WO2022186248A1 - Composition de résine, procédé de production de fines particules polymères et procédé de production d'une composition de résine - Google Patents

Composition de résine, procédé de production de fines particules polymères et procédé de production d'une composition de résine Download PDF

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WO2022186248A1
WO2022186248A1 PCT/JP2022/008754 JP2022008754W WO2022186248A1 WO 2022186248 A1 WO2022186248 A1 WO 2022186248A1 JP 2022008754 W JP2022008754 W JP 2022008754W WO 2022186248 A1 WO2022186248 A1 WO 2022186248A1
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weight
polymer
monomer
meth
fine particles
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PCT/JP2022/008754
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Japanese (ja)
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展祥 舞鶴
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株式会社カネカ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters

Definitions

  • the present invention relates to a resin composition, a method for producing polymer fine particles, and a method for producing a resin composition.
  • Radically curable resins such as unsaturated polyester resins and vinyl ester resins are widely used in various applications such as coating materials and molding compositions containing reinforcing materials such as glass fibers. .
  • curable resins have the problem that they are accompanied by large curing shrinkage during curing, and cracks occur in the cured product due to internal stress within the cured product. Therefore, various attempts have been made to impart toughness to these curable resins, which are very brittle materials.
  • Elastomers include polymer microparticles (eg, crosslinked polymer microparticles).
  • Patent Document 1 a specific amount of polymer microparticles (polymer microparticles) as an elastomer are dispersed in a curable resin in the state of primary particles, and if necessary, a specific amount of an epoxy resin and at least one polymerizable non-polymeric polymer in the molecule.
  • a curable resin composition containing a low molecular weight compound having a saturated bond and a molecular weight of less than 300 is disclosed.
  • the curable resin composition of Patent Document 1 has toughness and crack resistance without reducing the heat resistance (Tg), transparency, elastic modulus, surface tackiness, and weather resistance (yellowing) of the resulting cured product. It is disclosed that the adhesive properties can be significantly improved, the viscosity of the composition is low, and the adhesion to the substrate can be improved.
  • One aspect of the present invention has been made in view of the above problems, and its object is to provide a resin composition that is excellent in handleability and storage stability.
  • the present inventors have found that by including a specific amount of a specific polyfunctional monomer as a cross-linking agent in the monomer constituting the graft portion of the polymer fine particles, The inventors have found new knowledge that a resin composition excellent in handleability and storage stability can be provided, and have completed the present invention.
  • the resin composition according to one embodiment of the present invention contains polymer fine particles (A) and a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule
  • the coalesced fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body, and the elastic body is a diene-based rubber, a (meth)acrylate-based One or more selected from the group consisting of rubber and organosiloxane rubber, wherein the graft portion is derived from a first structural unit derived from a first monomer and a second monomer second structural unit, wherein the first monomer is selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers One or more types, the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and the first structural unit in the graft portion and the When the total
  • the composition according to one embodiment of the present invention contains polymer fine particles (A) and a low molecular weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule.
  • the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body, and the elastic body is a diene rubber, ( One or more selected from the group consisting of meth)acrylate-based rubbers and organosiloxane-based rubbers, wherein the graft portion comprises a first structural unit derived from a first monomer and a second monomer the first monomer is an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer.
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and the first monomer in the graft portion
  • the second structural unit is more than 0.00% by weight and less than 2.00% by weight
  • the polymer fine particles When the total amount of A) and the low molecular compound (C) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the low molecular compound (C) is 50 to 99% by weight. %.
  • the first monomer is one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers;
  • the monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and in the graft part preparation step, the first monomer and the second monomer
  • the second monomer is used in an amount of more than 0.00% by weight and less than 2.00% by weight when the total of the above is 100% by weight.
  • Embodiment 1 [1. Technical idea of Embodiment 1 of the present invention]
  • a resin composition containing polymer fine particles and a matrix resin having two or more polymerizable unsaturated bonds in the molecule from the viewpoint of handling when using the resin composition, A low viscosity is preferred.
  • phase separation may occur between the polymer fine particles in the resin composition and the matrix resin, which improves the storage stability of the resin composition.
  • the content of the matrix resin having two or more polymerizable unsaturated bonds in the molecule is large in the resin composition (for example, the matrix resin is 90% by weight in 100% by weight of the resin composition).
  • phase separation between the polymer fine particles and the matrix resin was remarkable during long-term storage of the resin composition.
  • the phase separation between the polymer fine particles in the resin composition and the matrix resin was caused by aggregation of the polymer fine particles in the resin composition.
  • the viscosity of the resin composition can be reduced by using a specific polyfunctional monomer as a monomer in the formation (polymerization) of the graft portion of the polymer fine particles.
  • the specific polyfunctional monomer can function as a cross-linking agent.
  • the present inventors conducted further intensive studies in order to achieve both reduction in the viscosity of the resin composition and maintenance of the dispersed state of the polymer fine particles in the resin composition.
  • the present inventors have newly discovered the following knowledge and completed the present invention: in the formation (polymerization) of the graft portion of polymer fine particles, a specific polyfunctional monomer (crosslinking agent) By using a specific amount of, it is possible to reduce the viscosity of the resin composition and maintain the dispersion state of the polymer fine particles in the resin composition.
  • the resin composition according to Embodiment 1 of the present invention contains fine polymer particles (A) and a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule.
  • the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body.
  • the elastic body of the fine polymer particles (A) contains one or more selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers.
  • the graft portion of the fine polymer particles (A) is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer, and
  • the first monomer is one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers
  • the second monomer is , is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule.
  • the second structural unit is 0.00%. % by weight and less than 2.00% by weight.
  • the polymer fine particles (A) are 1 to 50% by weight and the matrix resin (B) is 50 to 99% by weight. is.
  • the polymer constituting the graft portion of the polymer fine particles (A) contains the second structural unit derived from the second monomer, whereby the polymer The viscosity of the resin composition can be reduced as compared with the case where the grafted portion of the fine particles (A) does not contain the second structural unit. Therefore, the resin composition according to Embodiment 1 of the present invention has the advantage of being excellent in handleability.
  • the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight.
  • the content of the second structural unit is more than 0.00% by weight and less than 2.00% by weight, the dispersed state of the polymer fine particles (A) in the resin composition can be maintained. Aggregation of the polymer fine particles (A) can be prevented. As a result, phase separation is less likely to occur when the resin composition is stored for a long period of time. Therefore, the resin composition according to Embodiment 1 of the present invention has an advantage of excellent storage stability.
  • polymerizable unsaturated bond means a polymerizable unsaturated bond.
  • the polymerizable unsaturated bond can be said to be a bond that initiates a polymerization reaction with the bond as a starting point.
  • a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule means "a polyfunctional monomer having two or more radically polymerizable reactive groups in the same molecule. ” can also be said.
  • a “radical polymerizable reactive group” means a reactive group having radical polymerizability.
  • the radically polymerizable reactive group can be said to be a reactive group that initiates a radical polymerization reaction with the reactive group as a starting point when a radical attacks the reactive group.
  • the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body.
  • the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber.
  • the elastic body may contain natural rubber in addition to the rubbers described above.
  • the elastic body can also be called an elastic portion or a rubber particle.
  • (Meth)acrylate as used herein means acrylate and/or methacrylate.
  • the elastic body contains diene rubber (Case A)
  • Case A the resulting resin composition can provide a cured product with excellent toughness and impact resistance.
  • a cured product having excellent toughness and/or impact resistance can also be said to be a cured product having excellent durability.
  • a diene-based rubber is an elastic body containing structural units derived from diene-based monomers.
  • the diene-based monomer can also be called a conjugated diene-based monomer.
  • the diene-based rubber contains (i) 50% to 100% by weight of structural units derived from a diene-based monomer and a diene copolymerizable with the diene-based monomer, out of 100% by weight of the structural units.
  • ком ⁇ онентs derived from vinyl monomers other than system monomers may contain 0% to 50% by weight of structural units derived from vinyl monomers other than system monomers, and (ii) 50% by weight of structural units derived from diene monomers; 100% by weight or less, and 0% by weight or more and less than 50% by weight of structural units derived from vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers, (iii) 60% to 100% by weight of structural units derived from diene-based monomers, and derived from vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers (iv) 70% to 100% by weight of structural units derived from a diene-based monomer, and copolymerized with a diene-based monomer It may contain 0% to 30% by weight of structural units derived from vinyl monomers other than diene monomers, and (v) 80 structural units derived from diene monomers
  • the diene-based rubber may contain, as structural units, structural units derived from (meth)acrylate-based monomers in an amount smaller than the structural units derived from diene-based monomers.
  • diene-based monomers examples include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene. These diene-based monomers may be used alone or in combination of two or more.
  • Vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers include, for example, styrene, ⁇ -methylstyrene, and monochlorostyrene.
  • Vinylarenes such as , dichlorostyrene; Vinylcarboxylic acids such as acrylic acid and methacrylic acid; Vinyl cyanides such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; , propylene, butylene, and isobutylene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene.
  • the vinyl-based monomer A described above may be used alone or in combination of two or more. Among the vinyl-based monomers A described above, styrene is particularly preferable.
  • the structural unit derived from the vinyl-based monomer A is an optional component.
  • the diene-based rubber may be composed only of structural units derived from diene-based monomers.
  • the diene-based rubber may be butadiene rubber (also referred to as polybutadiene rubber) composed of structural units derived from 1,3-butadiene, or butadiene- Styrene rubber (also called polystyrene-butadiene) is preferred, and butadiene rubber is more preferred.
  • the polymer fine particles (A) containing the diene rubber can more effectively exhibit the desired effects.
  • butadiene-styrene rubber is more preferable in that the transparency of the resulting cured product can be enhanced by adjusting the refractive index.
  • the butadiene-styrene rubber contains (i) more than 50% by weight and 100% by weight or less of butadiene-derived structural units and 0% by weight or more and 50% by weight of styrene-derived structural units in 100% by weight of butadiene-styrene rubber. (ii) 60% to 100% by weight of structural units derived from butadiene and 0% to 40% by weight of structural units derived from styrene.
  • (iii) may contain 70% to 100% by weight of structural units derived from butadiene and 0% to 30% by weight of structural units derived from styrene, and (iv) a structure derived from butadiene It may contain 80% to 100% by weight of units and 0% to 20% by weight of structural units derived from styrene, and (v) 90% to 100% by weight of structural units derived from butadiene. , and 0% to 10% by weight of structural units derived from styrene.
  • the butadiene-styrene rubber contains (vi) 70% to 90% by weight of butadiene-derived structural units and 10% to 30% by weight of styrene-derived structural units in 100% by weight of butadiene-styrene rubber.
  • (vii) may contain 70% to 85% by weight of structural units derived from butadiene and 15% to 30% by weight of structural units derived from styrene, and
  • (viii) It may contain 70% to 80% by weight of structural units derived from butadiene and 20% to 30% by weight of structural units derived from styrene, and (ix) 75% by weight of structural units derived from butadiene. % to 80% by weight, and 20% to 25% by weight of structural units derived from styrene.
  • (Meth)acrylate-based rubber is an elastic body containing, as a structural unit, a structural unit derived from a (meth)acrylate-based monomer.
  • the (meth)acrylate rubber contains (i) 50% to 100% by weight of structural units derived from (meth)acrylate monomers in 100% by weight of structural units, and (meth)acrylate 0% to 50% by weight of a structural unit derived from a vinyl monomer other than a (meth)acrylate monomer copolymerizable with the monomer may be included, (ii) (meth ) More than 50% by weight but not more than 100% by weight of structural units derived from acrylate-based monomers, and vinyl units other than (meth)acrylate-based monomers copolymerizable with (meth)acrylate-based monomers It may contain 0% by weight or more and less than 50% by weight of structural units derived from a monomer, (iii) 60% to 100% by weight of structural units derived from a (meth)acrylate mono
  • the (meth)acrylate-based rubber may contain structural units derived from a diene-based monomer in an amount smaller than the structural units derived from the (meth)acrylate-based monomer. good.
  • (meth)acrylate monomers examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and dodecyl (meth)acrylate.
  • Alkyl (meth)acrylates such as stearyl (meth)acrylate and behenyl (meth)acrylate; Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; ) acrylate, hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate; glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate; alkoxyalkyl (meth)acrylates; Allylalkyl (meth)acrylates such as allyl (meth)acrylate and allylalkyl (meth)acrylate; monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc.
  • Examples include polyfunctional (meth)acrylates. These (meth)acrylate monomers may be used alone or in combination of two or more. Among these (meth)acrylate monomers, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate is more preferred.
  • the (meth)acrylate rubber is preferably one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber and 2-ethylhexyl (meth)acrylate rubber.
  • butyl (meth)acrylate rubber is more preferred.
  • Ethyl (meth)acrylate rubber is rubber composed of structural units derived from ethyl (meth)acrylate
  • butyl (meth)acrylate rubber is rubber composed of structural units derived from butyl (meth)acrylate
  • a meth)acrylate rubber is a rubber composed of structural units derived from 2-ethylhexyl (meth)acrylate.
  • the glass transition temperature (Tg) of the elastic body is lowered, so that the polymer fine particles (A) and the resin composition having a low Tg can be obtained.
  • the obtained resin composition can provide a cured product having excellent toughness, and (ii) the viscosity of the resin composition can be made lower.
  • the vinyl-based monomer other than the (meth)acrylate-based monomer copolymerizable with the (meth)acrylate-based monomer (hereinafter also referred to as vinyl-based monomer B), the vinyl-based monomer The monomers listed in Form A are included. Only one kind of the vinyl-based monomer B may be used, or two or more kinds thereof may be used in combination. Among the vinyl-based monomers B, styrene is particularly preferred.
  • the structural unit derived from the vinyl monomer B is an optional component.
  • the (meth)acrylate rubber may be composed only of structural units derived from (meth)acrylate monomers.
  • the elastic body contains organosiloxane rubber (Case C)
  • Case C the resulting resin composition has sufficient heat resistance and can provide a cured product with excellent impact resistance at low temperatures.
  • Organosiloxane-based rubbers include, for example, (i) composed of alkyl- or aryl-disubstituted silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy.
  • Organosiloxane polymers (ii) organosiloxane polymers composed of alkyl- or aryl-monosubstituted silyloxy units such as organohydrogensilyloxy in which some of the alkyl side chains are substituted with hydrogen atoms. be done. These organosiloxane polymers may be used alone or in combination of two or more.
  • a polymer composed of dimethylsilyloxy units is referred to as dimethylsilyloxy rubber
  • a polymer composed of methylphenylsilyloxy units is referred to as methylphenylsilyloxy rubber.
  • Polymers composed of oxy units are called dimethylsilyloxy-diphenylsilyloxy rubbers.
  • the organosiloxane rubber is (i) dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenyl, since the resulting resin composition can provide a cured product having excellent heat resistance. It is preferably one or more selected from the group consisting of silyloxy rubbers, and (ii) more preferably dimethylsilyloxy rubber because it is readily available and economical.
  • the fine polymer particles (A) preferably contain 80% by weight or more, more preferably 90% by weight or more, of the organosiloxane rubber in 100% by weight of the elastic material contained in the fine polymer particles (A). It is more preferable to have According to the configuration, the obtained resin composition can provide a cured product having excellent heat resistance.
  • the elastic body may further contain an elastic body other than diene rubber, (meth)acrylate rubber and organosiloxane rubber.
  • elastic bodies other than diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers include natural rubbers.
  • the elastomer is butadiene rubber, butadiene-styrene rubber, butadiene-(meth)acrylate rubber, ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, 2-ethylhexyl (meth)acrylate rubber. , dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyloxy rubber, preferably one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber, butyl (meth)acrylate It is more preferably one or more selected from the group consisting of rubber and dimethylsilyloxy rubber.
  • a crosslinked structure of elastic body From the viewpoint of maintaining the dispersion stability of the polymer fine particles (A) in the thermosetting resin, it is preferable that a crosslinked structure is introduced into the elastic body.
  • a method for introducing a crosslinked structure into the elastic body a generally used method can be adopted, and examples thereof include the following methods. That is, in the production of the elastic body, a monomer capable of constituting the elastic body is mixed with a cross-linkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound, and then polymerized. . In this specification, manufacturing a polymer such as an elastomer is also referred to as polymerizing the polymer.
  • Methods for introducing a crosslinked structure into an organosiloxane rubber include the following methods: (A) when polymerizing an organosiloxane rubber, a polyfunctional alkoxysilane compound and another material are combined; (B) introducing a reactive group (e.g., (i) a mercapto group and (ii) a reactive vinyl group, etc.) into an organosiloxane-based rubber, and then to the resulting reaction product, (i) a method of radical reaction by adding an organic peroxide or (ii) a polymerizable vinyl monomer or the like, or (C) a polyfunctional monomer when polymerizing an organosiloxane rubber; and/or a method of mixing a crosslinkable monomer such as a mercapto group-containing compound with other materials, followed by polymerization, and the like.
  • a reactive group e.g., (i) a mercapto group and (ii) a reactive vinyl group, etc.
  • a polyfunctional monomer is a monomer having two or more polymerizable unsaturated bonds in the molecule. Said polymerizable unsaturated bond is preferably a carbon-carbon double bond.
  • Examples of polyfunctional monomers include (meth)acrylates having an ethylenically unsaturated double bond, such as allylalkyl (meth)acrylates and allyloxyalkyl (meth)acrylates, butadiene is not included. be done.
  • Examples of monomers having two (meth)acrylic groups include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and cyclohexanedimethanol.
  • Examples of the polyethylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, and the like. are exemplified.
  • alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxy tri(meth)acrylate.
  • examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, dipentaerythritol penta(meth)acrylate etc. are illustrated as a monomer which has five (meth)acrylic groups. Furthermore, examples of monomers having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Polyfunctional monomers also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.
  • polyfunctional monomers that can be preferably used in the polymerization of the elastic body include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol. Di(meth)acrylates, hexanediol di(meth)acrylates, cyclohexanedimethanol di(meth)acrylates, and polyethylene glycol di(meth)acrylates. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.
  • Mercapto group-containing compounds include alkyl group-substituted mercaptans, allyl group-substituted mercaptans, aryl group-substituted mercaptans, hydroxy group-substituted mercaptans, alkoxy group-substituted mercaptans, cyano group-substituted mercaptans, amino group-substituted mercaptans, silyl group-substituted mercaptans, and acid group-substituted mercaptans. mercaptans, halo group-substituted mercaptans, acyl group-substituted mercaptans, and the like.
  • alkyl-substituted mercaptan an alkyl-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkyl-substituted mercaptan having 1 to 10 carbon atoms is more preferable.
  • aryl group-substituted mercaptan a phenyl group-substituted mercaptan is preferred.
  • alkoxy-substituted mercaptan an alkoxy-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkoxy-substituted mercaptan having 1 to 10 carbon atoms is more preferable.
  • the acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and having 1 to 10 carbon atoms or an aryl group-substituted mercaptan having a carboxyl group and having 1 to 12 carbon atoms.
  • the glass transition temperature of the elastic body is preferably 80° C. or lower, more preferably 70° C. or lower, more preferably 60° C. or lower, more preferably 50° C. or lower, more preferably 40° C. or lower, more preferably 30° C. or lower.
  • ° C. or lower is more preferred, 10 ° C. or lower is more preferred, 0 ° C. or lower is more preferred, -20 ° C. or lower is more preferred, -40 ° C. or lower is more preferred, -45 ° C. or lower is more preferred, and -50 ° C. or lower is more preferred.
  • glass transition temperature may be referred to as "Tg”.
  • polymer fine particles (A) having a low Tg and a resin composition having a low Tg can be obtained.
  • the obtained resin composition can provide a cured product having excellent toughness.
  • the viscosity of the resin composition obtained can be made lower.
  • the Tg of the elastic body can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles (A).
  • Tg can be measured as follows: (1) For a flat plate made of polymer fine particles (A), a dynamic viscoelasticity measuring device (eg, DVA-200 manufactured by IT Keisoku Co., Ltd.) ) is used to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan ⁇ graph; (2) Regarding the obtained tan ⁇ graph, the tan ⁇ peak temperature is taken as the glass transition temperature.
  • a dynamic viscoelasticity measuring device eg, DVA-200 manufactured by IT Keisoku Co., Ltd.
  • the elastic modulus (rigidity) of the resulting cured product can be suppressed from decreasing, that is, a cured product having a sufficient elastic modulus (rigidity) can be obtained. 20° C. or higher is more preferred, 50° C. or higher is even more preferred, 80° C. or higher is particularly preferred, and 120° C. or higher is most preferred.
  • the Tg of the elastic body can be determined by the composition of the constituent units contained in the elastic body. In other words, the Tg of the resulting elastic body can be adjusted by changing the composition of the monomers used when manufacturing (polymerizing) the elastic body.
  • a group of monomers that provide a homopolymer having a Tg greater than 0 ° C. is referred to as a monomer group a.
  • a group of monomers that provide a homopolymer having a Tg of less than 0° C. when only one type of monomer is polymerized is referred to as a monomer group b.
  • An elastic body G is defined as an elastic body containing 0 to 50% by weight (more preferably 1 to 35% by weight) of structural units derived from one type of monomer.
  • the elastic body G has a Tg greater than 0°C. Moreover, when the elastic body contains the elastic body G, the obtained resin composition can provide a cured product having sufficient rigidity.
  • a crosslinked structure is introduced into the elastic body.
  • Methods for introducing the crosslinked structure include the methods described above.
  • Examples of monomers that can be included in the monomer group a include, but are not limited to, styrene, unsubstituted vinyl aromatic compounds such as 2-vinylnaphthalene; vinyl-substituted compounds such as ⁇ -methylstyrene; Aromatic compounds; ring-alkylated vinyls such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene and 2,4,6-trimethylstyrene Aromatic compounds; Ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; Ring halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; 4-acetoxystyrene and the like ring-ester-substituted vinyl aromatic compounds; ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene
  • Examples of the monomer group b include ethyl acrylate, butyl acrylate (also known as butyl acrylate), 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. etc. Only one type of these monomer group b may be used, or two or more types may be used in combination. Among these monomer groups b, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the volume average particle diameter of the elastic body is preferably 0.03 ⁇ m to 50.00 ⁇ m, more preferably 0.05 ⁇ m to 10.00 ⁇ m, more preferably 0.08 ⁇ m to 2.00 ⁇ m, and further preferably 0.10 ⁇ m to 1.00 ⁇ m. It is preferably 0.10 ⁇ m to 0.80 ⁇ m, and particularly preferably 0.10 ⁇ m to 0.50 ⁇ m.
  • the volume average particle diameter of the elastic body is (i) 0.03 ⁇ m or more, an elastic body having a desired volume average particle diameter can be stably obtained, and (ii) when it is 50.00 ⁇ m or less, it can be obtained. The heat resistance and impact resistance of the resulting cured product are improved.
  • the volume-average particle size of the elastic body can be measured by using an aqueous suspension containing the elastic body as a sample and using a dynamic light scattering particle size distribution analyzer or the like.
  • the proportion of the elastic body in the polymer microparticles (A) is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, more preferably 60 to 93% by weight, based on 100% by weight of the entire polymer microparticles (A). is more preferable, 70 to 93% by weight is more preferable, 70 to 90% by weight is more preferable, 70 to 87% by weight is more preferable, and 70 to 85% by weight is even more preferable.
  • the proportion of the elastic body is (i) 40% by weight or more, the resulting resin composition can provide a cured product having excellent toughness and impact resistance, and (ii) is 97% by weight or less. In this case, since the polymer fine particles (A) do not easily aggregate, the resin composition does not become highly viscous, and as a result, the obtained resin composition can be excellent in handleability.
  • the ratio of the elastic material in the fine polymer particles (A) when the ratio of the elastic material in the fine polymer particles (A) increases and the ratio of the graft portion decreases, the elastic material is absorbed by the graft portion. It is exposed as an elastic body without being fully covered, and tends to aggregate. This is because aggregation of the fine polymer particles (A) is prevented by the steric repulsion effect of the graft portion. This aggregation increases the viscosity of the resin composition. This aggregation occurs during production of the resin composition containing the polymer fine particles (A) or over time.
  • the cross-linking of the graft part fixes the graft chain to some extent, suppressing entanglement and reducing the viscosity.
  • the fixation of the grafted chains suppresses the steric repulsion effect, making aggregation more likely to occur over time.
  • the elastomer is swellable in a suitable solvent, but substantially insoluble.
  • the elastic body is preferably insoluble in the thermosetting resin used.
  • the elastic body preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • the obtained resin composition can provide a cured product having excellent toughness.
  • the method for calculating the gel content is as follows. First, an aqueous suspension containing the polymer fine particles (A) is obtained, and then powder particles of the polymer fine particles (A) are obtained from the aqueous suspension.
  • the method for obtaining powdery particles of the polymer microparticles (A) from the aqueous suspension is not particularly limited. For example, (i) aggregate the polymer microparticles (A) in the aqueous suspension, ) dehydrating the obtained aggregates, and (iii) further drying the aggregates to obtain powder particles of the polymer fine particles (A). Next, 2.0 g of powder particles of polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • the obtained MEK melt is separated into a component soluble in MEK (MEK soluble matter) and a component insoluble in MEK (MEK insoluble matter).
  • MEK soluble matter MEK soluble matter
  • MEK insoluble matter MEK insoluble matter
  • a centrifuge manufactured by Hitachi Koki Co., Ltd., CP60E
  • the obtained MEK lysate was subjected to centrifugation for 1 hour at a rotation speed of 30000 rpm, and the lysate was subjected to MEK soluble. It is separated into a soluble portion and an MEK insoluble portion.
  • a total of 3 sets of centrifugation operations are carried out.
  • the weights of the obtained MEK soluble matter and MEK insoluble matter are measured, and the gel content is calculated from the following formula.
  • the "elastic body" of the fine polymer particles (A) may consist of only one type of elastic body having the same composition of structural units.
  • the "elastic body” of the fine polymer particles (A) is one selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.
  • the "elastic body" of the fine polymer particles (A) may consist of a plurality of types of elastic bodies having different compositions of structural units.
  • the "elastic body” of the fine polymer particles (A) may be two or more selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.
  • the "elastic body” of the fine polymer particles (A) may be one selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.
  • the "elastic body" of the fine polymer particles (A) may be a plurality of types of diene-based rubbers, (meth)acrylate-based rubbers, or organosiloxane-based rubbers each having a different composition of structural units.
  • the "elastic body" of the fine polymer particles (A) is composed of a plurality of types of elastic bodies having different compositions of structural units.
  • each of the plurality of types of elastic bodies is defined as elastic body 1 , elastic body 2 , . . . , and elastic body n .
  • n is an integer of 2 or more.
  • the "elastic body" of the fine polymer particles (A) may include a composite of separately polymerized elastic bodies 1 , 2 , . . . , and elastic body n .
  • the "elastic body" of the fine polymer particles (A) may include one elastic body obtained by polymerizing the elastic body 1 , the elastic body 2 , . . . and the elastic body n in order. Such polymerization of a plurality of elastic bodies (polymers) in order is also called multistage polymerization. A single elastic body obtained by multi-stage polymerization of a plurality of types of elastic bodies is also referred to as a multi-stage polymerized elastic body. A method for producing the multi-stage polymer elastic body will be described in detail later.
  • a multistage polymerized elastic body composed of elastic body 1 , elastic body 2 , . . . , and elastic body n will be described.
  • the elastic body n may cover at least a portion of the elastic body n - 1 or may cover the entire elastic body n-1 .
  • part of the elastic body n may be inside the elastic body n-1 .
  • each of the plurality of elastic bodies may form a layered structure.
  • elastic body 1 forms the innermost layer
  • elastic body 2 is formed outside elastic body 1
  • elastic body 2 is formed on the outer side of elastic body 1.
  • a mode in which a layer of the elastic body 3 is formed as the outermost layer of the elastic body outside the layer of the elastic body 2 is also one mode of the present invention.
  • a multi-stage polymerized elastic body in which each of a plurality of elastic bodies forms a layered structure can also be called a multi-layered elastic body.
  • the “elastic body” of the fine polymer particles (A) is (i) a composite of multiple types of elastic bodies, (ii) a multi-stage polymerized elastic body and/or (iii) a multi-layered elastic It may contain a body.
  • the elastic body may further contain a surface-crosslinked polymer in addition to one or more rubbers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.
  • a surface-crosslinked polymer in addition to one or more rubbers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.
  • the portion of the elastic body containing the above-mentioned rubber as a main component may be referred to as the "elastic core of the elastic body".
  • the elastic body has an elastic core formed by polymerizing at least one monomer selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber.
  • a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer. is preferred.
  • An embodiment of the present invention will be described below, taking as an example the case where the elastic body further has a surface-crosslinked polymer in addition to the elastic core of the elastic body. In this case, (i) blocking resistance can be improved in the production of the polymer fine particles (A), and (ii) dispersibility of the polymer fine particles (A) in the thermosetting resin becomes better.
  • the surface cross-linked polymer covers at least a part of the elastic core of the elastic body, thereby increasing the elasticity of the elastic body of the fine polymer particles (A).
  • the exposure of the core is reduced, and as a result, the elastic bodies are less likely to stick to each other, thereby improving the dispersibility of the fine polymer particles (A).
  • the elastic body When the elastic body has a surface-crosslinked polymer, it may also have the following effects: (i) the effect of lowering the viscosity of the present resin composition, (ii) the effect of increasing the crosslink density of the elastic body as a whole, and ( iii) The effect of increasing the grafting efficiency of the grafted part.
  • the crosslink density in the elastic core of the elastic means the degree of the number of crosslinked structures in the entire elastic core of the elastic.
  • the surface-crosslinked polymer contains, as structural units, 30 to 100% by weight of structural units derived from a polyfunctional monomer and 0 to 70% by weight of structural units derived from other vinyl monomers, a total of 100 % by weight of the polymer.
  • polyfunctional monomers that can be used for polymerization of the surface-crosslinked polymer include the polyfunctional monomers exemplified in the above section "Crosslinked structure of elastic body".
  • polyfunctional monomers that can be preferably used for polymerization of the surface-crosslinked polymer include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate (e.g. 1,3-butylene glycol dimethacrylate), butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.
  • the elastomer may comprise a surface cross-linked polymer polymerized independently of the polymerisation of the elastic core of the elastomer, or it may comprise a surface cross-linked polymer polymerized with the elastic core of the elastomer.
  • the fine polymer particles (A) may be a multistage polymer obtained by polymerizing the elastic core of the elastic body and the surface-crosslinked polymer together, and then polymerizing the graft portion.
  • the polymer fine particles (A) may be a multi-stage polymer obtained by multi-stage polymerization of an elastic core of an elastic body, a surface-crosslinked polymer and a graft portion in this order.
  • the surface cross-linked polymer may coat at least a portion of the elastic core of the elastomer.
  • the surface cross-linked polymer can be regarded as a part of the elastic body, and the surface cross-linked polymer can be said to be the surface cross-linked part of the elastic body, as opposed to the elastic core of the elastic body.
  • the graft portion may be (i) graft-bonded to an elastic body other than the surface-crosslinked polymer (that is, the elastic core of the elastic body); It may be grafted to the crosslinked polymer, or (iii) grafted to both the elastic body other than the surface crosslinked polymer (that is, the elastic core of the elastic body) and the surface crosslinked polymer. good.
  • the volume-average particle size of the elastic means the volume-average particle size of the elastic containing the surface-crosslinked polymer.
  • the polymer graft-bonded to the elastic body is referred to as a graft portion.
  • the graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer.
  • the first structural unit is the first monomer (hereinafter, “first monomer”) among the structural units constituting the polymer contained in the graft portion. refers to the part derived from A 1st monomer is 1 or more types selected from the group which consists of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer.
  • the graft part has the first structural unit derived from the first monomer, so that (i) the compatibility between the polymer fine particles (A) and the matrix resin (B) is improved, and (ii) the matrix resin.
  • the dispersibility of the polymer fine particles (A) in (B) is improved, and (iii) the polymer fine particles (A) can be dispersed in the state of primary particles in the resin composition or its cured product.
  • aromatic vinyl monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, and divinylbenzene.
  • vinyl cyan monomers include acrylonitrile and methacrylonitrile.
  • (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
  • (Meth)acrylate as used herein means acrylate and/or methacrylate.
  • the first monomer selected from the group consisting of the above-mentioned aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
  • only one type is used as the first monomer. may be used, or two or more may be used in combination as the first monomer.
  • the second structural unit (hereinafter, “second structural unit”) is the second monomer (hereinafter, “second monomer”) among the structural units constituting the polymer contained in the graft portion. refers to the part derived from The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in its molecule.
  • the graft portion having the second structural unit derived from the second monomer can be produced by using the second monomer in addition to the first monomer in the production (polymerization) of the graft portion.
  • the second monomer can crosslink the polymer obtained by polymerizing the first monomer in the production of the graft. Therefore, the second monomer can be said to be a "crosslinking agent", and the second structural unit can be said to be a "structural unit derived from the crosslinking agent".
  • the graft part has the second structural unit derived from the second monomer, so that (i) the polymer fine particles (A) can be prevented from swelling in the resin composition, (ii) the resin composition (iii) the dispersibility of the fine polymer particles (A) in the matrix resin (B) is improved.
  • polyfunctional monomers having two or more polymerizable unsaturated bonds in the molecule include the polyfunctional monomers exemplified in the above section "Crosslinked structure of elastic body”.
  • polyfunctional monomers having two or more polymerizable unsaturated bonds in the molecule include allyl methacrylate. , ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylate types are mentioned. Only one type of these polyfunctional monomers may be used as the second monomer, or two or more types may be combined and used as the second monomer.
  • the graft portion preferably contains 10 to 95% by weight, more preferably 30 to 92% by weight, more preferably 50 to 90% by weight of the first structural unit in 100% by weight of the polymer constituting the graft portion. More preferably, 60 to 87% by weight is particularly preferable, and 70 to 85% by weight is most preferable.
  • the content of the second constitutional unit in the polymer constituting the graft portion is 0.00% when the total of the first constitutional unit and the second constitutional unit in the polymer constituting the graft portion is 100% by weight. 00% by weight and less than 2.00% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion is within the above range, the viscosity of the resin composition is reduced and the state of dispersion of the polymer fine particles (A) in the resin composition is maintained. It has the advantage that it is possible to make both
  • the content of the second structural unit in the polymer that constitutes the graft portion is the same as that of the first structural unit in the polymer that constitutes the graft portion.
  • the viscosity of the resin composition is reduced and the polymer in the resin composition It is compatible with maintenance of the dispersed state of the fine particles (A).
  • the content of the second structural unit in the polymer constituting the graft portion is preferably 0.10% by weight or more, more preferably 0.20% by weight or more, and 0.20% by weight or more. It is more preferably 30% by weight or more, more preferably 0.40% by weight or more, more preferably 0.50% by weight or more, and even more preferably 0.55% by weight or more.
  • the content of the second structural unit in the polymer constituting the graft portion is When the total of one structural unit and the second structural unit is 100% by weight, it is preferably 1.80% by weight or less, more preferably 1.70% by weight or less, and 1.60% by weight. is more preferably 1.40% by weight or less, more preferably 1.20% by weight or less, even more preferably 1.00% by weight or less, and 0.80 % by weight or less is even more preferable, and 0.60% by weight or less is particularly preferable.
  • the graft portion may further contain a structural unit derived from a monomer having a reactive group, in addition to the above-described first structural unit and second structural unit.
  • the monomer having a reactive group includes an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group.
  • the grafted portion of the fine polymer particles (A) and the matrix resin (B) (for example, thermosetting resin) can be chemically bonded in the resin composition.
  • the fine polymer particles (A) can be maintained in a good dispersed state without agglomeration of the fine polymer particles (A) in the resin composition or the cured product thereof.
  • epoxy group-containing monomers include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.
  • monomers having a hydroxyl group include, for example, (i) 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxy straight-chain alkyl (meth)acrylates; Acrylates (especially hydroxy linear C1-6 alkyl (meth)acrylates); (ii) caprolactone-modified hydroxy (meth)acrylates; (iii) ⁇ -(hydroxymethyl)methyl acrylate, ⁇ -(hydroxymethyl)ethyl acrylate hydroxy-branched alkyl (meth)acrylates such as; (iv) mono(meth)acrylates of polyester diols (particularly saturated polyester diols) obtained from dihydric carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol); hydroxyl group-containing (meth)acrylates, and the like.
  • polyester diols particularly saturated polyester diols obtained from dihydric carboxy
  • monomers having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid.
  • monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid
  • dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid.
  • the monocarboxylic acid is preferably used as the monocarboxylic acid.
  • the graft portion preferably contains 0.5 to 90% by weight, and preferably 1 to 50% by weight, of structural units derived from a monomer having a reactive group in 100% by weight of the polymer constituting the graft portion. is more preferable, more preferably 2 to 35% by weight, and particularly preferably 3 to 20% by weight.
  • the resulting resin composition is A cured product having sufficient impact resistance can be provided, and (ii) when the content is 90% by weight or less, the resulting resin composition can provide a cured product having sufficient impact resistance, and , has the advantage that the storage stability of the resin composition is improved.
  • the structural unit derived from a monomer having a reactive group is preferably contained in the graft portion, and more preferably contained only in the graft portion.
  • the graft portion may contain, as structural units, structural units derived from other monomers in addition to the structural units derived from the monomers described above.
  • the glass transition temperature of the graft portion is preferably 190°C or lower, more preferably 160°C or lower, more preferably 140°C or lower, more preferably 120°C or lower, preferably 80°C or lower, more preferably 70°C or lower, and 60°C.
  • the following is more preferable, 50° C. or less is more preferable, 40° C. or less is more preferable, 30° C. or less is more preferable, 20° C. or less is more preferable, 10° C. or less is more preferable, 0° C. or less is more preferable, and ⁇ 20° C.
  • -40°C or less is more preferable, -45°C or less is more preferable, -50°C or less is more preferable, -55°C or less is more preferable, -60°C or less is more preferable, -65°C or less is More preferably -70°C or less, more preferably -75°C or less, more preferably -80°C or less, more preferably -85°C or less, more preferably -90°C or less, more preferably -95°C or less , -100°C or lower is more preferred, -105°C or lower is more preferred, -110°C or lower is more preferred, -115°C or lower is more preferred, -120°C or lower is even more preferred, and -125°C or lower is particularly preferred.
  • the glass transition temperature of the graft portion is preferably 0° C. or higher, more preferably 30° C. or higher, more preferably 50° C. or higher, more preferably 70° C. or higher, still more preferably 90° C. or higher, and particularly preferably 110° C. or lower. preferable.
  • the Tg of the graft part can be determined by the composition of the constituent units contained in the graft part.
  • the Tg of the obtained graft portion can be adjusted by changing the composition of the monomers used when manufacturing (polymerizing) the graft portion.
  • the Tg of the graft portion can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) For a flat plate made of polymer fine particles (A), a dynamic viscoelasticity measuring device (eg, DVA-200 manufactured by IT Keisoku Co., Ltd.) ) is used to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan ⁇ graph; (2) Regarding the obtained tan ⁇ graph, the tan ⁇ peak temperature is taken as the glass transition temperature.
  • the highest peak temperature is taken as the glass transition temperature of the graft portion.
  • the fine polymer particles (A) may be a polymer having the same structure as the graft portion and may have a polymer that is not graft-bonded to the elastic body.
  • a polymer having the same structure as the graft portion and not graft-bonded to the elastic body is also referred to as a non-grafted polymer.
  • the non-grafted polymer also constitutes a part of the fine polymer particles (A) according to Embodiment 1 of the present invention.
  • the non-graft polymer can also be said to be a polymer that is not graft-bonded to the elastic body, among the polymers produced in the polymerization of the graft portion.
  • the ratio of the polymer graft-bonded to the elastic body, that is, the graft portion, out of the polymer produced in the polymerization of the graft portion is referred to as the graft ratio.
  • the graft ratio can also be said to be a value represented by (weight of grafted portion)/ ⁇ (weight of grafted portion)+(weight of non-grafted polymer) ⁇ 100.
  • the graft ratio of the graft portion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the graft ratio is 70% or more, there is an advantage that the viscosity of the resin composition does not become too high.
  • the method for calculating the graft ratio is as follows. First, an aqueous suspension containing the polymer fine particles (A) is obtained, and then powder particles of the polymer fine particles (A) are obtained from the aqueous suspension. Specifically, the method for obtaining powdery particles of the polymer microparticles (A) from the aqueous suspension includes (i) coagulating the polymer microparticles (A) in the aqueous suspension, and (ii) A method of obtaining powder particles of polymer fine particles (A) by dehydrating the obtained coagulate and (iii) further drying the coagulate can be mentioned.
  • MEK methyl ethyl ketone
  • the obtained MEK melt is separated into a component soluble in MEK (MEK soluble matter) and a component insoluble in MEK (MEK insoluble matter).
  • (1) to (3) are performed: (1) Using a centrifuge (CP60E, manufactured by Hitachi Koki Co., Ltd.), the obtained MEK is dissolved at a rotation speed of 30000 rpm for 1 hour.
  • the weight of the polymer other than the graft portion is the charged amount of the monomer constituting the polymer other than the graft portion.
  • a polymer other than the graft portion is, for example, an elastic body.
  • the fine polymer particles (A) contain a surface-crosslinked polymer, which will be described later, the polymer other than the graft portion contains both the elastic body and the surface-crosslinked polymer.
  • the weight of the polymer of the graft portion is the charged amount of the monomers constituting the polymer of the graft portion.
  • the method of coagulating the polymer microparticles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous suspension, or the like can be used. .
  • the graft portion may consist of only one type of graft portion having structural units of the same composition. In one embodiment of the present invention, the graft portion may consist of a plurality of types of graft portions each having a different composition of structural units.
  • each of the plurality of types of graft portions is designated as graft portion 1 , graft portion 2 , . . . , graft portion n (n is an integer of 2 or more).
  • the graft portion may comprise a composite of graft portion 1 1 , graft portion 2 2 , . . . , and graft portion n , each polymerized separately.
  • the graft portion may contain one polymer obtained by sequentially polymerizing graft portion 1 1 , graft portion 2 2 , . . . , and graft portion n .
  • Such polymerization of a plurality of polymerized portions (graft portions) in order is also referred to as multi-stage polymerization.
  • a polymer obtained by multistage polymerization of a plurality of types of graft portions is also referred to as a multistage polymerization graft portion.
  • a method for producing the multistage polymerized graft portion will be described in detail later.
  • the graft portion When the graft portion consists of multiple types of graft portions, not all of these multiple types of graft portions may be graft-bonded to the elastic body. At least a part of at least one type of graft portion may be graft-bonded to the elastic body, and other types (a plurality of other types) of graft portions are graft portions that are graft-bonded to the elastic body. may be grafted to. Further, when the graft portion is composed of a plurality of types of graft portions, a plurality of types of polymers that are polymers having the same configuration as the plurality of types of graft portions and are not graft-bonded to the elastic body graft polymer).
  • a multi-stage polymerized graft portion composed of graft portion 1 , graft portion 2 , . . . , and graft portion n will be described.
  • the graft portion n may cover at least a portion of the graft portion n ⁇ 1 , or may cover the entirety of the graft portion n ⁇ 1 .
  • a part of the graft portion n may be inside the graft portion n ⁇ 1 .
  • each of the plurality of graft portions may form a layered structure.
  • graft portion 1 forms the innermost layer in the graft portion
  • graft portion 2 is formed on the outer side of graft portion 1 .
  • an aspect in which the layer of the graft portion 3 is formed as the outermost layer outside the layer of the graft portion 2 is also an aspect of the present invention.
  • a multi-stage polymerized graft portion in which each of a plurality of graft portions forms a layered structure can also be called a multi-layer graft portion. That is, in one embodiment of the present invention, the graft portion may include (i) a composite of multiple types of graft portions, (ii) a multi-stage polymerization graft portion and/or (iii) a multi-layer graft portion.
  • the elastic body and the graft portion are polymerized in this order in the production of the polymer microparticles (A), at least a portion of the graft portion may cover at least a portion of the elastic body in the resulting polymer microparticles (A). .
  • the elastic body and the graft portion are polymerized in this order, which means that the elastic body and the graft portion are polymerized in multiple stages.
  • the polymer microparticles (A) obtained by multi-stage polymerization of the elastic body and the graft portion can be said to be a multi-stage polymer.
  • the graft part can cover at least a part of the elastic body, or can cover the entire elastic body.
  • part of the graft portion may enter the inside of the elastic body.
  • At least a portion of the graft portion preferably covers at least a portion of the elastic body. In other words, at least part of the graft portion is preferably present on the outermost side of the fine polymer particles (A).
  • the elastic body and the graft portion may form a layered structure.
  • the elastic body forms the innermost layer (also referred to as a core layer) and the layer of the graft portion is formed as the outermost layer (also referred to as a shell layer) on the outside of the elastic body is also an aspect of the present invention.
  • a structure in which an elastic body is used as a core layer and a graft portion is used as a shell layer can be called a core-shell structure.
  • the polymer fine particles (A) in which the elastic body and the graft part form a layered structure (core-shell structure) can be called a multi-layered polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particle (A) may be a multi-stage polymer and/or a multi-layer polymer or core-shell polymer. However, as long as it has an elastic body and a graft portion, the fine polymer particles (A) are not limited to the above configuration.
  • Case D where the polymer fine particles (A) is a multi-stage polymer obtained by multi-stage polymerization of the elastic core of the elastic body, the surface-crosslinked polymer, and the graft portion in this order will be described.
  • the surface-crosslinked polymer impregnates (incorporates) a portion of the surface of the elastic core of the elastic, or impregnates the entire surface of the elastic core of the elastic ( inside).
  • the graft portion may cover a portion of the surface cross-linked polymer or may cover the entire surface cross-linked polymer.
  • the graft part may form a layer of the graft part on the outside of the surface cross-linked polymer while partially impregnating the surface of the surface cross-linked polymer (entering inside). Further, in case D, part of the graft part may impregnate the surface of the elastic core of the elastic body (entering inside) to form a layer of the graft part on the outside of the elastic core of the elastic body. .
  • the elastic core of the elastic body, the surface-crosslinked polymer and the graft portion may have a layered structure.
  • the elastic core of the elastic body is the innermost layer (core layer)
  • the layer of the surface-crosslinked polymer is present as the intermediate layer outside the elastic core of the elastic body
  • the layer of the graft portion is the outermost layer of the surface-crosslinked polymer.
  • An aspect in which it exists as an outer layer (shell layer) is also an aspect of the present invention.
  • the volume average particle diameter (Mv) of the fine polymer particles (A) is preferably from 0.03 ⁇ m to 50.00 ⁇ m, since a highly stable resin composition having a desired viscosity can be obtained.
  • 05 ⁇ m to 10.00 ⁇ m is more preferable, 0.08 ⁇ m to 2.00 ⁇ m is more preferable, 0.10 ⁇ m to 1.00 ⁇ m is still more preferable, 0.10 ⁇ m to 0.80 ⁇ m is even more preferable, 0.10 ⁇ m to 0.50 ⁇ m is particularly preferred.
  • the polymer fine particles (A) are said to have good dispersibility in the matrix resin (B) (for example, thermosetting resin). It also has advantages.
  • the "volume average particle diameter (Mv) of the polymer microparticles (A)” means the volume average particle diameter of the primary particles of the polymer microparticles (A), unless otherwise specified. do.
  • the volume average particle size of the polymer fine particles (A) can be measured using a dynamic light scattering particle size distribution analyzer or the like using an aqueous latex containing the polymer fine particles (A) as a sample.
  • the fine polymer particles (A) can be produced, for example, by polymerizing an elastic body and then graft-polymerizing a polymer forming a graft portion to the elastic body in the presence of the elastic body.
  • the method for producing such polymer microparticles (A) is also included in the scope of the present invention.
  • the method for producing polymer microparticles is a method for producing polymer microparticles (A), in which a diene-based monomer, a (meth)acrylate-based monomer, and an organosiloxane-based monomer an elastic body preparing step of polymerizing one or more monomers selected from the group consisting of a first monomer and a second monomer to the elastic body prepared by the elastic body preparing step; and the first monomer is selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer.
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and in the graft part preparation step, the first monomer When the total of the monomer and the second monomer is 100% by weight, the second monomer is used in an amount of more than 0.00% by weight and less than 2.00% by weight. .
  • the elastic body preparation step is a step of polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers.
  • the elastic body contains at least one selected from the group consisting of diene-based rubbers and (meth)acrylate-based rubbers.
  • one or more monomers selected from the group consisting of diene-based monomers and (meth)acrylate-based monomers may be polymerized.
  • Polymerization of the monomers in this case can be carried out, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. can.
  • the organosiloxane-based monomer may be polymerized in the elastic body preparation step.
  • Polymerization of the monomers in this case can be carried out, for example, by methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. can.
  • the elastic body of the fine polymer particles (A) consists of a plurality of types of elastic bodies (eg, elastic body 1 , elastic body 2 , . . . , elastic body n ) will be described.
  • the elastic bodies 1 1 , 2 2 , . may be manufactured. That is, in this case, the elastic body preparation process includes a preparation process for elastic body 1 , a preparation process for elastic body 2 , . , . Alternatively, in the elastic body preparation step, elastic body 1 , elastic body 2 , . good too.
  • the following steps (1) to (4) can be performed in order to obtain a multi-stage polymerized elastic body: (1) Polymerize the elastic body 1 to obtain the elastic body 1 . (2) then elastic 2 is polymerized in the presence of elastic 1 to obtain a two-step elastic 1+2 ; (3) elastic 3 is then polymerized in the presence of elastic 1+2 to give a three-step elastic; (4) After the same procedure, the elastic body n is polymerized in the presence of the elastic body 1+ 2 +...+(n-1) to obtain the multistage polymerized elastic body 1+2+...+n . obtain.
  • the elastic body preparation step may include the following steps (a) and (b): (a) polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers; (b) one or more monomers selected from the group consisting of polyfunctional monomers having two or more polymerizable unsaturated bonds in the molecule and vinyl monomers other than the polyfunctional monomers A step of polymerizing the monomer.
  • An elastic core of an elastic body can be prepared by step (a).
  • the step (b) can prepare a surface-crosslinked polymer of an elastic body.
  • the surface-crosslinked polymer can be formed by polymerizing the monomers used for forming the surface-crosslinked polymer by known radical polymerization in the presence of any polymer (eg, elastic core).
  • any polymer eg, elastic core.
  • the polymerization of the surface-crosslinked polymer is preferably carried out by an emulsion polymerization method.
  • the elastic body preparation step includes step (a) and step (b), said step (b) may be performed simultaneously with said (a), or may be performed after said (a).
  • the elastic body preparation step (i) one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers; , a polyfunctional monomer and a vinyl monomer other than the polyfunctional monomer may be used together to prepare the elastic core and the surface crosslinked polymer at the same time, (ii ) After the use of one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers, polyfunctional monomers and the polyfunctional It is also possible to use a vinyl-based monomer other than the organic monomer and prepare (polymerize) the surface-crosslinked polymer after completing the preparation (polymerization) of the elastic core.
  • the graft portion preparation step is a step of graft-polymerizing the first monomer and the second monomer onto the elastic body prepared in the elastic body preparation step.
  • the graft portion can be formed, for example, by polymerizing a monomer used for forming the graft portion by known radical polymerization in the presence of an elastic body.
  • an elastic body comprising an elastic core or (ii) an elastic body comprising an elastic core and a surface-crosslinked polymer is obtained as an aqueous suspension
  • the graft portion is polymerized by emulsion polymerization. It is preferable to carry out by
  • the graft portion can be manufactured, for example, according to the method described in WO2005/028546.
  • a method of manufacturing a graft portion when the graft portion is composed of a plurality of types of graft portions (for example, graft portion 1 1 , graft portion 2 2 , . . . , graft portion n 2 ) will be described.
  • the graft portion 1 1 , the graft portion 2 2 , . (composite) may be produced. That is, in this case, the graft portion preparation process includes a preparation step for graft portion 1 , a preparation step for graft portion 2 , . , .
  • the graft portion preparation step is a step of sequentially polymerizing the graft portion 1 , the graft portion 2 , . good too.
  • a multistage polymerized graft portion can be obtained by sequentially performing steps (1) to (4) in the graft portion preparation step: (1) Graft portion 1 is polymerized to obtain graft portion 1 . (2) then graft portion 2 is polymerized in the presence of graft portion 1 to obtain a two-step graft portion 1+2 ; (3) graft portion 3 is then polymerized in the presence of graft portion 1 +2 to obtain a three-step graft; (4) After the same procedure, graft portion n is polymerized in the presence of graft portion 1 + 2 + . obtain.
  • the graft portion is composed of a plurality of types of graft portions
  • the graft portions having a plurality of types of graft portions are polymerized, and then the graft portions are graft-polymerized to the elastic body prepared in the elastic body preparation step to obtain fine polymer particles.
  • (A) may be produced.
  • a plurality of types of polymers constituting the graft portion are sequentially subjected to multistage graft polymerization to the elastic body to produce the polymer microparticles (A).
  • the production (polymerization) of the graft portion uses a first monomer and a second monomer.
  • the second monomer can crosslink the polymer obtained from the first monomer. Therefore, in the production of the graft portion, (i) the second monomer is used together with the first monomer, and the cross-linking reaction by the second monomer proceeds simultaneously with the polymerization of the first monomer; Alternatively, (ii) it is preferable to use the second monomer after using the first monomer and allow the cross-linking reaction by the second polymer to proceed after the completion of the polymerization of the first monomer.
  • Polymerization of the elastic body, polymerization of the graft portion (graft polymerization), and polymerization of the surface-crosslinked polymer in the fine polymer particles (A) are performed by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. It can be implemented by the method of Among these, the emulsion polymerization method is particularly preferable as the method for producing the polymer fine particles (A).
  • the emulsion polymerization method has the advantages of (i) facilitating compositional design of the polymer microparticles (A) and (ii) facilitating industrial production of the polymer microparticles (A).
  • the method for producing the elastic body, the graft portion, and the surface-crosslinked polymer having any configuration that can be contained in the fine polymer particles (A) will be described.
  • a known emulsifier can be used as an emulsifier (dispersant) for the production of the polymer fine particles (A).
  • emulsifiers include anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives.
  • anionic emulsifiers include sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosic acid-based emulsifiers, and carboxylic acid-based emulsifiers.
  • sulfur-based emulsifiers include sodium dodecylbenzenesulfonate (abbreviation: SDBS).
  • Phosphorus-based emulsifiers include sodium polyoxyethylene lauryl ether phosphate and the like.
  • thermal decomposition initiator When an emulsion polymerization method is adopted as the method for producing the polymer fine particles (A), a thermal decomposition initiator can be used for the production of the polymer fine particles (A).
  • the thermal decomposition initiators include, for example, (i) 2,2′-azobisisobutyronitrile, and (ii) peroxides such as organic and inorganic peroxides, and other known initiators. agents can be mentioned.
  • organic peroxides examples include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t- and hexyl peroxide.
  • inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.
  • a redox initiator can also be used for the production of polymer fine particles (A).
  • the redox initiator includes (i) peroxides such as organic peroxides and inorganic peroxides, and (ii) transition metal salts such as iron (II) sulfate, sodium formaldehyde sulfoxylate, glucose and the like. It is an initiator used in combination with a reducing agent.
  • a chelating agent such as disodium ethylenediaminetetraacetate and, if necessary, a phosphorus-containing compound such as sodium pyrophosphate may be used in combination.
  • a redox initiator When a redox initiator is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set in a wide range. Therefore, it is preferable to use a redox initiator.
  • redox initiators using organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide, and t-butyl hydroperoxide as peroxides are preferred.
  • the amount of the thermal decomposition type initiator used, the amount of the redox type initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when the redox type initiator is used are within a known range. can be used.
  • a known chain transfer agent is used for the purpose of introducing a crosslinked structure into the elastic body, the graft part or the surface crosslinked polymer, when using a polyfunctional monomer in the polymerization of the elastic body, the graft part or the surface crosslinked polymer.
  • a chain transfer agent can be used within the range of the amount used.
  • a surfactant can be used in the production of the polymer microparticles (A).
  • the types and amounts of the surfactants used are within known ranges.
  • polymer microparticles (A) produced by the method for producing polymer microparticles (A) described above are also included in the scope of the present invention.
  • the polymer microparticles (A) according to Embodiment 1 of the present invention may have the following configuration: from a diene-based monomer, a (meth)acrylate-based monomer, and an organosiloxane-based monomer an elastic body obtained by polymerizing one or more monomers selected from the group consisting of; a graft portion obtained by graft-polymerizing a first monomer and a second monomer to the elastic body; wherein the first monomer is one selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and the first structural unit and the second The second structural unit is more than 0.00% by weight and less than 2.00% by weight, when the total amount of the second structural unit is 100% by weight.
  • the matrix resin (B) is a resin having two or more polymerizable unsaturated bonds in its molecule. Resins having two or more polymerizable unsaturated bonds in the molecule are not particularly limited, and examples thereof include curable resins having radically polymerizable reactive groups (eg, carbon-carbon double bonds). More specifically, the matrix resin (B) is a curable resin containing an ester bond in the repeating unit constituting the main chain, epoxy (meth)acrylate, urethane (meth)acrylate, polyether (meth)acrylate, acrylic (meth)acrylates, and the like. These curable resins may be used alone or in combination of two or more.
  • Epoxy (meth)acrylate is obtained by addition reaction of polyepoxide such as bisphenol A epoxy resin, unsaturated monobasic acid such as (meth)acrylic acid, and optionally polybasic acid in the presence of a catalyst. It is an addition reaction product obtained by The addition reaction product and, if necessary, a mixture of the addition reaction product and a vinyl monomer are generally referred to as a vinyl ester resin. This production method inevitably leaves a small amount of the raw material polyepoxide. If the polyepoxide does not have a polymerizable unsaturated bond in its molecule, it may remain uncured and adversely affect the physical properties of the cured product (heat resistance, etc.).
  • the content of epoxy (meth)acrylate in 100 parts by weight of the total amount of matrix resin (B) is preferably less than 99 parts by weight, preferably 95 parts by weight. Less than 90 parts by weight is more preferred, less than 80 parts by weight is even more preferred, less than 50 parts by weight is particularly preferred, and less than 30 parts by weight is most preferred. More preferably, the matrix resin (B) does not contain epoxy (meth)acrylate.
  • the "curable resin containing an ester bond in the repeating unit constituting the main chain” is particularly limited as long as it is a curable compound having an ester group and two or more polymerizable unsaturated bonds in the molecule.
  • examples include unsaturated polyesters and polyester (meth)acrylates.
  • the matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates. More than one kind of curable resin is preferred.
  • the matrix resin (B) is one or more selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates from the viewpoint of economy. is preferred. Further, the matrix resin (B) is more preferably one or more selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, and urethane (meth)acrylates, since there is little residual epoxide. Further, from the viewpoint of heat resistance, the matrix resin (B) is more preferably unsaturated polyester or polyester (meth)acrylate. , and that the polymer fine particles (A) are easily dispersed, the matrix resin (B) is particularly preferably polyester (meth)acrylate.
  • the matrix resin (B) preferably contains polyether (meth)acrylate or is polyether (meth)acrylate. From the viewpoint of low viscosity and excellent workability, the matrix resin (B) preferably contains an acrylated (meth)acrylate or is an acrylated (meth)acrylate.
  • the unsaturated polyester is not particularly limited, and examples thereof include those obtained from a condensation reaction between a polyhydric alcohol and an unsaturated polycarboxylic acid or its anhydride.
  • polyhydric alcohols include those having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, and neopentyl glycol.
  • dihydric alcohols preferably dihydric alcohols having 2 to 6 carbon atoms, more preferably propylene glycol. Only one type of these dihydric alcohols may be used, or two or more types may be used in combination.
  • unsaturated polycarboxylic acids include divalent carboxylic acids having 3 to 12 carbon atoms, more preferably divalent carboxylic acids having 4 to 8 carbon atoms. Specific examples include fumaric acid and maleic acid. Only one type of these divalent carboxylic acids may be used, or two or more types may be used in combination.
  • a saturated polycarboxylic acid or an anhydride thereof may be used in combination with the unsaturated polycarboxylic acid or anhydride thereof. It is preferable that the amount of the unsaturated polycarboxylic acid or its anhydride is at least 30 mol % or more based on the total amount (100 mol %) of the acid or its anhydride.
  • saturated polycarboxylic acids or anhydrides thereof include phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid and glutaric acid. These saturated polycarboxylic acids or their anhydrides may be used alone or in combination of two or more.
  • the unsaturated polyester is prepared by combining the polyhydric alcohol and the unsaturated polycarboxylic acid or its anhydride in the presence of an esterification catalyst such as an organic titanate such as tetrabutyl titanate or an organic tin compound such as dibutyltin oxide. It can be obtained by condensation reaction below.
  • an esterification catalyst such as an organic titanate such as tetrabutyl titanate or an organic tin compound such as dibutyltin oxide. It can be obtained by condensation reaction below.
  • the curable unsaturated polyester compound is also commercially available, for example, from Ashland, Reichhold, AOC, and the like.
  • the number average molecular weight of the unsaturated polyester is not particularly limited, but is preferably 400-10,000, more preferably 450-5,000, and particularly preferably 500-3,000.
  • Polyester (meth)acrylate is not particularly limited, for example, polyvalent carboxylic acid or anhydride thereof having a valence of 2 or more, unsaturated monocarboxylic acid having a (meth)acryloyl group, and polyvalence of 2 or more Examples include those obtained by esterifying alcohol as an essential component. Further, the polyester (meth)acrylate is obtained, for example, by subjecting the hydroxyl group of the polyester obtained by the condensation reaction of a polyhydric carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction with an unsaturated monocarboxylic acid. Obtainable.
  • the polyester (meth)acrylate is obtained, for example, by subjecting the carboxyl group of the polyester obtained by the condensation reaction of a polyvalent carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction with an unsaturated glycidyl ester compound.
  • the carboxyl group of the polyester obtained by the condensation reaction of a polyvalent carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction with an unsaturated glycidyl ester compound.
  • polycarboxylic acids or anhydrides thereof include unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid, or anhydrides thereof.
  • phthalic acid phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, adipic acid, Azelaic acid, sebacic acid, 1,12-dodecanedioic acid, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride , 4,4′-biphenyldicarboxylic acid and other saturated carboxylic acids or their anhydrides.
  • the polyvalent carboxylic acid or its anhydride is preferably maleic anhydride, fumaric acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, adipic acid or sebacic acid, and phthalic anhydride. More preferred are acids, isophthalic acid and terephthalic acid. Isophthalic acid is particularly preferred from the viewpoint of the low viscosity of the resulting matrix resin (B) and the water resistance of the cured product.
  • polyhydric alcohols examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methylpropane-1,3-diol,
  • Examples include hydrogenated bisphenol A, adducts of bisphenol A and alkylene oxides such as propylene oxide and ethylene oxide, and trimethylolpropane.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and hydrogenated bisphenol.
  • A, an adduct of bisphenol A and propylene oxide is preferred, and propylene glycol, neopentyl glycol, hydrogenated bisphenol A, and an adduct of bisphenol A and propylene oxide are more preferred.
  • Neopentyl glycol is particularly preferable from the viewpoint of the resulting matrix resin (B) having a low viscosity and the water resistance and weather resistance of the cured product.
  • a known method can be used for the reaction method for the condensation reaction.
  • the mixing ratio of polyhydric carboxylic acids and polyhydric alcohols is not particularly limited.
  • the presence or absence of additives such as other catalysts and antifoaming agents, and the amounts used are not particularly limited.
  • the reaction temperature and reaction time in the condensation reaction may be appropriately set so that the reaction is completed.
  • the unsaturated monocarboxylic acid is a monobasic acid having at least one (meth)acryloyl group in the molecule.
  • the unsaturated glycidyl ester compound is a glycidyl ester compound having at least one (meth)acryloyl group in the molecule.
  • examples include glycidyl acrylate and glycidyl methacrylate.
  • the polymerization inhibitor is not particularly limited, and conventionally known compounds can be used.
  • hydroquinone methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, trihydroquinone, p-benzoquinone, naphthoquinone, methoxyhydroquinone, phenothiazine, hydroquinone monomethyl ether, trimethylhydroquinone, methylbenzoquinone, 2,6-dihydroquinone, -t-butyl-4-(dimethylaminomethyl)phenol, 2,5-di-t-butylhydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, copper naphthenate, etc. mentioned.
  • molecular oxygen for example, (i) air and (ii) mixed gas of air and inert gas such as nitrogen can be used. In this case, molecular oxygen may be blown into the reaction system (so-called bubbling). In order to sufficiently prevent gelation due to polymerization, it is preferable to use both a polymerization inhibitor and molecular oxygen.
  • the reaction conditions such as reaction temperature and reaction time in the esterification reaction may be appropriately set so as to complete the reaction, and are not particularly limited.
  • Specific examples of the solvent include, but are not particularly limited to, aromatic hydrocarbons such as toluene.
  • the amount of solvent used and the method for removing the solvent after the reaction are not particularly limited. Since water is produced as a by-product in the esterification reaction, it is preferable to remove water, which is a by-product, from the reaction system in order to promote the esterification reaction. A removal method is not particularly limited.
  • the number average molecular weight of the polyester (meth)acrylate is not particularly limited, and is preferably 400 to 10,000, more preferably 450 to 5,000, and particularly preferably 500 to 3,000. .
  • Epoxy (meth)acrylate is not particularly limited, and for example, a polyfunctional epoxy compound having two or more epoxy groups in the molecule, an unsaturated monocarboxylic acid, and optionally a polyvalent carboxylic acid. It can be obtained by an esterification reaction in the presence of an esterification catalyst.
  • polyfunctional epoxy compounds include bisphenol-type epoxy compounds, novolac-type epoxy compounds, hydrogenated bisphenol-type epoxy compounds, hydrogenated novolak-type epoxy compounds, and one of the hydrogen atoms of the bisphenol-type epoxy compounds and novolak-type epoxy compounds.
  • examples include halogenated epoxy compounds obtained by substituting a portion with a halogen atom (eg, bromine atom, chlorine atom, etc.). These polyfunctional epoxy compounds may be used alone or in combination of two or more.
  • the bisphenol-type epoxy compound includes, for example, a glycidyl ether-type epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with bisphenol A or bisphenol F, or a reaction of an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin. Epoxy compounds obtained by.
  • Hydrogenated bisphenol type epoxy compounds include, for example, glycidyl ether type epoxy compounds obtained by reacting epichlorohydrin or methyl epichlorohydrin with hydrogenated bisphenol A or hydrogenated bisphenol F, or alkylene oxide adducts of hydrogenated bisphenol A. and epichlorohydrin or methyl epichlorohydrin and epoxy compounds obtained by the reaction.
  • novolak-type epoxy compounds include epoxy compounds obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
  • hydrogenated novolak-type epoxy compounds include epoxy compounds obtained by reacting hydrogenated phenol novolak or hydrogenated cresol novolac with epichlorohydrin or methyl epichlorohydrin.
  • the average epoxy equivalent of the polyfunctional epoxy compound is preferably in the range of 150-900, particularly preferably in the range of 150-400.
  • Epoxy (meth)acrylates using polyfunctional epoxy compounds having an average epoxy equivalent of more than 900 are likely to lower reactivity and curability of the composition.
  • a polyfunctional epoxy compound having an average epoxy equivalent of less than 150 is used, the physical properties of the composition tend to deteriorate.
  • the unsaturated monocarboxylic acid is a monobasic acid having at least one (meth)acryloyl group in the molecule.
  • examples include acrylic acid and methacrylic acid.
  • Some of these unsaturated monocarboxylic acids can also be converted to cinnamic acid, crotonic acid, sorbic acid, and half esters of unsaturated dibasic acids (mono-2-(methacryloyloxy)ethyl maleate, mono-2-(acryloyloxy) ethyl maleate, mono-2-(methacryloyloxy)propyl maleate, mono-2-(acryloyloxy)propyl maleate, etc.).
  • polyvalent carboxylic acid examples include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, adipic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, anhydride trimellitic acid, hexahydrophthalic anhydride, 1,6-cyclohexanedicarboxylic acid, dodecanedioic acid, dimer acid and the like.
  • the ratio of the unsaturated monocarboxylic acid and optionally used polyvalent carboxylic acid to the polyfunctional epoxy compound is the total carboxyl groups possessed by the unsaturated monocarboxylic acid and polyvalent carboxylic acid and the polyfunctional epoxy compound. It is preferable that the ratio with the epoxy group is in the range of 1:1.2 to 1.2:1.
  • esterification catalyst conventionally known compounds can be used. Specific examples include tertiary amines such as triethylamine, N,N-dimethylbenzylamine, and N,N-dimethylaniline; trimethyl benzylammonium chloride, quaternary ammonium salts such as pyridinium chloride; phosphonium compounds such as triphenylphosphine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium idodide; sulfonic acids; and organic metal salts such as zinc octenoate.
  • tertiary amines such as triethylamine, N,N-dimethylbenzylamine, and N,N-dimethylaniline
  • trimethyl benzylammonium chloride quaternary ammonium salts such as pyridinium chloride
  • phosphonium compounds such as triphenylpho
  • reaction method and reaction conditions for carrying out the above reaction are not particularly limited. Moreover, in the esterification reaction, it is more preferable to add a polymerization inhibitor or molecular oxygen to the reaction system in order to prevent gelation due to polymerization.
  • a polymerization inhibitor or molecular oxygen those mentioned in the polyester (meth)acrylate can be used in the same manner.
  • the number average molecular weight of the epoxy (meth)acrylate is not particularly limited, and is preferably 300 to 10,000, more preferably 350 to 5,000, and particularly preferably 400 to 2,500. .
  • Urethane (meth)acrylates are not particularly limited, and examples thereof include those obtained by a urethanization reaction of a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth)acrylate compound. Further, those obtained by the urethanization reaction between a polyol compound and a (meth)acryloyl group-containing isocyanate compound, and those obtained by a urethanization reaction between a hydroxyl group-containing (meth)acrylate compound and a polyisocyanate compound.
  • polyisocyanate compounds include 2,4-tolylene diisocyanate and its hydrides, 2,4-tolylene diisocyanate isomers and their hydrides, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and hexamethylene.
  • Diisocyanate trimer of hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate; or Millionate MR, Coronate L (Nippon Polyurethane Industry Co., Ltd.
  • polyol compounds include polyether polyols, polyester polyols, polybutadiene polyols, adducts of bisphenol A and alkylene oxides such as propylene oxide and ethylene oxide.
  • the number average molecular weight of the polyether polyol is preferably in the range of 300-5,000, particularly preferably in the range of 500-3,000.
  • Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, and polyoxymethylene glycol.
  • the polyester polyol preferably has a number average molecular weight in the range of 1,000 to 3,000.
  • a hydroxyl group-containing (meth)acrylate compound is a (meth)acrylate compound having at least one hydroxyl group in the molecule.
  • the hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol. mono (meth) acrylate and the like.
  • a (meth)acryloyl group-containing isocyanate compound is a type of compound that shares at least one (meth)acryloyl group and an isocyanate group in the molecule.
  • the reaction method in the urethanization reaction is not particularly limited, and reaction conditions such as reaction temperature and reaction time may be appropriately set so as to complete the reaction, and are not particularly limited.
  • reaction conditions such as reaction temperature and reaction time may be appropriately set so as to complete the reaction, and are not particularly limited.
  • reaction conditions such as reaction temperature and reaction time may be appropriately set so as to complete the reaction, and are not particularly limited.
  • the ratio of the isocyanate groups possessed by the polyisocyanate compound to the hydroxyl groups possessed by the polyol compound is in the range of 3.0 to 2.0 to produce a prepolymer having an isocyanate group at the end, and then the hydroxyl group of the hydroxyl group-containing (meth) acrylate. and the isocyanate groups of the prepolymer are approximately equivalent to each other, so that the urethanization reaction can be carried out.
  • a urethanization catalyst is preferably used in the above reaction to promote the urethanization reaction.
  • the urethanization catalyst include tertiary amines such as triethylamine and metal salts such as di-n-butyltin dilaurate, but any general urethanization catalyst can be used.
  • a polymerization inhibitor or molecular oxygen it is preferable to add a polymerization inhibitor or molecular oxygen to prevent gelation due to polymerization.
  • the polymerization inhibitor and molecular oxygen those mentioned in the polyester (meth)acrylate can be used in the same manner.
  • the number average molecular weight of the urethane (meth)acrylate is not particularly limited, preferably 400 to 10,000, more preferably 800 to 8,000, particularly preferably 1,000 to 5,000. is.
  • Polyether (meth)acrylate is not particularly limited, and examples thereof include those obtained by an esterification reaction of polyether polyol and (meth)acrylic acid, but can be obtained by other known techniques. Anything can be used.
  • the number average molecular weight of the polyether polyol is preferably within the range of 100 to 5,000, particularly preferably within the range of 100 to 3,000.
  • Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, and polyoxymethylene glycol.
  • the number average molecular weight of the polyether (meth)acrylate is not particularly limited, but is preferably 100-5000, more preferably 100-3000, and particularly preferably 100-1000.
  • the acrylated (meth)acrylate is not particularly limited, and includes, for example, those obtained by reacting an epoxy group-containing acrylic resin having two or more epoxy groups in the molecule with (meth)acrylic acid. However, those obtained by known techniques other than this can be arbitrarily used.
  • the number average molecular weight of the acrylated (meth)acrylate is not particularly limited, but is preferably 100-5000, more preferably 100-3000, and particularly preferably 100-1000.
  • the properties of the matrix resin (B) are not particularly limited.
  • the matrix resin (B) preferably has a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25°C.
  • the viscosity of the matrix resin (B) at 25° C. is more preferably 50,000 mPa ⁇ s or less, still more preferably 30,000 mPa ⁇ s or less, and particularly preferably 15,000 mPa ⁇ s or less. preferable.
  • the matrix resin (B) has an advantage of excellent fluidity.
  • the matrix resin (B) having a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25° C. can also be said to be liquid.
  • the viscosity of the matrix resin (B) is 100 mPa ⁇ at 25° C., since the matrix resin (B) enters the polymer fine particles (A) to prevent fusion between the polymer fine particles (A). s or more, more preferably 500 mPa ⁇ s or more, even more preferably 1000 mPa ⁇ s or more, and particularly preferably 1500 mPa ⁇ s or more.
  • the matrix resin (B) may have a viscosity of greater than 1,000,000 mPa ⁇ s.
  • the matrix resin (B) may be semi-solid (semi-liquid) or solid.
  • the obtained resin composition has the advantage of being less sticky and easier to handle.
  • the matrix resin (B) preferably has an endothermic peak at 25°C or lower, more preferably at 0°C or lower, in a differential scanning calorimetry (DSC) thermogram. According to the above configuration, the matrix resin (B) has an advantage of excellent fluidity.
  • the polymer fine particles (A) when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 10 to 50% by weight. and the matrix resin (B) may be 50 to 90% by weight.
  • the blending ratio of the polymer fine particles (A) and the matrix resin (B) in the resin composition is within the above range, there is an advantage that the resin composition can be used as a high-concentration masterbatch.
  • the polymer fine particles (A) when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 5% by weight to 50% by weight. %, the matrix resin (B) is preferably 50 wt % to 95 wt %, the fine polymer particles (A) are 6 wt % to 50 wt %, and the matrix resin (B) is 50 wt % to 94 wt %. It is more preferable that the polymer fine particles (A) are 7% by weight to 50% by weight, the matrix resin (B) is 50% by weight to 93% by weight, and the polymer fine particles (A) are 8% by weight.
  • the matrix resin (B) is more preferably 50% to 92% by weight, the fine polymer particles (A) are 9% to 50% by weight, and the matrix resin (B) is 50% by weight. It is more preferably 91% by weight, more preferably 10% by weight to 50% by weight of the polymer fine particles (A), and more preferably 50% by weight to 90% by weight of the matrix resin (B), and the polymer fine particles ( More preferably, A) is 15% by weight to 50% by weight, matrix resin (B) is 50% by weight to 85% by weight, polymer fine particles (A) is 20% by weight to 50% by weight, matrix resin (B ) is more preferably 50% to 80% by weight, the fine polymer particles (A) are more preferably 25% to 50% by weight, and the matrix resin (B) is more preferably 50% to 75% by weight.
  • the polymer fine particles (A) are 30% by weight to 50% by weight
  • the matrix resin (B) is 50% by weight to 70% by weight
  • the polymer fine particles (A) are 35% by weight to 50% by weight.
  • the matrix resin (B) is more preferably 50% by weight to 65% by weight.
  • the polymer fine particles (A) are 40% by weight to 50% by weight.
  • the matrix resin (B) may be 50 wt % to 60 wt %
  • the fine polymer particles (A) may be 45 wt % to 50 wt %
  • the matrix resin (B) may be 50 wt % to 55 wt %. There may be.
  • a low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule (hereinafter simply referred to as "low-molecular-weight compound ( C)”) can be added.
  • the low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule has a low molecular weight, it reduces the viscosity of the resin composition according to Embodiment 1 of the present invention, and Improve handling. Further, when the resin composition according to Embodiment 1 of the present invention is cured, it is copolymerized with the matrix resin (B) and incorporated into the cross-linking points of the cured product. Furthermore, in the later-described step of dispersing the polymer fine particles (A) in the state of primary particles in the resin composition, the low-molecular-weight compound (C) can be used as a mixture with the matrix resin (B). It has the effect of facilitating the production process due to the viscosity-lowering effect of the molecular compound (C).
  • the mixing ratio (B/C) of the matrix resin (B) and the low-molecular-weight compound (C) is not particularly limited, but the weight ratio is preferably 9/1 to 3/7.
  • a more preferable upper limit of B/C is 8/2, more preferably 7/3.
  • B/C exceeds 9/1 the viscosity of the resin composition according to Embodiment 1 of the present invention is high, and it may become difficult to handle.
  • a more preferred lower limit for B/C is 4/6, more preferably 5/5. If B/C is less than 3/7, the cured product of the resin composition according to Embodiment 1 of the present invention may become thin due to the volatility of the low-molecular-weight compound (C), or the matrix resin (B) may be left behind.
  • the fine polymer particles (A) may aggregate to reduce the effect of improving toughness.
  • Reaction speed between the (meth)acryloyl group-containing compound and the matrix resin (B) (reaction speed when the (meth)acryloyl group-containing compound is copolymerized with the matrix resin (B) and incorporated into the crosslink points of the cured product) is close to the reaction rate between matrix resins (B) (curing rate between matrix resins (B)). Therefore, the (meth)acryloyl group-containing compound is incorporated into the cross-linking points of the matrix resin (B) when the resin composition according to Embodiment 1 of the present invention containing the low-molecular-weight compound (C) is cured. It is easy to use, that is, it is preferable in terms of the physical properties of the cured product.
  • (meth)acryloyl group-containing compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, n-hexyl (meth)acrylate, ) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, allyl (meth) ) acrylate, phenyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, ⁇ -fluoromethyl acrylate, ⁇ -chloromethyl acrylate, ⁇ -benz
  • a compound having a hydroxyl group improves the cured product by hybrid curing of radical crosslinking and urethane crosslinking by adding an isocyanate compound to the resin composition according to Embodiment 1 of the present invention. It is preferred because it allows quality. Only one type of the low-molecular compound (C) described above may be used, or two or more types may be used in combination.
  • isocyanate compounds added to the resin composition according to Embodiment 1 of the present invention include diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI).
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • Resin (D)> The resin composition according to Embodiment 1 of the present invention may further contain a resin (D).
  • the resin (D) may be a resin of the same type (composition) as the matrix resin (B), or may be a resin of a different type from the matrix resin (B).
  • the resin composition further comprises a resin (D)
  • the resin (D) is the same type of resin as the matrix resin (B).
  • the resin composition obtained contains only the matrix resin (B). looks like
  • the resin (D) is used in the method for producing the resin composition, and the resin (D) is a different type of resin from the matrix resin (B).
  • the matrix resin (B) and the resin (D) can be distinguished from each other in the resulting resin composition.
  • the finally obtained resin composition may contain the resin (D) as a resin other than the matrix resin (B).
  • the resin (D) is, for example, (i) a resin having two or more polymerizable unsaturated bonds in the molecule, (ii) a thermosetting resin, (iii) a thermoplastic resin, or (iv) these (i) Any combination of the resins of (iii).
  • Resins having two or more polymerizable unsaturated bonds in the molecule that can be suitably used as the resin (D) include unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, One or more curable resins selected from the group consisting of polyether (meth)acrylates and acrylated (meth)acrylates.
  • thermosetting resins in the resin (D) include resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenol resins, polyol resins and amino-formaldehyde resins.
  • the content of the resin (D) in the resin composition according to Embodiment 1 of the present invention is 10 parts by weight or more when the total of the fine polymer particles (A) and the matrix resin (B) is 100 parts by weight. is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, even more preferably 50 parts by weight or more, and particularly preferably 70 parts by weight or more.
  • the content of the resin (D) in the resin composition according to Embodiment 1 of the present invention is within the above range, there is an advantage that more of the desired effects of the resin (D) can be enjoyed.
  • the upper limit of the content of the resin (D) in the resin composition according to Embodiment 1 of the present invention is not particularly limited.
  • the total amount of the combined fine particles (A) and the matrix resin (B) is 100 parts by weight, it is preferably 10,000 parts by weight or less, more preferably 5,000 parts by weight or less. It is more preferably 000 parts by weight or less, more preferably 1,000 parts by weight or less, more preferably 750 parts by weight or less, more preferably 500 parts by weight or less, and 300 parts by weight or less. is more preferably 100 parts by weight or less, more preferably 90 parts by weight or less, even more preferably 80 parts by weight or less, and particularly preferably 70 parts by weight or less .
  • the resin composition according to Embodiment 1 of the present invention may further contain a known thermosetting resin other than the matrix resin (B), or may further contain a known thermoplastic resin.
  • the resin composition according to Embodiment 1 of the present invention may further contain an epoxy resin as the resin (D).
  • the content of the epoxy resin is preferably less than 0.5 parts by weight with respect to 100 parts by weight of the total amount of the matrix resin (B) and the low-molecular-weight compound (C). Since the epoxy resin is not incorporated into the cross-linking of the matrix resin (B), which is the main component, if the content is 0.5 parts by weight or more, the heat resistance (Tg) of the cured product may decrease, and the surface of the cured product may deteriorate. Stickiness (surface tackiness) may develop, and the solvent may be easily absorbed, resulting in a decrease in chemical resistance.
  • the content of the epoxy resin is preferably less than 0.3 parts by weight and less than 0.2 parts by weight with respect to 100 parts by weight as the total amount of the matrix resin (B) and the low-molecular-weight compound (C). is more preferred, less than 0.1 part by weight is particularly preferred, and it is most preferred to contain no epoxy resin.
  • Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, hydrogenated bisphenol A (or F) type epoxy resin, glycidyl ether type epoxy resin, and aminoglycidyl ether-containing resin.
  • Known epoxy resins such as resins and epoxy compounds obtained by subjecting these epoxy resins to addition reactions with bisphenol A (or F) compounds, polybasic acids and the like can be mentioned.
  • epoxy group-containing compounds such as low-molecular-weight monomers
  • Other epoxy group-containing compounds that do not have a polymerizable unsaturated bond may also adversely affect the physical properties of the cured product if they remain without being incorporated into the cross-linking of the matrix resin (B).
  • the content in the composition is small because it has properties. Specifically, it is preferably 0.5 parts by weight or less, more preferably 0.1 parts by weight or less, relative to 100 parts by weight of the total amount of the matrix resin (B) and the low-molecular-weight compound (C).
  • the resin (D) is at least one thermosetting resin selected from the group consisting of resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenol resins, polyol resins and amino-formaldehyde resins. It may contain a flexible resin.
  • the thermoplastic resin in the resin (D) includes, for example, one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers as structural units. Examples thereof include polymers containing one or more structural units derived from a polymer. Examples of thermoplastic resins for resin (D) include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes and polyvinyl acetates. In the resin (D), only one type of thermoplastic resin may be used, or two or more types may be used in combination.
  • the resin composition according to Embodiment 1 of the present invention may further contain a radical polymerization initiator.
  • the radical polymerization initiator is a curing agent for the matrix resin (B) and the low-molecular-weight compound (C), and is an initiator for cross-linking reaction of polymerizable unsaturated bonds (carbon-carbon double bonds, etc.) in this resin. .
  • a radical polymerization initiator is used together with a curing accelerator and a co-catalyst, if necessary.
  • radical polymerization initiators include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t- organic peroxides such as butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy octanoate; and azo compounds such as azobisisobutyronitrile.
  • one or more selected from the group consisting of benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, and methyl ethyl ketone peroxide are preferred, and cumene is more preferred.
  • Hydroperoxide, methyl ethyl ketone peroxide Only one type of the radical polymerization initiator described above may be used, or two or more types may be used in combination.
  • Radical polymerization initiators can be classified according to their optimum use temperature. There are relatively high temperature acting initiators such as cumene hydroperoxide and dicumyl peroxide, and relatively low temperature acting initiators such as benzoyl peroxide and azobisisobutyronitrile. It is preferable to use a combination of two or more radical polymerization initiators having different decomposition temperatures because it is possible to obtain a resin composition having curing activity in a wide temperature range. By combining two or more radical polymerization initiators, for example, while controlling the curing start temperature relatively low, curing progresses and the composition has curing activity even in the late stage of curing when the temperature reaches a high temperature. The reaction rate of the polymerizable unsaturated bonds can be increased, and the physical properties of the cured product can be enhanced.
  • relatively high temperature acting initiators such as cumene hydroperoxide and dicumyl peroxide
  • relatively low temperature acting initiators such as benzoyl peroxide and azobisisobuty
  • the combination of two or more radical polymerization initiators is not particularly limited, but specific examples include a combination of cumene hydroperoxide and methyl ethyl ketone peroxide, t-butyl peroxybenzoate and t-butyl peroxyoctanoate. A combination with, and the like.
  • the 10-hour half-life temperature is an index of the decomposition temperature of the radical polymerization initiator.
  • the difference in 10-hour half-life temperature between the two or more radical polymerization initiators used is preferably 10°C or more, more preferably 20°C or more, and particularly preferably 20°C or more.
  • the curing accelerator is an additive that acts as a catalyst for the decomposition reaction (radical generation reaction) of the radical polymerization initiator, and includes metal salts of naphthenic acid and octenic acid (cobalt salts, tin salts, lead salts, etc.). Cobalt naphthenate is preferred from the viewpoint of improving toughness and appearance.
  • a curing accelerator it should be added in an amount of 0.1 to 1 part by weight per 100 parts by weight of the matrix resin (B) immediately before the curing reaction in order to prevent the curing reaction from occurring rapidly. is preferred.
  • the co-catalyst is an additive for causing radical generation at low temperatures by decomposing the radical polymerization initiator even at low temperatures, and examples thereof include amine compounds such as N,N-dimethylaniline, triethylamine, and triethanolamine. However, N,N-dimethylaniline is preferred because efficient reaction is possible.
  • a co-catalyst it is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the matrix resin (B) of the present invention, or 1 to 15 parts by weight with respect to 100 parts by weight of the radical polymerization initiator. is preferably added in the range of
  • the resin composition according to Embodiment 1 of the present invention may optionally include, for example, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (anti-gelling agents), plasticizers, agent, leveling agent, antifoaming agent, silane coupling agent, antistatic agent, flame retardant, lubricant, thickener, viscosity reducer, low shrinkage agent, fiber reinforcement, inorganic filler, organic filler, internal release agent agents, wetting agents, polymerization modifiers, thermoplastic resins, drying agents, dispersing agents, and the like.
  • colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (anti-gelling agents), plasticizers, agent, leveling agent, antifoaming agent, silane coupling agent, antistatic agent, flame retardant, lubricant, thickener, viscosity reducer, low shrinkage agent, fiber reinforcement, inorganic filler, organic filler, internal release agent agents
  • fillers include calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, dry silica such as fumed silica, wet silica, crystalline silica, fused silica, bentonite, montmorillonite, silica.
  • Inorganic fillers such as carbon nanotubes and organic fillers such as polymer beads are included.
  • At least one inorganic filler selected from the group consisting of calcium carbonate, aluminum hydroxide, dry silica, clay, talc and glass powder is particularly preferred. Only one filler may be used, or two or more fillers may be used in combination.
  • a filler When a filler is used, it is preferably 5 to 400 parts by weight, more preferably 30 to 300 parts by weight, with respect to 100 parts by weight of the matrix resin (B) contained in the resin composition according to Embodiment 1 of the present invention. 100 to 200 parts by weight is particularly preferred. If the amount of the filler compounded is less than 5 parts by weight, the surface hardness and rigidity of the resulting cured product may not be sufficiently obtained. When the amount of the filler compounded exceeds 400 parts by weight, the viscosity of the resin composition tends to be too high, and workability during molding tends to deteriorate, and the fluidity of the resin composition in the mold decreases. However, the mechanical properties of the obtained molding may deteriorate.
  • the filler may be subjected to a coupling treatment in order to improve adhesion with the matrix resin (B).
  • a coupling treatment in order to improve adhesion with the matrix resin (B).
  • These coupling agents are not particularly limited, but include silane-based coupling agents, chromium-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, zirconium-based coupling agents, and the like. be done. Moreover, only one type of these may be used, or two or more types may be used in combination.
  • the thickener is not particularly limited, but inorganic thickeners such as oxides and hydroxides of alkaline earth metals are preferred. Specific examples include magnesium oxide, calcium oxide, magnesium hydroxide and calcium hydroxide.
  • Thermoplastic polymers such as polymethyl methacrylate, which have swelling properties, can also be used as thickeners. Only one type of these thickeners may be used, or two or more types may be used in combination.
  • a thickener When a thickener is used, it is preferably 0.1 to 30 parts by weight, preferably 0.3 to 10 parts by weight is more preferred, and 1 to 3 parts by weight is particularly preferred. If the amount of the thickening agent is less than 0.1 parts by weight, sufficient thickening may not be obtained. If the amount of the filler compounded exceeds 30 parts by weight, the viscosity of the resin composition tends to be too high, resulting in poor workability during molding.
  • low shrinkage agents include polystyrene, polyethylene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycaprolactam, saturated polyester, styrene-acrylonitrile copolymer, vinyl acetate-styrene copolymer, styrene.
  • -Divinylbenzene copolymer, methyl methacrylate-polyfunctional methacrylate copolymer, polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and other rubber-like polymers are used.
  • thermoplastic polymers may be partially introduced with a crosslinked structure.
  • These low shrinkage agents may be used alone or in combination of two or more. When using a low shrinkage agent, it is preferably 2 to 20 parts by weight with respect to 100 parts by weight of the matrix resin (B) contained in the resin composition according to the first embodiment of the present invention. If the amount is less than 2 parts by weight, the shrinkage reduction effect may not be sufficient, and if the amount exceeds 20 parts by weight, the transparency of the molded product may be lowered and the cost may be increased.
  • fiber reinforcing materials include inorganic fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers; organic fibers such as aramid and polyester; natural fibers; not to be
  • the form of the fiber includes roving, cloth, mat, woven fabric, chopped roving, chopped strand, etc., but is not particularly limited. Only one type of these fiber reinforcing materials may be used, or two or more types may be used in combination.
  • a fiber reinforcing material it is preferably 1 to 400 parts by weight with respect to 100 parts by weight of the matrix resin (B) contained in the resin composition according to Embodiment 1 of the present invention. If it is less than 1 part by weight, the reinforcing effect may not be sufficient, and if it exceeds 400 parts by weight, the surface condition of the cured product may deteriorate.
  • internal release agents include stearic acid, zinc stearate, aluminum stearate, calcium stearate, barium stearate, stearamide, triphenyl phosphate, alkyl phosphate, commonly used waxes, silicone oil and the like.
  • wetting agent commercially available products can be used as they are.
  • commercially available from BYK Chemie Co., Ltd. "W-995", “W-996”, “W-9010”, “W-960”, “W-965", “W-990” and the like. However, these are appropriately selected and used depending on the purpose of use.
  • polymerization modifiers examples include polymerization inhibitors such as hydroquinone, methylhydroquinone, methoxyhydroquinone, and t-butylhydroquinone. These polymerization modifiers are preferably sufficiently dissolved in the thermosetting resin in advance. As antioxidants, hindered phenols such as 2,6-di-t-butylhydroxytoluene are preferably used.
  • UV absorbers such as benzophenone
  • thixotropy imparting agents such as silica
  • flame retardants such as phosphate esters
  • the resin composition according to Embodiment 1 of the present invention is excellent in handleability due to its low viscosity.
  • the resin composition according to Embodiment 1 of the present invention may have a viscosity of less than 6000 mPa ⁇ s at a shear rate (SR) of 10 s ⁇ 1 .
  • SR shear rate
  • the resin composition according to Embodiment 1 of the present invention can maintain the state of dispersion of the polymer fine particles (A) in the resin composition, aggregation of the polymer fine particles (A) can be prevented. As a result, phase separation is less likely to occur when the resin composition is stored for a long period of time. Therefore, the resin composition according to Embodiment 1 of the present invention has excellent storage stability. Conventionally, particularly when the content of a matrix resin having two or more polymerizable unsaturated bonds in the molecule in 100% by weight of the resin composition is large (for example, in 100% by weight of the resin composition, the matrix resin is 90% by weight or more), there is a problem that phase separation is more likely to occur during long-term storage of the resin composition.
  • the content of the matrix resin in the resin composition is 90% by weight or more, when stored for a long period of time, at 60 ° C. It can be stored for days without phase separation.
  • a method for measuring the storage stability of the resin composition will be described in detail in Examples described later.
  • Embodiment 2 [Technical idea of Embodiment 2 of the present invention]
  • a composition containing fine polymer particles and a low-molecular-weight compound having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule from the viewpoint of handleability when using the composition, it is preferable that the viscosity of the material is low.
  • a composition (resin composition) conventionally, when the resin composition is stored for a long period of time, the polymer fine particles in the resin composition and the resin may undergo phase separation, that is, there is room for improvement in the storage stability of the resin composition. there were.
  • the resin composition contains a large amount of resin having two or more polymerizable unsaturated bonds in the molecule (for example, the resin is 90% by weight or more in 100% by weight of the resin composition.
  • the resin is 90% by weight or more in 100% by weight of the resin composition.
  • phase separation between the polymer fine particles and the resin was remarkable due to long-term storage of the resin composition.
  • the phase separation between the polymer fine particles in the resin composition and the matrix resin was caused by aggregation of the polymer fine particles in the resin composition.
  • a composition containing fine polymer particles and the low-molecular-weight compound has handleability and two or more polymerizable unsaturated bonds in the molecule of the fine polymer particles and the low-molecular-weight compound.
  • the inventors conducted extensive studies.
  • the present inventor newly found the following findings: (1) A composition containing the polymer microparticles and the low-molecular-weight compound by using a specific polyfunctional monomer as a monomer in the formation (polymerization) of the graft portion of the polymer microparticles. Being able to reduce the viscosity of things.
  • the specific polyfunctional monomer can function as a cross-linking agent.
  • the present inventors have found that the viscosity of a composition containing fine polymer particles and the low-molecular-weight compound is reduced, and that two or more molecules are present in the molecule of the fine polymer particles and the low-molecular-weight compound.
  • a composition resin composition
  • further studies were conducted.
  • the present inventors have newly discovered the following knowledge and completed the present invention: in the formation (polymerization) of the graft portion of polymer fine particles, a specific polyfunctional monomer (crosslinking agent) By using a specific amount of, the viscosity of the composition containing the polymer fine particles and the low-molecular compound is reduced, and the polymer fine particles and the low-molecular-weight compound have two or more polymerizable heteroatoms in the molecule. It is possible to achieve both maintenance of the dispersed state of the polymer fine particles in the composition (resin composition) containing the resin having a saturated bond.
  • the second composition according to Embodiment 2 of the present invention contains polymer fine particles (A) and a low molecular weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule. is doing.
  • the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body.
  • the elastic body of the fine polymer particles (A) contains one or more selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers.
  • the graft portion of the fine polymer particles (A) is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer, and
  • the first monomer is one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers
  • the second monomer is , is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule.
  • the second structural unit is 0.00%. % by weight and less than 2.00% by weight.
  • the polymer fine particles (A) and the low molecular weight compound (C) are 100% by weight, the polymer fine particles (A) are 1 to 50% by weight and the low molecular compound (C) is 50 to 99% by weight. % by weight.
  • the polymer constituting the graft portion of the polymer fine particles (A) contains the second structural unit derived from the second monomer, thereby The viscosity of the second composition can be reduced as compared with the case where the graft portion of the coalesced fine particles (A) does not contain the second constitutional unit. Therefore, the second composition according to Embodiment 2 of the present invention has the advantage of being excellent in handleability.
  • the second composition may further contain a resin (D).
  • a resin (D) in the second composition according to Embodiment 2 of the present invention, when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight Furthermore, since the content of the second structural unit is more than 0.00% by weight and less than 2.00% by weight, the dispersed state of the polymer fine particles (A) in the second composition can be maintained. Aggregation of the polymer fine particles (A) can be prevented. As a result, when the second composition further contains the resin (D), phase separation between the polymer fine particles (A) and the resin (D) in the second composition occurs when the second composition is stored for a long period of time. has the advantage of being less likely to occur. Therefore, the second composition according to Embodiment 2 of the present invention has the advantage of being excellent in storage stability.
  • the polymer fine particles (A) when the total amount of the polymer fine particles (A) and the low-molecular compound (C) is 100% by weight, the polymer fine particles (A) is 10 to 50% by weight. %, and the low molecular weight compound (C) may be 50 to 90% by weight.
  • the mixing ratio of the polymer fine particles (A) and the low-molecular-weight compound (C) in the second composition is within the above range, there is an advantage that the second composition can be used as a high-concentration masterbatch.
  • the polymer fine particles (A) are 5% by weight to 50% by weight, preferably 50% to 95% by weight of the low molecular weight compound (C), 6% to 50% by weight of the fine polymer particles (A), and 50% to 50% by weight of the low molecular weight compound (C) It is more preferably 94% by weight, more preferably 7% to 50% by weight of the polymer fine particles (A) and 50% to 93% by weight of the low-molecular-weight compound (C), and the polymer fine particles ( More preferably, A) is 8% to 50% by weight, the low molecular weight compound (C) is 50% to 92% by weight, and the polymer fine particles (A) is 9% to 50% by weight, and the low molecular compound (C) is more preferably 50% to 91% by weight, the fine polymer particles (A) are 10% to 50% by weight, and
  • the polymer fine particles (A) are 15% by weight to 50% by weight, the low-molecular-weight compound (C) is 50% by weight to 85% by weight, and the polymer fine particles (A) are 20% by weight. It is more preferable that the content of the polymer fine particles (A) is 25% to 50% by weight and the low molecular weight compound (C) is 50% by weight. % to 75% by weight, more preferably 30% to 50% by weight of the fine polymer particles (A) and 50% to 70% by weight of the low-molecular-weight compound (C). More preferably, the fine particles (A) are 35% by weight to 50% by weight, and the low molecular weight compound (C) is 50% by weight to 65% by weight.
  • the second composition according to Embodiment 2 of the present invention when the total amount of the polymer fine particles (A) and the low-molecular weight compound (C) is 100% by weight, the polymer fine particles (A) are 40% by weight to 50% by weight, the low molecular weight compound (C) may be 50% to 60% by weight, the polymer fine particle (A) is 45% to 50% by weight, and the low molecular weight compound (C) is 50% by weight to It may be 55% by weight.
  • the second composition according to Embodiment 2 of the present invention when the blending ratio of the polymer fine particles (A) and the low-molecular-weight compound (C) in the second composition according to Embodiment 2 of the present invention is within the above range, the second composition is used as a higher-concentration masterbatch. It has the further advantage of being able to
  • the second composition according to Embodiment 2 of the present invention may further contain a resin (D).
  • "Resin (D)" is as described for the resin composition according to Embodiment 1, and will not be repeated here.
  • the content of the resin (D) in the second composition according to Embodiment 2 of the present invention is 10 parts by weight when the total of the fine polymer particles (A) and the low-molecular-weight compound (C) is 100 parts by weight. parts by weight or more, more preferably 20 parts by weight or more, more preferably 30 parts by weight or more, even more preferably 50 parts by weight or more, particularly 70 parts by weight or more preferable.
  • the content of the resin (D) in the second composition according to Embodiment 2 of the present invention is within the above range, there is an advantage that more of the desired effects of the resin (D) can be enjoyed.
  • the upper limit of the content of the resin (D) in the second composition according to Embodiment 2 of the present invention is not particularly limited, but from the viewpoint of maintaining excellent handleability and storage stability of the present second composition .
  • the total of the fine polymer particles (A) and the low-molecular-weight compound (C) is 100 parts by weight, it is preferably 10,000 parts by weight or less, more preferably 5,000 parts by weight or less. , more preferably 2,000 parts by weight or less, more preferably 1,000 parts by weight or less, more preferably 750 parts by weight or less, more preferably 500 parts by weight or less, It is more preferably 100 parts by weight or less, more preferably 90 parts by weight or less, even more preferably 80 parts by weight or less, and 70 parts by weight or less. is particularly preferred.
  • the second composition according to Embodiment 2 of the present invention may further contain a known thermosetting resin, or may further contain a known thermoplastic resin.
  • the second composition according to Embodiment 2 of the present invention may further contain an epoxy resin as the resin (D).
  • the content of the epoxy resin is preferably less than 0.5 parts by weight with respect to 100 parts by weight of the low molecular weight compound (C).
  • the content of the epoxy resin is 0.5 parts by weight or more, the heat resistance (Tg) of the cured product is lowered, the surface of the cured product is sticky (surface tackiness), and the solvent is easily absorbed.
  • the chemical resistance may decrease.
  • the content of the epoxy resin is preferably less than 0.3 parts by weight, more preferably less than 0.2 parts by weight, and 0.1 parts by weight with respect to 100 parts by weight of the low molecular weight compound (C). It is particularly preferred that the content is less than, and most preferred that it contains no epoxy resin.
  • the second composition according to Embodiment 2 of the present invention further contains other components, they are as described for the resin composition according to Embodiment 1, and will not be repeated here. Regarding the amounts of other components to be added, the description of the resin composition according to Embodiment 1 is applied by replacing the “matrix resin (B)” with the “low molecular weight compound (C)”. are omitted.
  • the second composition according to Embodiment 2 of the present invention has excellent handleability due to its low viscosity.
  • the second composition according to Embodiment 2 of the present invention may have a viscosity of less than 1600 mPa ⁇ s at a shear rate (SR) of 10 s ⁇ 1 .
  • the second composition according to Embodiment 2 of the present invention can maintain the dispersion state of the polymer fine particles (A) in the composition, aggregation of the polymer fine particles (A) can be prevented. As a result, phase separation is less likely to occur when the second composition is stored for a long period of time. Therefore, the second composition according to Embodiment 2 of the present invention has excellent storage stability. Conventionally, particularly when the content of a matrix resin having two or more polymerizable unsaturated bonds in the molecule in 100% by weight of the composition is large (for example, in 100% by weight of the composition, the matrix resin is 90 % by weight or more), there is a problem that phase separation is more likely to occur during long-term storage of the composition. For example, in the second composition according to Embodiment 2 of the present invention, even when the content of the matrix resin in the composition is 90% by weight or more, when stored for a long period of time, at 60 ° C. It can be stored for days without phase separation.
  • the method for producing a resin composition according to Embodiment 1 of the present invention includes polymer fine particles (A) produced by the above-described method for producing polymer fine particles, and two or more polymerizable unsaturated bonds in the molecule. and a matrix resin (B), wherein in the mixing step, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles A configuration in which the polymer fine particles (A) and the matrix resin (B) are mixed at a mixing ratio of 1 to 50% by weight of (A) and 50 to 99% by weight of the matrix resin (B). is.
  • the resin composition according to Embodiment 1 of the present invention is a composition in which polymer fine particles (A) are dispersed in the state of primary particles in a curable resin composition containing a matrix resin (B) as a main component. .
  • Various methods can be used for obtaining a composition in which the polymer fine particles (A) are dispersed in the state of primary particles.
  • a method of removing unnecessary components such as water after bringing into contact with the matrix resin (B) and/or the low-molecular-weight compound (C)
  • a method of extracting the polymer fine particles (A) once with an organic solvent and then extracting the matrix resin (B) and / Or a method of removing the organic solvent after mixing with the low-molecular-weight compound (C), etc., but it is preferable to use the method described in International Publication No. 2005/28546.
  • the mixing step in the method for producing the resin composition according to Embodiment 1 of the present invention may be configured to include the following first to third steps in this order: containing the fine polymer particles (A) After mixing the aqueous latex with an organic solvent that exhibits partial solubility in water, the resulting mixture is brought into contact with water to form aggregates of the polymer fine particles (A) containing the organic solvent in an aqueous phase.
  • the "organic solvent exhibiting partial solubility in water” means that when the aqueous latex of the polymer fine particles (A) is mixed with the organic solvent, the polymer fine particles (A) can be mixed without substantially solidifying and depositing. At least one or two or more organic solvents or organic solvent mixtures that can be achieved can be used without limitation. It is preferably 5% by weight or more and 30% by weight or less. When the solubility in water at 20° C. of the organic solvent partially soluble in water is 40% by weight or less, the aqueous latex of the polymer particles (A) is not coagulated, and the mixing operation can be performed smoothly. can. In addition, when the solubility in water at 20° C. of the organic solvent partially soluble in water is 5% by weight or more, it can be sufficiently mixed with the aqueous latex of the polymer particles (A), and can be smoothly mixed. operation can be performed.
  • organic solvent exhibiting partial solubility in water examples include esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; ethanol , (iso)propanol, butanol and other alcohols; tetrahydrofuran, tetrahydropyran, dioxane, diethyl ether and other ethers; benzene, toluene, xylene and other aromatic hydrocarbons; methylene chloride, chloroform and other halogenated hydrocarbons or a mixture thereof, which satisfies the above range of solubility in water at 20°C.
  • an organic solvent containing 50% by weight or more of methyl ethyl ketone is more preferably used as an organic solvent exhibiting partial solubility in water from the viewpoints of affinity with a reactive polymerizable organic compound and ease of availability. Furthermore, an organic solvent containing 75% by weight or more of methyl ethyl ketone is particularly preferably used.
  • the composition for example, the present resin composition
  • the polymer fine particles (A) in which the polymer fine particles (A) are dispersed in the state of primary particles in a resin containing the matrix resin (B) as a main component
  • An aqueous latex containing the coalesced fine particles (A) (specifically, a reaction mixture after the production of the polymer fine particles (A) by emulsion polymerization) is added to an aqueous latex having a solubility in water at 20°C of 5% by weight or more and 40% by weight or less.
  • the resulting mixture After mixing with an organic solvent, the resulting mixture is further mixed with an excess amount of water to form a first step of aggregating the polymer fine particles (A), and separating and separating the aggregated polymer fine particles (A) from the liquid phase.
  • the obtained aggregates of polymer fine particles (A) are mixed again with an organic solvent to obtain an organic solvent dispersion of polymer fine particles (A) in a second step; and a third step of distilling off the organic solvent from the resulting mixture after mixing with the resin (B) and/or the low-molecular-weight compound (C).
  • the matrix resin (B) or the mixture of the matrix resin (B) and the low-molecular-weight compound (C) is liquid at 23°C because the third step is facilitated. Furthermore, it is more preferable that the matrix resin (B) alone is liquid at 23°C.
  • liquid at 23°C means that the softening point is 23°C or lower and that the material exhibits fluidity at 23°C.
  • a resin composition produced by the method for producing a resin composition described above is also included in the scope of the present invention.
  • a cured product obtained by curing the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention in other words, the resin composition according to Embodiment 1 of the present invention or the present invention
  • the fine polymer particles (A) can be uniformly dispersed in the state of primary particles.
  • a cured product obtained by curing the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention is also an embodiment of the present invention.
  • the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention can be used for various uses, and the uses are not particularly limited.
  • the resin composition or the second composition is, for example, an adhesive, a coating material, a binder for reinforcing fibers, a composite material, a molding material for a 3D printer, a sealant, an electronic substrate, an ink binder, a wood chip binder, or a binder for rubber chips. , foam chip binders, binders for castings, bedrock consolidation materials for floor materials and ceramics, and urethane foams.
  • urethane foam examples include automobile seats, automobile interior parts, sound absorbing materials, vibration damping materials, shock absorbers (shock absorbing materials), heat insulating materials, construction floor material cushions, and the like.
  • the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention is used as an adhesive, a coating material, a binder for reinforcing fibers, a composite material, and a molding of a 3D printer. It is more preferably used as materials, encapsulants, and electronic substrates.
  • An embodiment of the present invention may have the following configuration.
  • the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
  • the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber,
  • the graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
  • the first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
  • the elastic body is an elastic core of an elastic body obtained by polymerizing one or more monomers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers, and organosiloxane-based rubbers; a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
  • the matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates.
  • the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
  • the elastic body includes one or more selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber,
  • the graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
  • the first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
  • the polymer fine-particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (C) is is 50 to 99% by weight.
  • the elastic body is an elastic core of an elastic body obtained by polymerizing one or more monomers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers, and organosiloxane-based rubbers; a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
  • the second structural unit exceeds 0.00% by weight and is 1.00% by weight. % by weight, the composition according to any one of [10] to [13].
  • the matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates.
  • the first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, In the graft portion preparation step, the second monomer exceeds 0.00% by weight when the total of the first monomer and the second monomer is 100% by weight.
  • the elastic body preparation step includes the following steps (a) and (b): (a) polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers; (b) a step of polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
  • the mixing step when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (C) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (C) is A method for producing a composition, wherein the fine polymer particles (A) and the low-molecular-weight compound (C) are mixed at a compounding ratio in which the molecular compound (C) is 50 to 99% by weight.
  • polymer microparticles (A); (i) a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule, or (ii) a low molecular weight compound (C ), and
  • the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
  • the elastic body includes one or more selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber
  • the graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
  • the first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer
  • the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds
  • the polymer fine particle (A) is 1 to 50% by weight when the total of the polymer fine particle (A) and the matrix resin (B) is 100% by weight. % by weight, and the matrix resin (B) is 50 to 99% by weight, (ii) when the low-molecular-weight compound (C) is contained, the polymer fine-particles (A) is 1 ⁇ 50% by weight, and the low molecular weight compound (C) is 50-99% by weight.
  • PGP paramenthane hydroperoxide
  • a water-based latex (R-1) containing an elastic body (elastic body core) mainly composed of polystyrene-butadiene rubber was obtained.
  • the volume-average particle size of the elastic body (core of the elastic body) contained in the obtained aqueous latex was 90 nm.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • BHP 0.035 parts by weight t-butyl hydroperoxide
  • an aqueous latex (L1) containing polymer fine particles (A) was obtained.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L1) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 0.00% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP butyl hydroperoxide
  • aqueous latex (L2) containing polymer fine particles (A) was obtained.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L2) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 0.59% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then, 5.7 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.3 parts by weight allyl methacrylate (AMA), and t- A mixture of 0.035 parts by weight of butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP butyl hydroperoxide
  • aqueous latex (L3) containing polymer fine particles (A) was obtained.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L3) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.76% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP butyl hydroperoxide
  • aqueous latex (L4) containing polymer fine particles (A) was obtained.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L4) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 3.53% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then, 5.0 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), 1.0 parts by weight allyl methacrylate (AMA), and t- A mixture of 0.035 parts by weight of butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP butyl hydroperoxide
  • aqueous latex (L5) containing polymer fine particles (A) was obtained.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L5) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 5.88% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP t-butyl hydroperoxide
  • aqueous latex (L6) containing polymer fine particles (A) was obtained.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the obtained aqueous latex (L6) was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.60% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
  • AMA allyl methacrylate
  • BHP t-butyl hydroperoxide
  • MMA methyl methacrylate
  • BA butyl acrylate
  • HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP t-butyl hydroperoxide
  • the volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L7) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.60% by weight when set to 100% by weight.
  • EDTA 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
  • AMA allyl methacrylate
  • BHP t-butyl hydroperoxide
  • MMA methyl methacrylate
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • AMA allyl methacrylate
  • BHP t-butyl hydroperoxide
  • the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm.
  • the solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L8) obtained was 30% by weight.
  • the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.67% by weight when set to 100% by weight.
  • methyl methacrylate (MMA), butyl acrylate (BA) and 4-hydroxybutyl acrylate (4HBA) are the first monomers.
  • monomer and allyl methacrylate (AMA) is the second monomer.
  • Table 1 summarizes the blending amounts of each component of the polymer microparticles (A).
  • the "content of the second structural unit” described in Table 1 is the second structural unit when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion is 100% by weight. It is the content of the structural unit of No. 2.
  • the resin composition (A-1) contains 40% by weight of the fine polymer particles (A) when the total amount of the fine polymer particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-2) was obtained in the same manner as in Example 1, except that the latex (L3) was used as the latex of the fine polymer particles (A).
  • the resin composition (A-2) contains 40% by weight of the polymer particles (A) when the total of the polymer particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-3) was obtained in the same manner as in Example 1, except that the latex (L1) was used as the latex of the polymer fine particles (A).
  • the resin composition (A-3) contains 40% by weight of the fine polymer particles (A) when the total amount of the fine polymer particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-4) was obtained in the same manner as in Example 1, except that the latex (L4) was used as the latex of the fine polymer particles (A).
  • the resin composition (A-4) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-5) was obtained in the same manner as in Example 1, except that the latex (L5) was used as the latex of the fine polymer particles (A).
  • the resin composition (A-5) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-6) was obtained in the same manner as in Example 1, except that the latex (L6) was used as the latex of the fine polymer particles (A).
  • the resin composition (A-6) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-7) was obtained in the same manner as in Example 1, except that the latex (L7) was used as the latex of the fine polymer particles (A).
  • the resin composition (A-7) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a resin composition (A-8) was obtained in the same manner as in Example 1, except that the latex (L8) was used as the latex of the fine polymer particles (A).
  • the resin composition (A-8) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).
  • a digital viscometer DV-II+Pro type manufactured by BROOKFIELD was used to measure the viscosity of the resin compositions prepared in Examples and Comparative Examples.
  • the viscosity was measured at a measurement temperature of 25° C. and a shear rate (SR) of 10 s ⁇ 1 using a spindle CPE-52 depending on the viscosity range.
  • the storage stability of the resin compositions prepared in Examples and Comparative Examples was evaluated by mixing 10 g of the resin composition and 90 g of unsaturated polyester resin 2731-1 manufactured by Eternal Co., Ltd. as the resin (D) using a rotation and revolution mixer. After mixing, the mixture was placed in a transparent bottle, stored in an oven at 60° C., and visually checked for separation over time.
  • the total content of the matrix resin (B) and the resin (D) in the resin composition after mixing the resin composition and the resin (D) i.e., two or more polymerizable unsaturated bonds in the molecule
  • the content of the matrix resin having was 94.2% by weight.
  • phase separation occurred on the X day does not indicate that phase separation started on the X day of the start of the test, but on the X day of the start of the test. It means that phase separation was observed in at least a part of the resin composition as a result of observation. Therefore, "phase-separated on the X day” also includes an embodiment in which at least a part of the resin composition is phase-separated before the X day.
  • the storage stability when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, It has been found that when the structural unit of 2 is less than 2.00% by weight, the resin composition containing such fine polymer particles (A) has excellent storage stability. In particular, when the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, the second structural unit is 1.00% by weight. %, the storage stability of the resin composition is particularly excellent.
  • the resin composition of Comparative Example 1 had a viscosity of 6000 mPa ⁇ s or more at a shear rate (SR) of 10 s ⁇ 1 .
  • the resin compositions of Examples 1 to 5 and Comparative Examples 2 to 3 all had low viscosities at a shear rate (SR) of 10 s ⁇ 1 , well below 6000 mPa ⁇ s. rice field.
  • the handleability when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, the second structural unit is more than 0.00% by weight, the resin composition containing the fine polymer particles (A) has excellent handleability.
  • the polyfunctional monomer component contained in the surface-crosslinked polymer surprisingly affects the viscosity of the resin composition. can be further reduced, but the compatibility of the resin composition is not affected.
  • Second composition> instead of 45 parts by weight of a liquid unsaturated polyester resin (manufactured by Eternal, Eterset 2010) as the matrix resin (B) and 19 parts by weight of 2-hydroxypropyl methacrylate (HPMA) as the low-molecular compound (C), a low-molecular A composition (A-9) was obtained in the same manner as in Example 1, except that 64 parts by weight of 2-hydroxypropyl methacrylate (HPMA), which is the compound (C), was used.
  • the composition (A-9) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.
  • Example 7 A composition (A-10) was obtained in the same manner as in Example 6, except that the latex (L3) was used as the latex of the fine polymer particles (A).
  • the composition (A-10) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.
  • composition (A-11) was obtained in the same manner as in Example 6, except that the latex (L1) was used as the latex of the fine polymer particles (A).
  • the composition (A-11) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.
  • composition (A-12) was obtained in the same manner as in Example 6, except that the latex (L5) was used as the latex of the fine polymer particles (A).
  • the composition (A-12) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.
  • phase separation was already observed in the resin composition of Comparative Example 5 in observation on the 23rd day from the start of the test.
  • both the resin compositions of Examples 6 and 7 and the resin composition of Comparative Example 4 were found to undergo phase separation when observed 65 days after the start of the test.
  • the observation results on the 50th day from the start of the test are also shown in parentheses.
  • the resin composition of Example 7 was found to undergo phase separation when observed 50 days after the start of the test.
  • no phase separation was observed in the resin compositions of Example 6 and Comparative Example 4 after 50 days from the start of the test.
  • the storage stability when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, It has been found that when the structural unit of 2 is less than 2.00% by weight, the resin composition containing such fine polymer particles (A) has excellent storage stability. In particular, when the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, the second structural unit is 1.00% by weight. %, the storage stability of the resin composition is particularly excellent.
  • the composition of Comparative Example 4 had a viscosity of 1650 mPa ⁇ s at a shear rate (SR) of 10 s ⁇ 1 .
  • SR shear rate
  • all of the compositions of Examples 6 to 7 and Comparative Example 5 had Shear Rate (SR, The viscosity at a shear rate of 10 s -1 was reduced by 10% or more, and the handleability was improved.
  • the handleability when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, the second structural unit exceeds 0.00% by weight, the composition containing such fine polymer particles (A) has improved handleability.
  • the second composition containing the polymer fine particles (A) and the low-molecular-weight compound (C) also constitutes the graft portion of the polymer fine particles (A).
  • the second structural unit is more than 0.00% by weight and less than 2.00% by weight, when the total of the first structural unit and the second structural unit in the polymer is 100% by weight , the second composition containing such polymer fine particles (A) was found to be excellent in both handleability and storage stability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une composition de résine durcissable qui présente d'excellentes propriétés de manipulation et une excellente stabilité au stockage. L'invention concerne une composition de résine qui contient une quantité spécifique de fines particules polymères (A) et une quantité spécifique d'une résine de matrice (B) qui comporte au moins deux liaisons insaturées polymérisables dans chaque molécule. Chacune des fines particules polymères (A) comporte un corps élastique et une partie de greffage ; et la partie de greffage est formée d'un polymère qui contient une quantité spécifique d'un premier motif constitutif spécifique et une quantité spécifique d'un second motif constitutif issu d'un monomère multifonctionnel qui comporte au moins deux liaisons insaturées polymérisables dans chaque molécule.
PCT/JP2022/008754 2021-03-05 2022-03-02 Composition de résine, procédé de production de fines particules polymères et procédé de production d'une composition de résine WO2022186248A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06184255A (ja) * 1992-12-22 1994-07-05 Asahi Chem Ind Co Ltd 硬化性の樹脂組成物並びにこれを用いた複合材料および積層体
JPH0733836A (ja) * 1993-07-22 1995-02-03 Mitsubishi Rayon Co Ltd グラフト共重合体の製法および熱可塑性樹脂組成物
JP2002003819A (ja) * 2000-06-21 2002-01-09 Nof Corp 制振用熱硬化性樹脂組成物及びその硬化物
WO2008020614A1 (fr) * 2006-08-18 2008-02-21 Kaneka Corporation Procédé destiné à produire un polymère vinylique ramifié ayant un groupe fonctionnel
JP2010106204A (ja) * 2008-10-31 2010-05-13 Kureha Corp グラフト共重合体粒子及びその製造方法、並びにそれを用いた制電性樹脂組成物
JP2016164283A (ja) * 2012-10-31 2016-09-08 三菱レイヨン株式会社 粉体、樹脂組成物及び成形体
JP2018090692A (ja) * 2016-12-02 2018-06-14 三菱ケミカル株式会社 ゴム含有グラフト重合体、熱可塑性樹脂組成物および成形体
WO2019131374A1 (fr) * 2017-12-25 2019-07-04 三菱ケミカル株式会社 Polymère greffé comprenant un caoutchouc, et composition de résine comprenant un polymère greffé à teneur en caoutchouc ainsi que corps moulé de celle-ci
JP2019131744A (ja) * 2018-02-01 2019-08-08 ユーエムジー・エービーエス株式会社 熱可塑性樹脂組成物およびその成形品
WO2020138263A1 (fr) * 2018-12-27 2020-07-02 株式会社カネカ Composition de résine et utilisation associée
WO2020196922A1 (fr) * 2019-03-28 2020-10-01 株式会社カネカ Matière particulaire et son utilisation

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06184255A (ja) * 1992-12-22 1994-07-05 Asahi Chem Ind Co Ltd 硬化性の樹脂組成物並びにこれを用いた複合材料および積層体
JPH0733836A (ja) * 1993-07-22 1995-02-03 Mitsubishi Rayon Co Ltd グラフト共重合体の製法および熱可塑性樹脂組成物
JP2002003819A (ja) * 2000-06-21 2002-01-09 Nof Corp 制振用熱硬化性樹脂組成物及びその硬化物
WO2008020614A1 (fr) * 2006-08-18 2008-02-21 Kaneka Corporation Procédé destiné à produire un polymère vinylique ramifié ayant un groupe fonctionnel
JP2010106204A (ja) * 2008-10-31 2010-05-13 Kureha Corp グラフト共重合体粒子及びその製造方法、並びにそれを用いた制電性樹脂組成物
JP2016164283A (ja) * 2012-10-31 2016-09-08 三菱レイヨン株式会社 粉体、樹脂組成物及び成形体
JP2018090692A (ja) * 2016-12-02 2018-06-14 三菱ケミカル株式会社 ゴム含有グラフト重合体、熱可塑性樹脂組成物および成形体
WO2019131374A1 (fr) * 2017-12-25 2019-07-04 三菱ケミカル株式会社 Polymère greffé comprenant un caoutchouc, et composition de résine comprenant un polymère greffé à teneur en caoutchouc ainsi que corps moulé de celle-ci
JP2019131744A (ja) * 2018-02-01 2019-08-08 ユーエムジー・エービーエス株式会社 熱可塑性樹脂組成物およびその成形品
WO2020138263A1 (fr) * 2018-12-27 2020-07-02 株式会社カネカ Composition de résine et utilisation associée
WO2020196922A1 (fr) * 2019-03-28 2020-10-01 株式会社カネカ Matière particulaire et son utilisation

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