Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • 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
  • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F120/10—Esters
  • C08F120/12—Esters of monohydric alcohols or phenols
  • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • 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

Definitions

• the present invention relates to compositions and methods for producing compositions.
• Radically curable resins such as unsaturated polyester resins and vinyl ester resins are widely used in a variety of applications, such as reinforcing materials such as glass fiber, molding compositions including coating materials, and the like.
• 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).
• the resin composition contains one or more polymerizable unsaturated bonds in the molecule. It is also known to add
• Patent Document 1 discloses a resin composition containing a vinyl ester resin (matrix resin), a vinyl monomer (a low-molecular-weight compound having one or more polymerizable unsaturated bonds in the molecule), and polymer fine particles (polymer fine particles).
• a resin composition is disclosed in which polymer fine particles are dispersed in the form of primary particles in the resin composition.
• Patent Documents 2 to 7 disclose a resin composition containing a matrix resin, polymer fine particles, and a hindered phenol-based antioxidant as an additive for preventing decomposition of the polymer.
• One aspect of the present invention has been made in view of the above problems, and its object is to provide a composition with excellent storage stability.
• the present inventor has completed the present invention as a result of diligent studies to solve the above problems.
• one embodiment of the present invention includes the following configuration.
• A polymer fine particles
• B low-molecular-weight compound
• C hindered phenol-based radical scavenger
• 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 polymer fine-particles (A) are 1 to 50% by weight
• the low-molecular-weight compound (B) is is 50 to 99% by weight.
• a first step of forming the aggregates of A) in the aqueous phase After separating and recovering the aggregates from the aqueous phase, a second step of mixing the aggregates with the organic solvent to obtain a first organic solvent dispersion containing the polymer fine particles (A);
• 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 polymer fine particles (A) are 1 to 50% by weight, and A method for producing a composition, comprising mixing the polymer fine particles (A) and the low-molecular-weight compound (B) at a mixing ratio of 50 to 99% by weight of the low
• the present inventors have proposed a resin composition containing (a) a curable resin before curing, (b) polymer fine particles, and (c) a low-molecular-weight compound having one or more polymerizable unsaturated bonds in the molecule.
• a method of preparing a composition containing fine polymer particles and the low-molecular-weight compound and adding the composition to a curable resin before curing was investigated.
• composition containing polymer fine particles and a low-molecular-weight compound having one or more polymerizable unsaturated bonds in the molecule.
• storage stability is a problem found independently.
• the present inventors have made it an object to provide a composition containing fine polymer particles and a low-molecular-weight compound having one or more polymerizable unsaturated bonds in the molecule and having excellent storage stability.
• an object of one embodiment of the present invention is to provide a composition containing fine polymer particles and a low-molecular-weight compound having one or more polymerizable unsaturated bonds in the molecule and having excellent storage stability. It is to be.
• a composition containing polymer microparticles and a low-molecular-weight compound having one or more polymerizable unsaturated bonds in the molecule contains a general radical scavenger
• H-TEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl
• composition (i) H-TEMPO, a radical scavenger; is added to the composition, the polymerization of the low-molecular-weight compound can be inhibited, and as a result, the gelation of the composition can be suppressed.
• a composition to which H-TEMPO is added can suppress gelation during storage of the composition, it has a new problem that the composition becomes highly viscous during storage. That is, the present inventor independently found that there is room for further improvement in the storage stability of the composition. Under such circumstances, the present inventor sought a radical scavenger capable of further improving the storage stability of the composition based on the above-mentioned new findings, and conducted further investigations. As a result, the present inventors found that the hindered phenol-based radical scavenger can not only suppress the gelation of the composition during storage, but also suppress the increase in the viscosity of the composition during storage. That is, the inventors have found new knowledge that the storage stability of the composition can be further improved.
• a low-molecular-weight compound having one or more polymer unsaturated bonds in the molecule and polymer fine particles By coexisting a hindered phenol-based radical scavenger in a composition containing, a composition having excellent storage stability without the risk of gelation or increase in viscosity during storage can be obtained.
• the composition according to one embodiment of the present invention comprises fine polymer particles (A), a low-molecular-weight compound (B) having a molecular weight of less than 1,000 and having one or more polymerizable unsaturated bonds in the molecule, and a hindered and a phenolic radical scavenger (C).
• 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 fine polymer particles (A) and the low molecular weight compound (B) are 100% by weight, the fine polymer particles (A) are 1 to 50% by weight, and the low molecular weight compound (B) is 50 to 99% by weight. % by weight.
• the composition according to one embodiment of the present invention has excellent storage stability because it has the configuration described above. More specifically, by containing the radical scavenger (C), the composition according to one embodiment of the present invention has significantly improved storage stability compared to a composition that does not contain the radical scavenger (C). It has the advantage of being superior. Furthermore, the composition according to one embodiment of the present invention contains a hindered phenol-based radical scavenger (C) as a radical scavenger. Therefore, the composition according to one embodiment of the present invention is said to have excellent storage stability compared to a composition containing a non-hindered phenol-based radical scavenger such as H-TEMPO, which is a general radical scavenger. have advantages.
• a non-hindered phenol-based radical scavenger such as H-TEMPO, which is a general radical scavenger.
• composition according to one embodiment of the present invention may be simply referred to as “this composition”.
• the storage stability of the composition can be evaluated by the viscosity change rate and the presence or absence of gelation.
• the viscosity change rate is the ratio of the difference between the viscosity of the composition before storage (immediately after production) and the viscosity after storage, and more specifically, it is a value represented by the following formula (1).
• Viscosity change rate (%) ⁇ (Viscosity of composition after storage (V 1 ) ⁇ Viscosity of composition before storage (V 0 ))/Viscosity of composition before storage (V 0 ) ⁇ 100. ⁇ (1)
• the composition has excellent storage stability means that the viscosity change rate is 30% or less when the composition is stored at 80 ° C.
• the composition is stored at 80 ° C. for 2 days. It is intended that the composition does not gel when stored.
• the present composition preferably has a viscosity change rate of 27% or less, more preferably 25% or less when the composition is stored at 80° C. for 7 days.
• the term "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 "compound having one or more polymerizable unsaturated bonds in the molecule” can also be said to be a "monomer having one or more radically polymerizable reactive groups in the same molecule”.
• radical polymerizable reactive group is intended 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 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 preferred.
• 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 effect.
• 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.
• (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 fine polymer particles (A) and a composition having a low Tg can be obtained.
• the resulting composition can provide a cured product with excellent toughness, and (ii) the viscosity of the composition can be 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 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.
• (i) dimethylsilyloxy rubber, methylphenylsilyloxy rubber and dimethylsilyloxy-diphenylsilyl are used because the obtained composition can provide a cured product having excellent heat resistance. It is preferably one or more selected from the group consisting of oxyrubbers, and (ii) more preferably dimethylsilyloxyrubber 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 above configuration, the obtained 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 composition, 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. The term "polymerizable unsaturated bond” can also be referred to as “polymerizable unsaturated bond”, and intends an unsaturated bond that can become a starting point for a polymerization reaction by a radical or 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 composition having a low Tg can be obtained.
• the obtained composition can provide a cured product having excellent toughness.
• the viscosity of the 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 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.
• the monomer that can be included in the monomer group a (hereinafter sometimes referred to as "monomer a") is not limited to the following, but for example, styrene, 2-vinylnaphthalene, etc. substituted vinyl aromatic compounds; vinyl substituted aromatic compounds such as ⁇ -methylstyrene; 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene , 2,4,6-trimethylstyrene and other ring-alkylated vinyl aromatic compounds; 4-methoxystyrene, 4-ethoxystyrene and other ring-alkoxylated vinyl aromatic compounds; 2-chlorostyrene, 3-chlorostyrene, etc.
• ring halogenated vinyl aromatic compounds such as 4-acetoxystyrene; ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl benzoate, vinylcyclohexanoate and the like.
• vinyl esters ; vinyl halides such as vinyl chloride; aromatic monomers such as acenaphthalene and indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as nil methacrylate and trimethylsilyl methacrylate; methacrylic monomers including methacrylic acid derivatives such as methacrylonitrile; certain acrylic acid esters such as isobornyl acrylate and tert-butyl acrylate; acrylic acid derivatives such as acrylonitrile; including acrylic monomers, and the like.
• monomers that can be included in the monomer group a include acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1- Monomers such as adamantyl acrylate and 1-adamantyl methacrylate that can provide a homopolymer having a Tg of 120° C. or higher when converted to a homopolymer are included. These monomers a may be used alone or in combination of two or more.
• Monomers that can be included in 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, 4-hydroxybutyl acrylate and the like. These monomers b may be used alone or in combination of two or more. Among these monomers b, particularly preferred are ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.
• 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 latex 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 fine particles (A) is preferably 40 to 97 wt%, more preferably 60 to 95 wt%, and 70 to 93 wt%, based on 100 wt% of the polymer fine particles (A) as a whole. is more preferred.
• the proportion of the elastic body is (i) 40% by weight or more, the obtained composition can provide a cured product having excellent toughness and impact resistance, and (ii) when it is 97% by weight or less. Since the polymer microparticles (A) do not easily aggregate, the composition containing the polymer microparticles (A) does not become highly viscous, and as a result, the obtained composition has excellent handleability. obtain.
• the elastomer is swellable in a suitable solvent, but substantially insoluble.
• the elastic body is preferably insoluble in the low-molecular-weight compound (B) used and the matrix resin (D) described below.
• 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 gel content of the elastic body is within the above range, the resulting composition can provide a cured product with excellent toughness.
• the method for calculating the gel content is as follows. First, an aqueous latex containing the polymer microparticles (A) is obtained, and then powder particles of the polymer microparticles (A) are obtained from the aqueous latex.
• the method for obtaining powdery particles of the polymer microparticles (A) from the aqueous latex is not particularly limited. For example, (i) the polymer microparticles (A) in the aqueous latex are aggregated, A method of dehydrating the substance and (iii) further drying the agglomerate to obtain powdery particles of the polymer fine particles (A) 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).
• MEK soluble matter component soluble in MEK
• MEK insoluble matter component insoluble in MEK
• 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 30,000 rpm, and the lysate was Separation into MEK soluble matter and MEK insoluble matter.
• a total of 3 sets of centrifugation operations are carried out.
• 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 entirety of the 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.
• the multi-stage polymerized elastic body is composed of elastic body 1 , elastic body 2 , and elastic body 3
• the elastic body 1 forms the innermost layer
• the elastic body 2 layer is formed on the outer side of the elastic body 1
• a mode in which the 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 polymer elastic body and/or (iii) a multi-layer 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.
• 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 It is preferable to contain a surface-crosslinked polymer obtained by polymerizing
• a surface-crosslinked polymer obtained by polymerizing 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.
• (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 composition is improved.
• 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 elastomer When the elastomer has a surface crosslinked polymer, it may also have the following effects: (i) the effect of lowering the viscosity of the present composition, (ii) the effect of increasing the crosslink density of the elastomer as a whole, and (iii) ) The effect of increasing the graft efficiency of the graft part.
• crosslink density in the elastic core of the elastomer is intended the degree of number of crosslink structures in the entire elastic core of the elastomer.
• 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 graft-bonded to the crosslinked polymer, and (iii) graft-bonded to both the elastic body other than the surface-crosslinked polymer (that is, the elastic core portion of the elastic body) and the surface-crosslinked polymer. good too.
• 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 contains, as structural units, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. It is preferably (including) a polymer.
• a graft section having the above configuration can serve a variety of purposes. "Various roles" include, for example, (i) compatibility between polymer fine particles (A) and other organic components of the composition (low-molecular-weight compound (B), matrix resin (D), etc., which will be described later). (ii) improve the dispersibility of the polymer fine particles (A) in other organic components of the composition, and (iii) the composition or its cured product contains 1 polymer fine particle (A). enabling dispersion in the form of sub-particles;
• 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 is intended herein acrylate and/or methacrylate.
• One or more monomers selected from the group consisting of the above-mentioned aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers may be used alone, Two or more kinds may be used in combination.
• a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyanide monomer, and a structural unit derived from a (meth)acrylate monomer are added to the graft portion.
• it preferably contains 10 to 95% by weight, more preferably 30 to 92% by weight, more preferably 50 to 90% by weight, and 60 to 87% by weight. It is particularly preferred and most preferably contains 70 to 85% by weight.
• the graft portion may contain, as a structural unit, a structural unit derived from a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule.
• the polyfunctional monomer can crosslink the polymer obtained by polymerizing the monofunctional monomer in the production of the graft portion. Therefore, the polyfunctional monomer can also be called a "crosslinking agent".
• the graft portion contains a structural unit derived from a polyfunctional monomer, (i) the polymer fine particles (A) can be prevented from swelling in the composition, and (ii) the viscosity of the composition is low. Therefore, there are advantages such as that the composition tends to be easier to handle, and (iii) the dispersibility of the fine polymer particles (A) in other organic components of the composition is improved.
• the graft portion does not contain a structural unit derived from a polyfunctional monomer
• the resulting composition exhibits improved toughness and resistance compared to the case where the graft portion contains a structural unit derived from a polyfunctional monomer. It is possible to provide a cured product that is more excellent in impact resistance.
• 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 and ethylene glycol di(meth) Acrylates, butylene glycol di(meth)acrylate, 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 as the second monomer, or two or more types may be combined and used as the second monomer.
• the graft portion preferably contains 1 to 20% by weight, more preferably 5 to 15% by weight, of a structural unit derived from a polyfunctional monomer in 100% by weight of the polymer contained in the graft portion.
• the graft portion may further contain, as a structural unit, a structural unit derived from a monomer having a reactive group.
• 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 (D), which will be described later, can be chemically bonded in the composition. Thereby, the fine polymer particles (A) can be maintained in a good dispersed state without agglomeration of the fine polymer particles (A) in the 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, (a) 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxy straight-chain alkyl (meth)acrylates; Acrylate (particularly preferably, hydroxy linear C1-6 alkyl (meth)acrylate); (b) caprolactone-modified hydroxy (meth)acrylate; (c) methyl ⁇ -(hydroxymethyl)acrylate, ⁇ -(hydroxymethyl)acryl hydroxy-branched alkyl (meth)acrylates such as ethyl acetate; (d) polyester diols (particularly preferably saturated polyester diols) obtained from dihydric carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol); and hydroxyl group-containing (meth)acrylates such as (meth)acrylates.
• the term “straight-chain C1-6 alkyl” means straight-chain alky
• monomers having a carboxylic acid group include (a) monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and (b) dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. etc.
• monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid
• dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. etc.
• 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 a structural unit derived from a monomer having a reactive group in 100% by weight of the polymer contained in the graft portion. is more preferable, more preferably 2 to 35% by weight, and particularly preferably 3 to 20% by weight.
• the obtained composition has a sufficient (ii) when it contains 90% by weight or less, the resulting composition can provide a cured product having sufficient impact resistance, and the It has the advantage that the composition has good storage stability.
• 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 above-described monomers may be used alone or in combination of two or more.
• 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 graft portion preferably does not contain a functional group Y having reactivity with a functional group X contained in the low-molecular-weight compound (B) described below.
• This configuration has the advantage that the composition has better storage stability.
• the graft portion does not contain a functional group Y reactive with the functional group X contained in the low-molecular-weight compound (B)
• the functional group X contained in the low-molecular-weight compound (B) is In some cases, it is intended that the graft portion does not contain multiple functional groups Y having reactivity with each of the multiple functional groups.
• Functional groups reactive with oxetane groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups and carboxylic acid anhydride groups.
• Functional groups reactive with hydroxyl groups include oxetane groups, epoxy groups, imide groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups.
• Functional groups reactive with epoxy groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups and carboxylic anhydride groups.
• Functional groups reactive with amino groups include oxetane groups, epoxy groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups.
• Functional groups reactive with imide groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups. is mentioned.
• Functional groups reactive with carboxylic acid groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups. etc.
• Functional groups reactive with carboxylic acid anhydride groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanic acid groups. and an ester group.
• Functional groups reactive with cyclic ester groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups. etc.
• Functional groups reactive with cyclic amide groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups. etc.
• a benzoxazine group etc. are mentioned as a functional group which has reactivity with a benzoxazine group.
• Functional groups reactive with cyanate ester groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups and cyanate ester groups. and the like.
• the composition has particularly excellent storage stability. It is also preferable not to include a reactive functional group.
• the grafted portion has a plurality of reactive groups with respect to each of all functional groups possessed by all compounds contained in the low-molecular-weight compound (B). It is preferred not to include all of the species' functional groups.
• a (meth)acryloyl group, a vinyl group, etc. are mentioned as a functional group which has reactivity with a (meth)acryloyl group.
• a benzoxazine group etc. are mentioned as a functional group which has reactivity with an aromatic group.
• Functional groups reactive with nitrile groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, A cyclic amide group, a cyanate ester group, and the like are included.
• Functional groups reactive with carbonyl groups include oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, and carboxylic anhydride groups. , a cyclic ester group, a cyclic amide group and a cyanate ester group.
• 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 -130°C or higher, more preferably -110°C or higher, more preferably -90°C or higher, more preferably -70°C or higher, more preferably -50°C or higher, and -30°C. more preferably -10°C or higher, more preferably 0°C or higher, more preferably 10°C or higher, more preferably 30°C or higher, more preferably 50°C or higher, more preferably 70°C or higher, 90°C 110° C. or higher is particularly preferred.
• 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 part of the fine polymer particles (A) according to one embodiment 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 composition does not become too high.
• the method for calculating the graft ratio is as follows. First, an aqueous latex containing the polymer microparticles (A) is obtained, and then powder particles of the polymer microparticles (A) are obtained from the aqueous latex. Specifically, the method for obtaining the powdery particles of the polymer microparticles (A) from the aqueous latex includes (i) coagulating the polymer microparticles (A) in the aqueous latex, and (ii) obtaining the coagulation A method of dehydrating the substance and (iii) further drying the coagulate to obtain powdery particles of the polymer fine particles (A) can be mentioned.
• MEK methyl ethyl ketone
• (1) to (3) are performed: (1) Using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E), the rotation speed was 30,000 rpm for 1 hour.
• aqueous calcium chloride solution of 0.01 g of calcium chloride dissolved in water is added to the resulting mixture and the resulting mixture is stirred for 1 hour. Thereafter, the resulting mixture is separated into a methanol-soluble portion and a methanol-insoluble portion, and the weight of the methanol-insoluble portion is defined as the free polymer (FP) amount.
• FP free polymer
• 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
• 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 fine polymer particles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous latex, 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 single 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 consists of multiple types of graft portions, not all of these multiple types of graft portions may be graft-bonded to the elastic body.
• the graft portion consists of a plurality of types of graft portions, it is sufficient that at least a portion of at least one type of graft portion is graft-bonded to the elastic body, and the graft portions of other types (a plurality of other types) are It may be grafted to a graft portion that is grafted to the elastic body.
• 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 multistage 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 (a) a composite of multiple types of graft portions, (b) a multi-stage polymerization graft portion and/or (c) 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 polymer fine particles (A) is preferably 0.03 ⁇ m to 50.00 ⁇ m, and is preferably 0.05 ⁇ m, since a highly stable composition having a desired viscosity can be obtained. ⁇ 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, and 0.10 ⁇ m to 0.50 ⁇ m is more preferable. Especially preferred.
• volume-average particle diameter (Mv) of the polymer fine particles (A) is within the above range, there is also the advantage that the polymer fine particles (A) have good dispersibility in other organic components of the composition.
• the "volume average particle diameter (Mv) of the polymer microparticles (A)” is intended to be 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 polymer microparticles (A) can be produced by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Specifically, the polymerization of the elastic body, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface-crosslinked polymer in the fine polymer particles (A) are performed by known methods such as emulsion polymerization, suspension polymerization, It can be carried out by a method such as a microsuspension polymerization method. Among these, the emulsion polymerization method is particularly preferable as the method for producing the polymer fine particles (A).
• composition design of the polymer microparticles (A) is easy, (ii) industrial production of the polymer microparticles (A) is easy, and (iii) the present production method described later It has the advantage that an aqueous latex suitable for use is readily available.
• 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.
• the elastic body can be produced by 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 rubber and (meth)acrylate rubber.
• the elastic body can be produced by polymerizing one or more monomers selected from the group consisting of diene-based monomers and (meth)acrylate-based monomers. 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 contains organosiloxane rubber.
• the elastic body can be produced by polymerizing organosiloxane monomers. 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 produced.
• a multi-stage polymerized elastic body can be obtained by sequentially performing the following steps (1) to (4): (1) elastic body 1 is polymerized to obtain elastic body 1 ; (3) Polymerize elastic 3 in the presence of elastic 1 +2 to obtain three-step elastic 1 +2+3 ; ( 4) Thereafter, following the same procedure, the elastic body n is polymerized in the presence of the elastic body 1+2+...+(n-1) to obtain the multi-stage polymerized elastic body 1+2+...+n .
• 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 latex
• polymerization of the graft portion is carried out by an emulsion polymerization method. is preferred.
• 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 will be described.
• the graft portion 1 1 , the graft portion 2 2 , . (composite) may be produced.
• a multi-stage polymerized graft portion can be obtained by sequentially performing the steps (1) to (4) below: (1) Graft portion 1 is polymerized to obtain graft portion 1 ; (3) then polymerize graft portion 3 in the presence of graft portion 1+2 to obtain three-step graft portion 1 +2+3 ; ( 4) Thereafter, after performing the same procedure, the graft portion n is polymerized in the presence of the graft portion 1+2 + .
• the polymer microparticles (A) may be produced by polymerizing the graft portions having a plurality of types of graft portions and then graft-polymerizing the graft portions onto the elastic body. .
• the polymer microparticles (A) may be produced by sequentially carrying out multistage graft polymerization of a plurality of types of polymers constituting the graft portion to the elastic body in the presence of the elastic body.
• a surface-crosslinked polymer can be formed by polymerizing a monomer used for forming the surface-crosslinked polymer by known radical polymerization in the presence of an arbitrary polymer (for example, an elastic core).
• an arbitrary polymer for example, an elastic core.
• the polymerization of the surface-crosslinked polymer is preferably carried out by an emulsion polymerization method.
• 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 (abbreviated as 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 initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox initiator is used, can be used within a known range.
• 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.
• a water-based latex containing the polymer fine particles (A) can be obtained by the method for producing the polymer fine particles (A) described above. That is, ⁇ 1-2. Method for producing fine polymer particles (A)> can be used as the description of the method for preparing the aqueous latex in the method for producing the present composition.
• Low-molecular weight compound (B) having a molecular weight of less than 1,000 and having one or more polymerizable unsaturated bonds in the molecule Since the low-molecular-weight compound (B) having a molecular weight of less than 1,000 and having one or more polymerizable unsaturated bonds in the molecule (hereinafter also simply referred to as "low-molecular-weight compound (B)") has a low molecular weight, It lowers the viscosity of the composition and improves handling. Further, when the present composition contains the matrix resin (D), upon curing of the present composition, it is copolymerized with the matrix resin (D) and incorporated into the cross-linking points of the cured product.
• the matrix resin (D) upon curing of the present composition, it is copolymerized with the matrix resin (D) and incorporated into the cross-linking points of the cured product.
• (meth)acryloyl group-containing compounds are preferable from the viewpoint of physical properties (toughness, impact resistance, etc.) of the cured product.
• physical properties such as toughness, impact resistance, etc.
• (meth)acryloyl group-containing compounds there are a wide variety of (meth)acryloyl group-containing compounds, and by selecting an appropriate (meth)acryloyl group-containing compound, cured products with various desired physical properties (such as toughness and impact resistance) can be produced. Obtainable.
• the (meth)acryloyl group-containing compound has the advantage of having a faster radical reaction rate than other low-molecular-weight compounds (B) (low-molecular-weight compounds (B) other than (meth)acryloyl-group-containing compounds), and , also has the advantage of being available at a relatively low cost.
• the present inventors have found that a composition containing a (meth)acryloyl group-containing compound as the low molecular compound (B) is , a new finding was obtained that gelation tends to occur more easily during storage.
• the present composition surprisingly exhibits excellent storage stability even when containing a (meth)acryloyl group-containing compound as the low-molecular-weight compound (B).
• the (meth)acryloyl group-containing compound has a reaction rate with the matrix resin (D) described later (when the (meth)acryloyl group-containing compound is copolymerized with the matrix resin (D) and incorporated into the crosslink points of the cured product reaction rate) is close to the reaction rate between the matrix resins (D) (curing rate between the matrix resins (D)).
• the (meth)acryloyl group-containing compound is easily incorporated into the cross-linking points of the matrix resin (D) when the present composition is cured. It has the advantage that it is easy to obtain a cured product with improved physical properties.
• (meth)acryloyl means acryloyl and/or methacryloyl.
• (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
• (meth)acryloyl group-containing compounds a compound having a hydroxyl group is more preferable because addition of an isocyanate compound to the present composition enables modification of the cured product by hybrid curing of radical crosslinking and urethane crosslinking.
• (Meth)acryloyl group-containing compounds having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
• isocyanate compounds added to the composition include diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI).
• MDI diphenylmethane diisocyanate
• HDI hexamethylene diisocyanate
• TDI toluene diisocyanate
• IPDI isophorone diisocyanate
• the low-molecular-weight compound (A) preferably contains 10% by weight or more of the (meth)acryloyl group-containing compound, more preferably 30% by weight or more, and 50% by weight or more, based on 100% by weight of the low-molecular-weight compound (A). It is more preferably contained, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
• the composition has the advantage of being able to provide a cured product with better physical properties (toughness, impact resistance, etc.).
• the molecular weight of the low molecular compound (B) is preferably 750 or less, more preferably less than 750, more preferably 500 or less, more preferably less than 500, and 300 or less. is more preferably less than 300, more preferably 200 or less, and particularly preferably less than 200. As the molecular weight of the low-molecular-weight compound (B) is smaller, there is an advantage that the viscosity-lowering effect of the present composition (viscosity-lowering effect) is enhanced.
• the low-molecular-weight compound (A) comprises an oxetane group, a hydroxyl group, an epoxy group, an amino group, an imide group, a carboxylic acid group, a carboxylic anhydride group, a cyclic ester group, a cyclic amide group, a benzoxazine group, and a cyanate ester group. It preferably contains a compound having at least one functional group X selected from the group consisting of: By including the compound having the functional group X in the low-molecular-weight compound (A), the composition has the advantage of being able to provide a cured product having excellent solvent resistance and mechanical properties.
• Examples of compounds having an oxetane group include (3-ethyloxetan-3-yl)methyl methacrylate and 3-[(allyloxy)methyl]-3-ethyloxetane.
• Examples of compounds having a hydroxyl group include hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.
• Examples of compounds having an epoxy group include glycidyl (meth)acrylate, allyl glycidyl ether, vinyl ethylene oxide, 1,2-epoxy-5-hexene and 1,2-epoxy-9-decene.
• Examples of compounds having an amino group include 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate and (meth)acryloylmorpholine.
• a "cyclic amino group” is also included in the "amino group”.
• Examples of compounds having an imide group include N-(meth)acryloxysuccinimide and the like.
• Examples of compounds having a carboxylic acid group include (meth)acrylic acid and 2-(trifluoromethyl)(meth)acrylic acid.
• Examples of compounds having a carboxylic anhydride group include acrylic anhydride.
• Examples of compounds having a cyclic ester include mevalonic acid lactone methacrylate.
• Examples of compounds having a cyclic amide group include N-vinyl-2-pyrrolidone.
• Examples of compounds having a benzoxazine group include 6-vinyl-2H-1,4-benzoxazin-3(4H)-one.
• Examples of compounds having a cyanate ester group include 2-methacryloyloxyethyl isocyanate.
• the compound having the functional group X contained in the low-molecular-weight compound (A) may further have a functional group other than the functional group X in addition to the functional group X.
• the low-molecular-weight compound (A) may contain (a) a functional group X and a compound having no functional group other than the functional group X, and (b) a functional group X and a functional group other than the functional group X. (c) a compound that does not have a functional group X and has a functional group other than the functional group X, (d ) may contain a compound having a functional group X and a functional group other than the functional group X, and (e) may contain any combination of the above compounds (a) to (d).
• the low-molecular-weight compound (A) preferably contains 10% by weight or more, more preferably 30% by weight or more, and 50% by weight or more of a compound having a functional group X in 100% by weight of the low-molecular-weight compound (A). more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
• the composition has the advantage of being able to provide a cured product with better solvent resistance and mechanical properties.
• the low-molecular-weight compound (A) may contain 100% by weight of a compound having a functional group X in 100% by weight of the low-molecular-weight compound (A). It may be composed only of
• the low-molecular-weight compound (A) preferably contains a total of 10% by weight or more, preferably 30% by weight or more, of the compound having a functional group X and the (meth)acryloyl group-containing compound in 100% by weight of the low-molecular-weight compound (A). More preferably, it contains 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
• the low-molecular-weight compound (A) has a compound having a functional group X and a (meth)acryloyl group-containing compound within the above-mentioned range in total, the composition has solvent resistance and mechanical properties (toughness, impact resistance, etc.). It has the advantage of being able to provide an excellent cured product.
• the "compound containing a functional group X and a (meth)acryloyl group-containing compound” also includes a "compound having a functional group X and a (meth)acryloyl group”.
• radical scavenger (C) scavenges radicals generated during storage of the present composition to form a low-molecular-weight compound (B) polymerization (increase in molecular weight) of the composition, and suppress gelation and viscosity change (increase in viscosity) of the present composition.
• the radical scavenger (C) improves the storage stability of the composition.
• the hindered phenol-based radical scavenger (C) has a radical scavenging power in a mixture of the polymer fine particles (A) and the low-molecular-weight compound (B) as compared with a radical scavenger other than the hindered phenol-based radical scavenger. It showed a surprising effect of being extremely high. Therefore, by containing the radical scavenger (C), the present composition has (a) excellent storage stability, and in particular, gels and It has the advantage of not increasing the viscosity, and (b) the advantage of being excellent in handleability even when used after storage. It can also be said that the radical scavenger (C) is an anti-gelling agent.
• radical scavengers examples include 2,6-di-t-butyl-4-dimethylaminomethylphenol (CAS registration number 88-27-7), 2,6-di-t-butyl - p-cresol (aka “butylated hydroxytoluene", CAS registry number 128-37-0), pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate] (CAS Registry No. 6683-19-8), 2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)mesitylene (CAS Registry No.
• radical scavengers (C) having an electron-donating group at the p-position are preferred because they have high radical scavenger ability and further improve the storage stability of the resulting composition.
• Radical scavengers (C) having an electron-donating group at the p-position include, for example, 2,6-di-t-butyl-4-dimethylaminomethylphenol, 2,6-di-t-butyl-p-cresol , 2,4,6-trimethylphenol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol, 4 -sec-butyl-2,6-di-t-butylphenol and 2,6-di-t-butyl-4-methoxyphenol.
• the radical scavenger (C) preferably does not have an amino group. This configuration has the advantage that discoloration due to storage of the present composition can be prevented.
• the present composition when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (B) is 100% by weight, the polymer fine-particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (B ) is 50 to 99% by weight.
• a mixture containing the polymer fine particles (A) and the low-molecular-weight compound (B) at this content ratio has a suitable viscosity and is excellent in handleability immediately after mixing, but tends to gel during storage, especially after long-term storage. In some cases, there is a problem that the mixture tends to be highly viscous.
• the present composition can maintain a suitable viscosity even after long-term storage as a result of suppressing gelation due to the presence of the radical scavenger (C) in the mixture.
• the polymer fine-particles (A) when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (B) is 100% by weight, the polymer fine-particles (A) are 10 to 50% by weight, and the low-molecular-weight compound (B ) may be from 50 to 90% by weight.
• the content ratio of the fine polymer particles (A) and the low-molecular-weight compound (B) in the present composition is within the above range, there is an advantage that the present composition can be used as a high-concentration masterbatch.
• the polymer fine-particles (A) are 5% by weight to 50% by weight, and the low-molecular-weight compound (B ) is preferably 50% to 95% by weight, more preferably 6% to 50% by weight of the fine polymer particles (A), and 50% to 94% by weight of the low-molecular-weight compound (B).
• the polymer fine particles (A) are 7 wt% to 50 wt%
• the matrix resin (B) is 50 wt% to 93 wt%
• the polymer fine particles (A) are 8 wt% to 50 wt%.
• the low molecular weight compound (B) is 50% to 92% by weight, the polymer fine particle (A) is 9% to 50% by weight, and the low molecular compound (B) is 50% to 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 low-molecular-weight compound (B), and the polymer fine particles (A) is 15 wt% to 50 wt%, the low molecular weight compound (B) is more preferably 50 wt% to 85 wt%, the fine polymer particles (A) is 20 wt% to 50 wt%, the low molecular compound (B ) is more preferably 50 wt% to 80 wt%, the polymer fine particles (A) is 25 wt% to 50 wt%, and the low molecular weight compound (B) is more preferably 50 wt% to 75 wt%.
• the polymer fine particles (A) are 30% by weight to 50% by weight, the low molecular compound (B) is 50% by weight to 70% by weight, and the polymer fine particles (A) are 35% by weight to 50% by weight. More preferably, the content of the low-molecular-weight compound (B) is from 50% to 65% by weight.
• the present composition when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (B) is 100% by weight, the polymer fine-particles (A) are 40% by weight to 50% by weight, and the low-molecular-weight compound (B ) may be 50% to 60% by weight, the fine polymer particles (A) may be 45% to 50% by weight, and the low molecular compound (B) may be 50% to 55% by weight.
• the content ratio of the fine polymer particles (A) and the low-molecular-weight compound (B) in the present composition is within the above range, there is a further advantage that the present composition can be used as a higher-concentration masterbatch.
• the content of the radical scavenger (C) in the present composition is preferably 0.075 parts by weight or more, preferably 0.125 parts by weight or more, relative to 100 parts by weight of the polymer microparticles (A). more preferably 0.200 parts by weight or more, more preferably 0.250 parts by weight or more, more preferably 0.325 parts by weight or more, and 0.375 parts by weight or more more preferably 0.450 parts by weight or more, and particularly preferably 0.500 parts by weight or more.
• the content of the radical scavenger (C) in the present composition is 0.075 parts by weight or more based on 100 parts by weight of the fine polymer particles (A), the storage stability of the composition is further improved. have advantages.
• the upper limit of the content of the radical scavenger (C) in the present composition is not particularly limited, it is preferably 1.500 parts by weight or less with respect to 100 parts by weight of the polymer fine particles (A), and 1.375 parts by weight. It is more preferably 1.250 parts by weight or less, more preferably 1.125 parts by weight or less, more preferably 1.000 parts by weight or less, and 0 It is more preferably 0.875 parts by weight or less, still more preferably 0.750 parts by weight or less, even more preferably 0.625 parts by weight or less, and particularly preferably 0.500 parts by weight or less. preferable.
• the content of the radical scavenger (C) in the present composition is 1.500 parts by weight or less per 100 parts by weight of the fine polymer particles (A), there is an advantage that the curing reaction of the composition is less likely to be inhibited.
• the composition may further contain a matrix resin (D) having two or more polymerizable unsaturated bonds in the molecule (hereinafter also simply referred to as "matrix resin (D)"). Further containing the matrix resin (D) in the present composition has the advantage of improving the strength and toughness of the resulting cured product. In addition, even when the composition contains the matrix resin (D), it can maintain good handleability and storage stability. When the composition contains the matrix resin (D), the composition can also be called a "resin composition".
• the matrix resin (D) in this specification is intended to be a resin having two or more polymerizable unsaturated bonds in the molecule and having a molecular weight of 1,000 or more.
• 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).
• the matrix resin (D) 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)acrylate 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 the 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 the total amount of 100 parts by weight of the matrix resin (D) 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 (D) 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 (D) 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 (D) 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 (D) 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 (D) is more preferably unsaturated polyester or polyester (meth)acrylate. , and that the polymer fine particles (A) are easily dispersed, the matrix resin (D) is particularly preferably polyester (meth)acrylate.
• the matrix resin (D) preferably contains polyether (meth)acrylate or is polyether (meth)acrylate. From the viewpoint of low viscosity and excellent workability, the matrix resin (D) 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 its anhydride may be used in combination with this unsaturated polycarboxylic acid or its anhydride.
• the amount of the unsaturated polycarboxylic acid or its anhydride is preferably at least 30 mol % or more.
• 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.
• Unsaturated polyesters are prepared by combining the polyhydric alcohol and unsaturated polycarboxylic acid or anhydride thereof 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 compounds are also commercially available from Ashland, Reichhold, AOC, etc., for example.
• the number average molecular weight of the unsaturated polyester is not particularly limited, and is preferably 10,000 or less, more preferably 5,000 or less, and particularly preferably 3,000 or less.
• the unsaturated polyester may have a molecular weight of 1,000 or more, and the lower limit of the number average molecular weight of the unsaturated polyester is not particularly limited.
• 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. Alternatively, it can be obtained, for example, by subjecting a hydroxyl group of a polyester obtained by a condensation reaction of a polyhydric carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction with an unsaturated monocarboxylic acid.
• it can be obtained by subjecting a carboxyl group of a polyester obtained by a condensation reaction of a polyhydric carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction of 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 the like, and anhydrides thereof.
• 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 (D) and the water resistance of the cured product.
• polyhydric alcohols 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 thereof include hydrogenated bisphenol A, adducts of bisphenol A and alkylene oxide 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 (D) 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 and the like when performing 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 above reaction may be appropriately set so that the above 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, air or a mixed gas of air and an inert gas such as nitrogen can be used. In this case, it 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 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 10,000 or less, more preferably 5,000 or less, and particularly preferably 3,000 or less.
• the polyester (meth)acrylate has a molecular weight of 1,000 or more, and the lower limit of the number average molecular weight of the polyester (meth)acrylate is not particularly limited.
• 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, reaction conditions, etc. 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 10,000 or less, more preferably 5,000 or less, and particularly preferably 2,500 or less.
• the epoxy (meth)acrylate has a molecular weight of 1,000 or more, and the lower limit of the number average molecular weight of the epoxy (meth)acrylate is not particularly limited.
• 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 examples include polyether polyols, polyester polyols, polybutadiene polyols, adducts of bisphenol A and alkylene oxides such as propylene oxide and ethylene oxide.
• polyether polyol examples include polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, and polyoxymethylene glycol.
• the number average molecular weight of the polyether polyol is not particularly limited, and is preferably 5,000 or less, particularly preferably 3,000 or less.
• the polyether polyol may have a molecular weight of 1,000 or more, and the lower limit of the number average molecular weight of the polyether polyol is not particularly limited.
• the number average molecular weight of the polyester polyol is not particularly limited, and is preferably 5,000 or less, particularly preferably 3,000 or less.
• the polyester polyol may have a molecular weight of 1,000 or more, and the lower limit of the number average molecular weight of the polyester polyol is not particularly limited.
• 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 during the reaction 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, and is preferably 10,000 or less, more preferably 8,000 or less, and particularly preferably 5,000 or less.
• the molecular weight of the urethane (meth)acrylate should be 1,000 or more, and the lower limit of the number average molecular weight of the urethane (meth)acrylate is not particularly limited.
• 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, and is preferably 5000 or less, more preferably 3000 or less.
• the polyether (meth)acrylate may have a molecular weight of 1,000 or more, and the lower limit of the number average molecular weight of the polyether (meth)acrylate is not particularly limited.
• 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, and is preferably 5000 or less, more preferably 3000 or less.
• the molecular weight of the acrylated (meth)acrylate should be 1,000 or more, and the lower limit of the number average molecular weight of the acrylated (meth)acrylate is not particularly limited.
• the properties of the matrix resin (D) are not particularly limited.
• the matrix resin (D) preferably has a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25°C.
• the viscosity of the matrix resin (D) 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 (D) has an advantage of excellent fluidity.
• the matrix resin (D) 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 (D) is 100 mPa ⁇ at 25° C., since the matrix resin (D) 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 1,000 mPa ⁇ s or more, and particularly preferably 1500 mPa ⁇ s or more.
• the matrix resin (D) may have a viscosity of greater than 1,000,000 mPa ⁇ s.
• the matrix resin (D) may be semi-solid (semi-liquid) or solid.
• the matrix resin (D) has a viscosity of more than 1,000,000 mPa ⁇ s, the resulting composition has the advantage of being less sticky and easier to handle.
• the matrix resin (D) preferably has an endothermic peak of 25°C or lower, more preferably 0°C or lower, in a thermogram of differential scanning calorimetry (DSC). According to the above configuration, the matrix resin (D) has an advantage of excellent fluidity.
• the content of the matrix resin (D) in the present composition is preferably 10 parts by weight or more when the total of the fine polymer particles (A) and the low-molecular-weight compound (B) is 100 parts by weight. It is more preferably at least 30 parts by weight, even more preferably at least 50 parts by weight, and particularly preferably at least 70 parts by weight.
• the content of the matrix resin (D) in the present composition is within the above range, there is an advantage that the strength and toughness of the resulting cured product are improved.
• the upper limit of the content of the matrix resin (D) in the present composition is not particularly limited, but from the viewpoint of maintaining excellent handleability and storage stability of the present composition, the polymer fine particles (A) and the low-molecular-weight compound
• the total with (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, and preferably 2,000 parts by weight or less. More preferably, it is 1,000 parts by weight or less, more preferably 750 parts by weight or less, more preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and 100 parts by weight or less. It is more preferably 90 parts by weight or less, still more preferably 80 parts by weight or less, and particularly preferably 70 parts by weight or less.
• the present composition may optionally contain, for example, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (anti-gelling agents), plasticizers, leveling agents, antifoaming agents. , Silane coupling agent, Antistatic agent, Flame retardant, Lubricant, Thickener, Viscosity reducer, Low shrinkage agent, Fiber reinforcement, Inorganic filler, Organic filler, Internal release agent, Wetting agent, Polymerization modifier , a thermoplastic resin, a desiccant, a dispersant, a radical polymerization initiator, a curing accelerator, a co-catalyst, and the like.
• colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (anti-gelling agents), plasticizers, leveling agents, antifoaming agents. , Silane coupling agent, Antistatic agent, Flame retardant, Lubricant, Thickener, Viscosity reducer, Low shrinkage agent,
• the present composition is a composition in which the polymer fine particles (A) are dispersed (preferably in the form of primary particles) in the low-molecular-weight compound (B) in the presence of the radical scavenger (C).
• a method for obtaining the present composition any known method for obtaining a composition in which the polymer fine particles (A) are dispersed in the low-molecular-weight compound (B) (preferably in the form of primary particles) is used. be able to.
• Examples of such a method include, for example, a method of contacting polymer fine particles (A) obtained as an aqueous latex with a low-molecular-weight compound (B), and then removing unnecessary components such as water; is once extracted into an organic solvent, mixed with the low-molecular-weight compound (B), and then the organic solvent is removed.
• a method for producing the present composition it is preferable to use the method described in WO 2005/28546.
• a method for producing a composition according to one embodiment of the present invention comprises mixing an aqueous latex containing polymer fine particles (A) with an organic solvent that exhibits partial solubility in water, and then adding water to the resulting mixture.
• a low molecular weight compound (B) having a saturated bond and a molecular weight of less than 1,000 is mixed with a hindered phenol-based radical scavenger (C), and the polymer fine particles (A) and the low molecular compound (B) are mixed.
• 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 At least one selected from the group consisting of rubbers and organosiloxane-based rubbers, and in the third step, the total amount of the fine polymer particles (A) and the low-molecular-weight compound (B) is 100% by weight.
• the polymer microparticles (A) and the low molecular It may be configured to be mixed with the compound (B).
• the "method for producing a composition according to one embodiment of the present invention” is also simply referred to as “this production method”.
• a “mixture obtained by mixing an aqueous latex containing polymer fine particles (A) with an organic solvent partially soluble in water” is sometimes referred to as “mixture X”.
• this production method has the above configuration, it is possible to provide a composition with excellent storage stability. Since this manufacturing method has the above configuration, it is possible to provide a composition excellent in handleability.
• a method for producing a composition according to an embodiment of the present invention includes [2. composition] can be suitably used for producing the composition described in the section. Therefore, in the method for producing a composition according to one embodiment of the present invention, the polymer fine particles (A), the low-molecular-weight compound (B), the radical scavenger (C), and the optionally added matrix resin (D) and the like are described in [2. Composition] can be used as appropriate.
• Aqueous latex containing polymer microparticles (A) can be an aqueous latex containing polymer microparticles (A) produced by the above-described method for producing polymer microparticles (A).
• the fine polymer particles (A) are preferably produced by emulsion polymerization and obtained as an aqueous latex.
• 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 (mixture) containing 50% by weight or more of methyl ethyl ketone is used as an organic solvent exhibiting partial solubility in water in terms of compatibility with a reactive polymerizable organic compound and availability.
• An organic solvent (mixture) containing more than 75% by weight is particularly preferably used.
• the amount of the organic solvent that exhibits partial solubility in water in the first step is not particularly limited. ) may be set as appropriate depending on the concentration of ).
• the amount of the organic solvent partially soluble in water in the first step may be, for example, 50 to 400 parts by weight with respect to 100 parts by weight of the aqueous latex containing the fine polymer particles (A). It may be up to 300 parts by weight.
• a typical apparatus includes a stirring vessel equipped with stirring blades.
• a mixture X is obtained by mixing an aqueous latex containing fine polymer particles (A) with an organic solvent that exhibits partial solubility in water.
• mixture X is further brought into contact with water. By such contact, part of the organic solvent contained in the mixture X may be dissolved in water to produce an aqueous phase.
• water from the aqueous latex contained in mixture X can also be expelled to the aqueous phase. Therefore, in the mixture obtained by contacting the mixture X with water, the polymer fine particles (A) are concentrated in the organic solvent containing a small amount of water, resulting in the aggregation of the polymer fine particles (A) in the aqueous phase. Aggregates are generated. That is, the aggregate of polymer fine particles (A) obtained in the first step may contain an organic solvent and may contain a small amount of water.
• the amount of water to be brought into contact with the mixture X is not particularly limited. , the type of the organic solvent partially soluble in water, the amount of the organic solvent partially soluble in water, and the like.
• the amount of water used in contact with the mixture X may be, for example, 40 to 350 parts by weight, or 60 to 250 parts by weight, with respect to 100 parts by weight of the organic solvent partially soluble in water. may
• the contact between the mixture X and water should be carried out under stirring or under a fluid state that can impart fluidity equivalent to stirring. is preferred.
• an aqueous latex containing polymer fine particles (A) and an organic solvent exhibiting partial solubility in water are mixed in an apparatus equipped with a stirring function (for example, a stirring vessel equipped with stirring blades).
• a stirring function for example, a stirring vessel equipped with stirring blades.
• water is added to the mixture X obtained in the device, and the mixture X and water are brought into contact with the device.
• the second step by separating the aggregates from the aqueous phase, water contained in the organic solvent that may accompany the aggregates can be removed.
• moisture may include emulsifiers and electrolytes from the manufacturing process of the aqueous latex of polymer microparticles (A). Therefore, by separating the aggregates from the aqueous phase, the emulsifier and electrolyte derived from the production process of the aqueous latex of the polymer fine particles (A), which are contained in the aggregates, are separated from the polymer fine particles (A) together with the aqueous phase. can be removed.
• the apparatus used for separating and recovering the aggregates from the aqueous phase and the method for separating and recovering the aggregates from the aqueous phase are not particularly limited, and known apparatuses and methods are appropriately used. Available. Separability between the aggregates and the aqueous phase is good, and specific embodiments for separating and recovering the aggregates from the aqueous phase include filtering operations using filter paper, filter cloth, and metal screens with relatively large openings. mentioned.
• the following operations may be repeated: (1) separating and recovering aggregates; further water is added to the resulting aggregates to obtain a mixture of aggregates and water; (2) separating and recovering the aggregates from the resulting mixture;
• the first organic solvent dispersion can be obtained in which the polymer fine particles (A) are dispersed in the organic solvent (preferably in the form of substantially primary particles).
• the amount of the organic solvent to be mixed with the aggregates is not particularly limited, and may be appropriately set depending on the type of polymer fine particles (A), the type of organic solvent used, and the like.
• the amount of the organic solvent to be mixed with the aggregate may be, for example, 40 to 1,400 parts by weight or 200 to 1,000 parts by weight with respect to 100 parts by weight of the polymer fine particles (A). .
• organic solvent to be mixed with the aggregates in addition to the above-described organic solvents partially soluble in water, aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, ethylcyclohexane, and mixtures thereof are also used. can. From the viewpoint of ensuring the dispersibility of the polymer fine particles (A) in the aggregates, the same organic solvent that exhibits partial solubility in water used in the first step is used as the organic solvent to be mixed with the aggregates. It is preferred to use one organic solvent.
• the device used for the mixing operation of the aggregate and the organic solvent and the method of the mixing operation are not particularly limited.
• the agglomerate and the organic solvent can be mixed with a general apparatus having a stirring and mixing function (for example, a stirring vessel equipped with stirring blades).
• the present inventor independently obtained the following findings: a first organic solvent dispersion (i.e., a dispersion containing polymer fine particles (A) and an organic solvent) and a low-molecular-weight compound (B) containing radicals
• a first organic solvent dispersion i.e., a dispersion containing polymer fine particles (A) and an organic solvent
• the present production method comprises a first organic solvent dispersion, a low molecular weight compound (B) having a molecular weight of less than 1,000 and having at least one or more polymerizable unsaturated bonds in the molecule, and a hindered phenol-based and a third step of mixing with the radical scavenger (C).
• a second organic solvent dispersion containing the polymer microparticles (A), the low-molecular-weight compound (B) and the hindered phenol-based radical scavenger (C) can be obtained.
• the fine polymer particles (A) are dispersed substantially in the form of primary particles in the organic solvent in the second organic solvent dispersion.
• the amount of the low-molecular-weight compound (B) mixed with the first organic solvent dispersion is set depending on the amount (concentration) of the polymer fine particles (A) in the first organic solvent dispersion.
• the third step when the total amount of the polymer fine particles (A) and the low-molecular weight compound (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, The fine polymer particles (A) and the low-molecular compound (B) are mixed at a mixing ratio of 50 to 99% by weight of the low-molecular compound (B).
• the amount of the radical scavenger (C) mixed with the first organic solvent dispersion is not particularly limited, and the amount (concentration) of the polymer fine particles (A) in the first organic solvent dispersion, and the amount of the low-molecular-weight compound (B) used in the third step.
• the amount of the radical scavenger (C) mixed with the first organic solvent dispersion is the amount of the radical scavenger (C) with respect to 100 parts by weight of the polymer fine particles (A) in the finally obtained composition. is preferably 0.075 parts by weight or more, more preferably 0.125 parts by weight or more, more preferably 0.200 parts by weight or more, and 0.200 parts by weight or more.
• the amount is more preferably 250 parts by weight or more, more preferably 0.325 parts by weight or more, still more preferably 0.375 parts by weight or more, and 0.450 parts by weight. More preferably, the amount is 0.500 parts by weight or more, and particularly preferably 0.500 parts by weight or more.
• the amount of the radical scavenger (C) to be mixed with the first organic solvent dispersion is such that in the finally obtained composition, the radical scavenger (C) is added to 100 parts by weight of the polymer fine particles (A)
• the amount is preferably 1.500 parts by weight or less, more preferably 1.375 parts by weight or less, more preferably 1.250 parts by weight or less, The amount of 1.125 parts by weight or less is more preferable, the amount of 1.000 parts by weight or less is more preferable, the amount of 0.875 parts by weight or less is more preferable, and the amount of 0.875 parts by weight or less is more preferable.
• the amount of 750 parts by weight or less is more preferable, the amount of 0.625 parts by weight or less is even more preferable, and the amount of 0.500 parts by weight or less is particularly preferable.
• the device used for the mixing operation of the first organic solvent dispersion, the low-molecular-weight compound (B) and the radical scavenger (C), the method of the mixing operation, and the order of mixing these are particularly limited. not.
• the first organic solvent dispersion, the low-molecular-weight compound (B), and the radical scavenger (C) are mixed with a device having a general stirring and mixing function (for example, a stirring device equipped with a stirring blade). tank).
• the order of mixing the first organic solvent dispersion, the low-molecular-weight compound (B), and the radical scavenger (C) is not particularly limited.
• the order may be (i) mixing the first organic solvent dispersion and the low-molecular-weight compound (B), mixing the resulting mixture with the radical scavenger (C), and (ii) (iii) the first organic solvent dispersion and the low
• the molecular compound (B) and the radical scavenger (C) may be mixed at the same time.
• the organic solvent is distilled off from the second organic solvent dispersion.
• the polymer fine particles (A) and the low molecular compound (B) containing the polymer fine particles (A), the low molecular compound (B) and the radical scavenger (C) are produced.
• a composition containing 1 to 50% by weight of the fine polymer particles (A) and 50 to 99% by weight of the low-molecular-weight compound (B) can be obtained when the total of the above is 100% by weight.
• the fine polymer particles (A) are dispersed in the low-molecular-weight compound (B) substantially in the form of primary particles in the composition.
• the device used for distilling off the organic solvent from the second organic solvent dispersion and the method for distilling off the organic solvent from the second organic solvent dispersion are not particularly limited and are known.
• can use the apparatus and method of Specific embodiments for distilling off the organic solvent from the second organic solvent dispersion include (a) a method of charging the mixture in a tank and distilling off the organic solvent by heating under reduced pressure; A method of contacting the mixture in a counter current, a continuous method using a thin-film evaporator, a method using an extruder equipped with a devolatilization mechanism or a continuous stirring tank, and the like can be mentioned.
• the organic solvent is removed from the resulting mixture. Distill off.
• a composition is obtained in which the polymer fine particles (A) are dispersed in the form of primary particles in the low-molecular-weight compound (B) and the matrix resin (D) in the presence of the radical scavenger (C). be able to.
• the mixture of the low-molecular-weight compound (B) and the matrix resin (D) is liquid at 23°C, because this facilitates mixing with the second organic solvent dispersion. Furthermore, it is more preferable that the matrix resin (D) 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.
• the present composition contains the matrix resin (D), the cured product obtained by curing the present composition, in other words, the cured product obtained by curing the present composition, the polymer fine particles (A) are primary particles can be uniformly dispersed in the state of A cured product obtained by curing the present composition is also an embodiment of the present invention.
• the present composition can be used for various uses, and those uses are not particularly limited.
• the 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, a binder for rubber chips, a foam chip binder, a casting. It is preferably used for applications such as binders for flooring, bedrock consolidation materials for flooring and ceramics, and urethane foams. Examples of urethane foam include automobile seats, automobile interior parts, sound absorbing materials, damping materials, shock absorbers (shock absorbing materials), heat insulating materials, construction floor material cushions, and the like.
• the present composition is more preferably used as materials such as adhesives, coating materials, binders for reinforcing fibers, composite materials, modeling materials for 3D printers, sealants, and electronic substrates.
• the present composition can be suitably used as a modeling material for 3D printers because it has the advantage of yielding a cured product with high toughness. That is, in one embodiment of the present invention, there is provided a composition for 3D printers (for 3D printing) comprising the present composition.
• the present composition when the present composition is used as a composition for 3D printers, the present composition may be used alone as a composition for 3D printers, and the combination of the present composition and the matrix resin (D) can be used as a 3D printer composition.
• compositions for printers it may be used as a composition for printers, and the present composition, other low-molecular compounds (low-molecular compounds other than the low-molecular compound (B)), other matrix resins (matrix resins other than the matrix resin (D) ) and other ingredients may be used as a composition for 3D printing.
• low-molecular compounds low-molecular compounds other than the low-molecular compound (B)
• matrix resins matrix resins other than the matrix resin (D)
• other ingredients may be used as a composition for 3D printing.
• 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 polymer fine-particles (A) are 1 to 50% by weight
• the low-molecular-weight compound (B) is is 50 to 99% by weight.
• the content of the radical scavenger (C) in the composition is 0.075 parts by weight or more with respect to 100 parts by weight of the polymer fine particles (A) [1] to [3]
• the polymer fine particles (A) when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (B) is 100% by weight, the polymer fine particles (A) are 10 to 50% by weight.
• the elastic body is an elastic core formed by polymerizing at least one monomer selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber; 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.
• the low-molecular-weight compound (B) includes an oxetane group, a hydroxyl group, an epoxy group, an amino group, an imide group, a carboxylic acid group, a carboxylic anhydride group, a cyclic ester group, a cyclic amide group, a benzoxazine group, and a cyanide group. [1] to [7] containing a compound having at least one functional group X selected from the group consisting of an acid ester group, wherein the graft portion does not contain a functional group Y reactive with the functional group X; ].
• the matrix resin (D) 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.
• a composition for a 3D printer comprising the composition according to any one of [1] to [10].
• Aqueous latex containing the polymer microparticles (A) After mixing the aqueous latex containing the polymer microparticles (A) with an organic solvent that exhibits partial solubility in water, the resulting mixture is brought into contact with water to remove the polymer containing the organic solvent.
• 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 polymer fine particles (A) are 1 to 50% by weight, and A method for producing a composition, comprising mixing the polymer fine particles (A) and the low-molecular-weight compound (B) at a mixing ratio of 50 to 99% by weight of the low
• aqueous latex containing fine polymer particles (A)> 1. Polymerization of elastic body Production Example 1-1; Preparation of aqueous latex (R-1) containing elastic body mainly composed of polybutadiene rubber In a pressure-resistant polymerization vessel, deionized water 200 parts by weight, tripotassium phosphate 0.03. 0.002 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.55 parts by weight of sodium dodecylbenzenesulfonate (SDBS) as an emulsifier. bottom.
• EDTA disodium ethylenediaminetetraacetate
• SDBS sodium dodecylbenzenesulfonate
• oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials.
• 100 parts by weight of butadiene (Bd) was charged into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C.
• 0.03 parts by weight of paramenthane hydroperoxide (PHP) was charged into the pressure-resistant polymerization vessel, and then 0.10 parts by weight of sodium formaldehyde sulfoxylate (SFS) was charged into the pressure-resistant polymerization vessel to initiate polymerization. started.
• aqueous latex (R-1) containing an elastic body containing polybutadiene rubber as a main component was obtained.
• the volume average particle size of the elastic body contained in the obtained aqueous latex (R-1) was 90 nm.
• Production Example 1-2 Preparation of water-based latex (R-2) containing elastic body mainly composed of polybutadiene rubber Into a pressure-resistant polymerization vessel, 7 parts by weight of solid content of the water-based latex (R-1) obtained above was added. , 200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA, and 0.001 parts by weight of ferrous sulfate heptahydrate were added. Next, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials.
• a water-based latex (R-2) containing an elastic body composed mainly of polybutadiene rubber was obtained.
• the volume-average particle size of the elastic body contained in the obtained aqueous latex (R-2) was 195 nm.
• a monomer for forming a graft portion (hereinafter also referred to as a graft monomer) (12.1 parts by weight of methyl methacrylate (MMA) and 0.9 parts by weight of butyl acrylate (BA)) and t-butyl hydroperoxide A mixture with 0.035 parts by weight of oxide (BHP) was continuously added into the glass reactor over 80 minutes.
• a latex (L-1) containing fine polymer particles (A) and an emulsifier was obtained.
• the polymerization conversion rate of the monomer component was 96% by weight or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained latex (L-1) was 200 nm.
• the solid content concentration (concentration of fine polymer particles (A)) in the obtained latex (L-1) was 30% by weight with respect to 100% by weight of latex (L-1).
• Latex (L-2) Containing Polymer Microparticles As graft monomers, 10.6 parts by weight of methyl methacrylate (MMA), 0.9 parts by weight of butyl acrylate (BA) and glycidyl methacrylate (GMA)
• MMA methyl methacrylate
• BA butyl acrylate
• GMA glycidyl methacrylate
• a latex (L-2) containing fine polymer particles and an emulsifier was obtained in the same manner as in Production Example 2-1, except that 1.5 parts by weight was used.
• the polymerization conversion rate of the monomer component was 96% by weight or more.
• the volume average particle diameter of the polymer fine particles contained in the obtained latex (L-2) was 196 nm.
• the solid content concentration (concentration of fine polymer particles (B)) in the obtained latex (L-2) was 30% by weight with respect to 100% by weight of latex (L-2).
• Example 1 Production of composition> [Example 1] (First step) A mixing vessel (volume 1 L) equipped with a stirrer was used as an apparatus. In addition, methyl ethyl ketone (MEK) was used as an organic solvent exhibiting partial solubility in water. After the temperature in the mixing tank was adjusted to 30° C., 126 parts by weight of MEK was added to the mixing tank. After that, 143 parts by weight of the latex (L-1) of the fine polymer particles (A) was added to the mixing tank while stirring the MEK in the mixing tank. By uniformly mixing the charged raw materials, a mixture (mixture X) of an aqueous latex containing polymer fine particles (A) and an organic solvent exhibiting partial solubility in water was obtained.
• MEK methyl ethyl ketone
• the third step when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (B) is 100% by weight, the polymer fine-particles (A) are 40% by weight, and the low-molecular-weight compound (B) is The fine polymer particles (A) and the low-molecular-weight compound (B) were mixed at a compounding ratio of 60% by weight.
• composition (A-1) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-1) contained 0.400 parts by weight of the radical scavenger (C) with respect to 100 parts by weight of the fine polymer particles (A).
• Example 2 A composition (A-2) was obtained in the same manner as in Example 1, except that 2,6-di-t-butyl-p-cresol was used as the radical scavenger (C).
• the composition (A-2) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-2) contained 0.400 parts by weight of the radical scavenger (C) with respect to 100 parts by weight of the fine polymer particles (A).
• the composition ( A-3) was obtained.
• the composition (A-3) contains 40% by weight of the polymer particles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-3) contained 0.400 parts by weight of the radical scavenger (C) with respect to 100 parts by weight of the fine polymer particles (A).
• Example 4 In the same manner as in Example 1 except that 2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)mesitylene was used as the radical scavenger (C), A composition (A-4) was obtained.
• the composition (A-4) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-4) contained 0.400 parts by weight of the radical scavenger (C) with respect to 100 parts by weight of the fine polymer particles (A).
• Example 5 A composition (A-5) was obtained in the same manner as in Example 1, except that 2,6-di-t-butyl-4-methoxyphenol was used as the radical scavenger (C).
• the composition (A-5) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-5) contained 0.400 parts by weight of the radical scavenger (C) with respect to 100 parts by weight of the fine polymer particles (A).
• Example 6 Acryloylmorpholine (molecular weight 141) was used as the low-molecular-weight compound (B), and 0.3432 parts by weight of 2,6-di-t-butyl-4-methoxyphenol was used as the radical scavenger (C).
• a composition (A-6) was obtained in the same manner as in Example 1.
• the composition (A-6) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-6) contained 0.800 parts by weight of the radical scavenger (C) with respect to 100 parts by weight of the fine polymer particles (A).
• composition (A-9) was obtained in the same manner as in Example 1, except that no radical scavenger was added.
• the composition (A-9) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• composition (A-10) was obtained in the same manner as in Example 1, except that H-TEMPO (not a hindered phenol radical polymerization scavenger) was used as the radical scavenger.
• the composition (A-10) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• Composition (A-10) contained 0.400 parts by weight of a radical scavenger with respect to 100 parts by weight of fine polymer particles (A).
• composition (A-11) was obtained in the same manner as in Example 1, except that 4-t-butylcatechol (not a hindered phenol radical polymerization scavenger) was used as the radical scavenger.
• the composition (A-11) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-11) contained 0.400 parts by weight of the radical scavenger with respect to 100 parts by weight of the fine polymer particles (A).
• composition (A-12) was obtained in the same manner as in Example 1, except that 4-methoxyphenol (not a hindered phenol radical polymerization scavenger) was used as the radical scavenger.
• the composition (A-12) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (B ) in an amount of 60% by weight.
• the composition (A-12) contained 0.400 parts by weight of the radical scavenger with respect to 100 parts by weight of the fine polymer particles (A).
• Storage stability test The storage stability test was carried out by encapsulating the compositions prepared in Examples and Comparative Examples in a sealed glass container and leaving them in a hot air dryer set at 80°C for 2 days and 7 days, respectively. rice field. As Reference Example 1, the low-molecular-weight compound (B) was similarly subjected to a storage stability test.
• Viscosity change rate (%) ⁇ (Viscosity of composition after storage (V 1 ) ⁇ Viscosity of composition before storage (V 0 ))/Viscosity of composition before storage (V 0 ) ⁇ 100. ⁇ (1)
• the viscosity (V 0 ) of the composition before storage is the viscosity of the composition immediately after being prepared in the above examples and comparative examples.
• the viscosity of the composition after storage (V 1 ) is the viscosity of the composition after standing at 80° C. for 7 days (after 7-day storage stability test).
• a digital viscometer DV-II+Pro type manufactured by BROOKFIELD was used to measure the viscosity of the composition.
• 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 composition was evaluated according to the following criteria based on the rate of change in viscosity, the presence or absence of gelation, and the presence or absence of discoloration. Excellent: The viscosity change rate of the composition after the 7-day storage stability test is 30% or less, and no gelling or discoloration is observed after the 7-day storage stability test. Good: The viscosity change rate of the composition after the 7-day storage stability test is 30% or less, and the composition after the 7-day storage stability test shows no gelation, but discoloration. Poor: The viscosity change rate of the composition after the 7-day storage stability test is greater than 30%, or the composition gels after the 2-day storage stability test or after the 7-day storage stability test.
• compositions of Examples 1 to 6 containing the hindered phenol-based radical scavenger (C) were tested for 7-day storage stability. It did not gel, had a viscosity change rate of 30% or less, and was excellent in storage stability. Furthermore, the compositions of Examples 2 to 6 containing the radical scavenger (C) having no amino group did not discolor after the 7-day storage stability test, and had an appearance immediately after preparation.
• Reference Example 1 containing only the low-molecular-weight compound (B) did not gel after the 2-day storage stability test, but gelled after the 7-day storage stability test.
• the compositions of Comparative Examples 1 to 4 containing no hindered phenol-based radical scavenger (C) either gelled after the 2-day storage stability test, or changed in viscosity after the 7-day storage stability test. The viscosity increased to more than 30%, and the storage stability was inferior to the compositions of Examples 1-4.
• compositions that are storage stable. Therefore, the composition according to one embodiment of the present invention can be particularly suitably used as materials such as adhesives, coating materials, reinforcing fiber binders, composite materials, molding materials for 3D printers, sealants, and electronic substrates. .

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