scope H100C (Fischer Instrument) (compression deformation recovery rate measurement method 1), the compression deformation recovery rate (%) is preferably 65 to 100, more preferably 70. ~ 100.
Further, when measured with a micro compression tester PCT-200 (manufactured by Shimadzu Corporation) (compression deformation recovery rate measurement method 2), the compression deformation recovery rate (%) is preferably 65 to 100, more preferably 68. ~ 100.

The reason why the elastic resin particles of the present invention have a high flexibility and a high compression deformation recovery property is at least one selected from the group consisting of polyester polyols, polyether polyols, polyether ester polyols, and polycarbonate polyols. Urethane resin having a carbon-carbon double bond comprising at least one of urethane prepolymer (c) and diisocyanate trimer (h) as essential components, high molecular polyol (a) and diisocyanate (b) as essential components It is presumed that (A) is to be copolymerized.
Further, when the compound (B) having two or more carbon-carbon double bonds is a compound having 5 to 7 (meth) acryloyl groups, it has a higher flexibility and a high compression deformation recovery property. Since it has, it is preferable.

The elastic resin particles of the present invention include a filler (t), an additive (u) (for example, a plasticizer, a filler, a release agent, a band charge control agent, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant). , Various additives such as antibacterial agents and preservatives).

  The total content of the filler (t) and the additive (u) can be appropriately added according to various uses. For example, 0 to 50% based on the total mass of (A) and (B). Is more preferable, 5 to 30% is more preferable, and 10 to 20% is particularly preferable.

As the filler (t), any of an inorganic filler (b1), an organic filler (b2), and a mixture thereof may be used.
Examples of the inorganic filler (b1) include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, Metal oxides such as samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy Calcium carbonate, light calcium carbonate, metal carbonate such as zinc carbonate, barium carbonate, dosonite, hydrotalcite, metal sulfate such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, Kure , Talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes and other metal silicates, aluminum nitride, boron nitride, silicon nitride and other metal nitrides, potassium titanate Metal titanates such as calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphoric acids such as tricalcium phosphate Examples thereof include salts, metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, and other fillers.

  Examples of the organic filler (b2) include vinyl resin, urethane resin, epoxy resin, ester resin, polyamide, polyimide, silicone resin, fluorine resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, aniline resin, and ionomer resin. Resin beads such as polycarbonate, cellulose and mixtures thereof.

Although it does not limit at all as a plasticizer (u1), For example, the following (u1-1)-(u1-5), these mixtures, etc. are used.
(U1-1) Phthalic acid ester having 8 to 60 carbon atoms [eg, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.].
(U1-2) Aliphatic dibasic acid ester having 6 to 60 carbon atoms [for example, di-2-ethylhexyl adipate and 2-ethylhexyl sebacate etc.].
(U1-3) Trimellitic acid ester having 10 to 70 carbon atoms [e.g., tri-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid].
(U1-4) C6-C60 phosphate [for example, triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.].
(U1-5) Fatty acid ester having 8 to 50 carbon atoms [eg, butyl oleate and the like].
The method for adding the additive (t) to the resin particles (A) is not particularly limited. For example, in the method for producing the resin particles of the present invention to be described later, they may be mixed in an aqueous medium, After mixing the resins (a) and (t), the mixture may be added and dispersed in an aqueous medium.

In general, a bead spacer for a display device is used to keep a gap between substrates disposed opposite to each other constant, but is required to have a hardness for keeping a cell gap constant and a flexibility not to damage the substrate. Examples of such a display device include a liquid crystal display and a touch panel display.

In general, printed image-receiving layer beads are used to improve the color developability and fixability of printed matter, and these performances can be improved by using elastic beads.

The elastic resin particles of the present invention can react with at least one of the urethane prepolymer (c) and the diisocyanate trimer (h), a carbon-carbon double bond and an isocyanate group using an aqueous solvent or a hydrophobic solvent. Compound (f) having both active hydrogen groups, compound (B) having two or more carbon-carbon double bonds, radical polymerization initiator (g), and dispersant (n), preferably chain extender (e More preferably, after the blocked chain extender (e1) is mixed to produce an emulsified dispersion, it can be polymerized by a production method for obtaining crosslinked urethane resin particles.

Further, a mixture comprising at least one of the above (e1), (c) and (h), (B), (f), (g) and (n) was emulsified and dispersed in an aqueous solvent or a hydrophobic solvent. It is preferable to polymerize afterwards.
Further, (n) is preferably contained in advance in an aqueous solvent or a hydrophobic solvent prior to emulsification and dispersion.
Moreover, it is preferable to produce an emulsified dispersion after reacting (c) or (h) and (f) in advance.
In addition, (f) can be contained in advance in an aqueous solvent or a hydrophobic solvent prior to emulsification and dispersion.
The polymerization is preferably polymerization by heating.

In the step of producing the urethane resin (A) having a carbon-carbon double bond, when (c) is used, since (c) is divalent, the mole of (c) :( f) :( e) The ratio is preferably 1: (0.1-2) :( 0-0.95), more preferably 1: (0.2-1.8) :( 0.1-0.9).
When (h) is used, since (h) is trivalent, the molar ratio of (h) :( f) :( e) is preferably 1: (0.1-3) :( 0-1 .45), more preferably 1: (0.5 to 2.8) :( 0.1 to 1.25).

The dispersant (n) is not particularly limited as long as it can disperse the urethane resin in an aqueous solvent or a hydrophobic solvent, but preferred is a sulfuric ester of an ethylene oxide adduct of polyvinyl alcohol or styrenated alkylphenol. Examples thereof include salts (Eleminol LD-7, manufactured by Sanyo Chemical Industries, Ltd.), sulfonates of alkylated diphenyl ether (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and the like.

Examples of the aqueous solvent include water and a mixed solvent of water and a water-soluble solvent. The ratio of water in the mixed solvent is preferably 0 to 30% by weight. Examples of the water-soluble solvent include alcohol (methanol, ethanol, etc.), ketone (acetone, etc.), ether (tetrahydrofuran, etc.) and the like.

Examples of the hydrophobic solvent include aliphatic hydrocarbons such as heptane and octane; aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatics such as n-hexane, n-heptane, mineral spirit and cyclohexane Or alicyclic hydrocarbon solvents; halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve Ester solvents such as acetate and ethyl cellosolve acetate; ether solvents such as diethyl ether and propylene glycol monomethyl ether; methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone What ketone solvents; amide solvents such as dimethylacetamide; heterocyclic compound-based solvents such as N- methylpyrrolidone, and mixed solvents of two or more thereof.
Of these, preferred are aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents.

It does not specifically limit as a radical polymerization initiator (g), For example, an organic peroxide, an azo compound, etc. are used suitably. Examples of the organic peroxide include benzoyl peroxide and derivatives thereof, lauroyl peroxide, acetyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxide, and t-butyl peroxide. Examples thereof include rate, t-butyl peroxybenzoate, t-butyl peroxyoctate, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl-2-ethylhexanoate, and the like.

Examples of the azo compound include azo compounds such as azobisisobutyronitrile, azobiscyclohexacarbonitrile, and azobis (2,4-dimethylvaleronitrile).
0.1-10 weight part is preferable with respect to 100 weight part of polymerizable monomers, and, as for the compounding quantity of the said radical polymerization initiator (g), 3-8 weight part is more preferable.

The emulsification dispersion is preferably performed at a temperature of 0 to 40 ° C., more preferably 10 to 30 ° C., a stirring rotational speed of preferably 6000 to 20000 rpm, more preferably 8000 to 15000 rpm, and a time of preferably 10 to 120 seconds. More preferably, it is performed in 20 to 90 seconds.

Production equipment for the above emulsifying dispersion is not particularly limited as long as it is generally commercially available as an emulsifying machine or dispersing machine. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer ( Batch type emulsifiers such as Special Machine Industries Co., Ltd., Ebara Milder (made by Aihara Seisakusho Co., Ltd.), TK Fill Mix, TK Pipeline Homo Mixer (made by Special Machine Industries), Colloid Mill (made by Shinko Pantech Co., Ltd.) ), Continuous emulsifiers such as slasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Captron (made by Eurotech), fine flow mill (made by Taiheiyo Kiko Co., Ltd.), microfluidizer (made by Mizuho Industries, Ltd.) ), Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin) Membrane emulsification machine etc., Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

After manufacturing the said emulsified dispersion, it is preferable to carry out at the temperature of 50-120 degreeC and time 3-20 hours in a heat polymerization process.

More preferably, after pre-reacting the urethane prepolymer (c) having two or more isocyanate groups and the compound (f) having both a carbon-carbon double bond and an active hydrogen group capable of reacting with the isocyanate group. It is to produce an emulsified dispersion.

When (f) has one carbon-carbon double bond and one active hydrogen group capable of reacting with an isocyanate group, and (c) is divalent, the mole of (c) :( f) It is preferable that the ratio is preliminarily reacted at 1: (0.1 to 2), and it is more preferable that the ratio is preliminarily reacted at 1: (0.5 to 1.5).
When (c) is trivalent, the molar ratio of (c) :( f) is preferably preliminarily reacted at 1: (0.2-3), and 1: (0.5-2.5) It is more preferable to react in advance.

Further, the compound (f) can be contained in advance in an aqueous solvent or a hydrophobic solvent prior to emulsification and dispersion.

After completion of the polymerization, the elastic resin particles of the present invention can be obtained by solid-liquid separation and / or washing by a known method (centrifugation, filtration, etc.). On the other hand, the product can be produced in a state dispersed in water or in a solvent or the like without performing solid-liquid separation.
In the case of solid-liquid separation and / or washing, this may be followed by drying and / or crushing. Drying and crushing can be performed by a known method, and an air dryer, a smooth air dryer, a Nauta mixer (manufactured by Hosokawa Micron), or the like can be used. Moreover, drying and crushing can also be performed simultaneously by a pulverizing dryer or the like.
The particle size distribution of the elastic resin particles of the present invention may be adjusted by classification if necessary.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. Hereinafter, unless otherwise specified, “parts” means “parts by weight” and% means% by weight.
The composition and symbols of the raw materials used in the following examples are as follows.
Polyol (a-1): Polybutylene adipate diol polyol (a-2) with Mn of 2,000 (hydroxyl number 56): Polycarbonate diol polyol (a-3) with Mn of 1,000 (hydroxyl number 112): Mn Is 2,000 (hydroxyl number 56) polyhexamethylene isophthalate diol compound (B-1): dipentaerythritol hexaacrylate compound (B-2): ethylene glycol dimethacrylate compound (B-3): pentaerythritol tetraacrylate

<Production Examples 1 to 3> Production of urethane prepolymers (c-1) to (c-3) Polyols (a-1) to (a-3) are charged into a reaction vessel in which a stirring bar and a thermometer are set. Dehydration was performed for 2 hours by heating to 120 ° C. under a reduced pressure of 3 mmHg. Subsequently, IPDI was added and reacted at 110 ° C. for 10 hours to synthesize urethane prepolymers (c-1) to (c-3) having an isocyanate group at the terminal. The charge mass ratio of each raw material and the isocyanate content of the urethane prepolymer (hereinafter referred to as NCO%) are as shown in Table 1.

<Production Examples 4 to 11> Production of urethane resins (A1-1) to (A1-6), (A2-1), and (A2-2) HEMA was charged into a reaction vessel in which a stirring bar and a thermometer were set. Dehydration was performed for 2 hours by heating to 120 ° C. under a reduced pressure of 3 mmHg. Subsequently, urethane prepolymers (c-1) to (c-3) or hexamethylene diisocyanate isocyanurate (HDI trimer) is added, the reaction is performed at 110 ° C. for 10 hours, and a urethane resin having a carbon-carbon double bond. (A1-1) to (A1-6), (A2-1), and (A2-2) were synthesized. The charge mass ratio, isocyanate content, and carbon-carbon double bond content of each raw material are as shown in Table 2.

<Production Example 12> Production of chain extender (e) In a reaction vessel equipped with a stirring rod and a thermometer, 54 parts of isophoronediamine (hereinafter referred to as IPDA), 46 parts of methyl ethyl ketone (hereinafter referred to as MEK), and normal After adding 200 parts of hexane and reacting at 70 ° C. for 10 hours, water was removed by liquid separation to obtain a diketimine compound [chain extender (e-1)] composed of one IPDA molecule and two MEK molecules.

<Examples 1-4>
Urethane resins (A1-1) to (A1-3) in the amounts shown in Table 3 in a beaker (A2-1) Compounds (B-1) to (B-) having two or more carbon-carbon double bonds 3), and polymerization initiator azobisisobutyronitrile, 737 parts of water in which 3 parts of polyvinyl alcohol [“PVA-235”, manufactured by Kuraray Co., Ltd.] was dissolved were added, and at room temperature, Using an ultradisperser (manufactured by Yamato Kagaku), mixing was performed at a rotation speed of 9,000 rpm for 1 minute.
After mixing, the mixture was reacted at 90 ° C. for 12 hours under a nitrogen atmosphere to obtain an aqueous dispersion. Subsequently, it was dried after classification to obtain elastic resin particles (F-1) to (F-4) having a volume average particle diameter and a particle size distribution shown in Table 3.

<Examples 5 to 8>
Urethane resins (A1-4) to (A1-6) and (A2-2) monomers (B-1) to (B-2) having two or more carbon-carbon double bonds in the amounts shown in Tables 3 and 4 in a beaker ( B-3), polymerization initiator azobisisobutyronitrile, and chain extender (e-1) are mixed and 3 parts of polyvinyl alcohol ["PVA-235", manufactured by Kuraray Co., Ltd.] are dissolved. 737 parts of the prepared water was added and mixed at room temperature for 1 minute using an ultradisperser (manufactured by Yamato Kagaku) at room temperature.
After mixing, the mixture was aged at 50 ° C. for 5 hours in a nitrogen atmosphere, and then reacted at 90 ° C. for 12 hours to obtain an aqueous dispersion. Subsequently, it was dried after classification to obtain elastic resin particles (F-5) to (F-8) having a volume average particle size and a particle size distribution shown in Tables 3 and 4.

<Comparative Example 1>
737 parts of divinylbenzene, 74 parts of styrene, and 12 parts of benzoyl peroxide are added to 737 parts of a dispersion in which 3 parts of polyvinyl alcohol ["PVA-235", manufactured by Kuraray Co., Ltd.] are dissolved. Polymerization was carried out at 20 ° C. for 20 hours. This was classified and further dried to obtain resin particles (R-1).

<Comparative example 2>
In Comparative Example 1, resin particles (R-2) were obtained by the same method as Comparative Example 1 except that ethylene di (meth) acrylate was used instead of divinylbenzene and methyl (meth) acrylate was used instead of styrene.

<Comparative Example 3>
In Comparative Example 1, Comparative Example 1 except that both ends urethane acrylate modified polybutadiene (manufactured by Nippon Soda Co., Ltd., TE-1000, Mn1000) was used instead of divinylbenzene, and methyl (meth) acrylate was used instead of styrene. Resin particles (R-3) were obtained by the same method.

<Number average molecular weight, volume average molecular weight>
The number average molecular weight and the volume average molecular weight were measured by the gel permeation chromatography method under the following conditions.
Measurement conditions: temperature 40 ° C., tetrahydrofuran solvent, polystyrene conversion

<Volume average particle size, particle size distribution>
The volume average particle size and particle size distribution were measured by the electrozone method and measured under the following conditions.
Equipment: Multitizer III manufactured by Beckman Coulter
Measurement range: 0.4 μm to 1200 μm
Measurement sample concentration: Set appropriately so that aperture clogging does not occur. Used diluted with water.
Particle size distribution: expressed in CV (value obtained by dividing the standard deviation by the center particle size in percentage).

  For elastic resin particles (F-1) to (F-8) and comparative resin particles (R-1) to (R-3), compression elastic modulus at 10% displacement (measurement method 1 and measurement method 2) and compression Deformation recovery rates (Measurement Method 1 and Measurement Method 2) were measured by the following methods, and the results are shown in Tables 3 and 4.

<Measurement method 1 of compressive elastic modulus at 10% displacement>
Using a Fischer Scope H100C (manufactured by Fischer Instrument), the load value when the particle is displaced to 10% of the particle diameter by applying a load to the particle center in the 25 ° C atmosphere on the sample stage. The compression elastic modulus at the time of 10% displacement calculated by the following formula described above from the value was measured. The measured value is an average value of five measured values. (The same applies to the following 10% displacement compression elastic modulus and compression deformation recovery rate.)
[Compressive modulus at 10% displacement] = 3F / (2S ³ R) ^1/2
Here, F represents a compressive load. S represents the compression displacement, and R represents the particle radius. The measurement was performed at 25 ° C. Measurement values were used for compressive load and compressive displacement. The volume average particle diameter was used as the particle radius.

<Measurement method 2 for compressive modulus at 10% displacement>
When a micro compression tester PCT-200 (manufactured by Shimadzu Corporation) is used, a load is applied to the particle in the direction of the center of the particle on a sample stage in an atmosphere at 25 ° C., and the particle is displaced to 10% of the particle diameter. The compression elastic modulus at 10% displacement calculated by the following formula described above from the load value and displacement value of was measured.
[Compressive modulus at 10% displacement] = 3F / (2S ³ R) ^1/2
Here, F represents a compressive load. S represents the compression displacement, and R represents the particle radius. The measurement was performed at 25 ° C. Measurement values were used for compressive load and compressive displacement. The volume average particle diameter was used as the particle radius.

<Compression deformation recovery rate measurement method 1>
Using a Fischer scope H100C (manufactured by Fischer Instrument), load the particles toward the center of the particles on the sample stage in an atmosphere at 25 ° C, hold the load up to 10 mN for 10 seconds, and hold for 10 seconds. Further, after unloading to 1.0 mN in 10 seconds, it was held for 10 seconds. A value obtained by dividing the displacement at the time of 1.0 mN load at this time by the displacement at the time of 10 mN load is obtained as a percentage. The difference obtained by subtracting the value from 100 is taken as the compression deformation recovery rate.
Compression deformation recovery rate = 100-(displacement at 1.0 mN load / displacement at 10 load) x 100

<Compression deformation recovery rate measurement method 2>
Using a micro compression tester PCT-200 (manufactured by Shimadzu Corporation) and applying a load to the center of the particle on the sample stage in a 25 ° C. atmosphere and applying a load up to 9.8 mN , 0.98 mN, and a value obtained by dividing the displacement at 0.98 mN load by the displacement at 9.8 mN load in percentage. The difference obtained by subtracting the value from 100 is taken as the compression deformation recovery rate.
Compression deformation recovery rate = 100-(Displacement at 0.98mN load / Displacement at 9.8mN load) x 100

As is apparent from the results in Tables 3 and 4, the elastic resin particles of the present invention have a high compression deformation recovery rate even when the compression elastic modulus is low.
This feature is not observed in the styrene resin particles of Comparative Example 1 and the acrylic resin particles of Comparative Example 2. Further, when a soft segment is formed in the molecule using polybutadiene diol as in Comparative Example 3, it becomes a plastic component and the compression elastic modulus is lowered, but the compression deformation recovery rate is also lowered.
Moreover, when Examples 1-4 and Examples 5-8 corresponding to them are compared, when the chain extender (e) is used, it is presumed that the linear molecular weight is increased. The compression elastic modulus at% displacement does not change much, and the compression deformation recovery rate tends to increase, which is preferable.
In Comparative Examples 1 to 3, the compression deformation recovery rate of Measurement Method 1 is smaller than the measurement value of Measurement Method 2, which is opposite to the tendency of Examples 1 to 8. This is because in measurement method 1, the load applied to the particles is increased by performing an operation that is not in measurement method 2, that is, holding the load for 10 seconds after applying and removing the load, respectively. This phenomenon occurs because the recovery rate of the particles used in the comparative example is low.

The resin particles obtained by the method for producing elastic resin particles of the present invention are characterized by excellent elasticity and recoverability.
Therefore, the elastic resin particles of the present invention are useful for spacers for manufacturing electronic parts such as liquid crystal displays, light diffusion plates, light diffusion films, paint additives, cosmetics applications and the like.

Claims (13)

At least one polymer polyol (a) selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol, and polycarbonate polyol and diisocyanate (b) are essential components, and a carbon-carbon double bond is formed. Containing a cross-linked copolymer of a urethane resin (A1) having a compound (B) having no urethane bond and a number average molecular weight of 100 to 1000 and having two or more carbon-carbon double bonds. Characteristic elastic resin particles. A diisocyanate trimer (h) as an essential component, a urethane resin (A2) having a carbon-carbon double bond, and a carbon-carbon double bond having no urethane bond and a number average molecular weight of 100 to 1000 An elastic resin particle comprising a cross-linked copolymer with a compound (B) having two or more thereof. The urethane resin (A1) has a mixture of the urethane prepolymer (c) having the high molecular polyol (a) and the diisocyanate (b) as essential components and the diisocyanate trimer (h) as essential components. The elastic resin particle according to claim 1. The elastic resin particles according to any one of claims 1 to 3, wherein the urethane resin (A1) and the urethane resin (A2) have one or more carbon-carbon double bonds. The elastic resin particles according to claim 1, 3 or 4, wherein the polymer polyol (a) has a number average molecular weight of 200 to 8000. The urethane resin (A1) comprises, as essential components, a urethane prepolymer (c) and a compound (f) having both a carbon-carbon double bond and an active hydrogen group capable of reacting with an isocyanate group. 4. The elastic resin particles according to 4 or 5. The elastic resin particles according to claim 2, 4 or 5, wherein the urethane resin (A2) comprises a diisocyanate trimer (h) and the compound (f) as essential components. The elastic resin particles according to any one of claims 1 to 7, wherein the urethane resin (A1) and the urethane resin (A2) further comprise a chain extender (e) as an essential component. The elastic resin particles according to any one of claims 1 to 8, wherein the compound (B) is a compound having 5 to 7 carbon-carbon double bonds. The elastic resin particle according to any one of claims 1 to 9, wherein the carbon-carbon double bond is a (meth) acryloyl group. The elastic compound particle according to any one of claims 1 to 10, wherein the compound (B) is a (meth) acrylate of a polyfunctional polyol. The bead spacer for display apparatuses which consists of the elastic resin particle of any one of Claims 1-11. The bead spacer for printing image receiving layers which consists of the elastic resin particle of any one of Claims 1-11.