Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes

Definitions

• the present invention relates to a stress reducing agent and a resin composition.
• Encapsulants containing epoxy resin, silica, etc. are mainly used as encapsulants for semiconductor materials.
• the sealant When the sealant is exposed to heat or light for a long period of time, cracks may occur inside the sealant. Therefore, in order to ensure the long-term reliability of the encapsulant, a method of adding a stress reducing agent to the encapsulant is widely used.
• a graft copolymer may be used as such a stress reducing agent.
• Patent Document 1 describes polyorganosiloxane and poly(meth)alkyl acrylate that were developed for the purpose of reducing the elastic modulus of curable resin compositions and molded objects and improving stress relaxation ability.
• Patent Document 2 discloses a liquid epoxy resin composition for sealing using a graft copolymer having a relatively low rubber content.
• the polymer fine particles disclosed in Patent Document 3 are also graft copolymers.
• the above-mentioned conventional stress-lowering agent has poor (i) dispersibility in matrix resin, and (ii) linear expansion coefficient of a cured product of a resin composition containing the stress-lowering agent and matrix resin. There was room for further improvement from this perspective.
• One aspect of the present invention provides (i) a stress reducing agent that has excellent dispersibility in a matrix resin, and (ii) when a resin composition comprising the stress reducing agent and the matrix resin is cured.
• An object of the present invention is to provide a stress reducing agent capable of providing a cured product having a good coefficient of linear expansion.
• the present inventor has completed the present invention as a result of intensive studies to solve the above problems.
• one embodiment of the present invention includes the following configuration.
• the stress reducing agent according to one embodiment of the present invention is a stress reducing agent containing polymer fine particles (A), wherein the polymer fine particles (A) are attached to an elastic body and to the elastic body.
• the proportion of the elastic body in the polymer fine particles (A) is 70% by weight based on 100% by weight of the polymer fine particles (A).
• the elastic body contains an organosiloxane rubber
• the graft part contains an epoxy group-containing structural unit
• the epoxy group-containing structural unit in the graft part is a rubber-containing graft compound. It is contained in an amount of 0.5% to 4.0% by weight based on 100% by weight of the polymer, and the stress reducing agent is in the form of powder.
• the stress reducing agent according to another embodiment of the present invention is a stress reducing agent containing polymer fine particles (A), wherein the polymer fine particles (A) are composed of an elastic body and the elastic body. a rubber-containing graft copolymer having a graft portion graft-bonded to the body, and the proportion of the elastic body in the polymer fine particles (A) is 100% by weight of the polymer fine particles (A).
• the elastic body contains an organosiloxane rubber
• the graft part contains an epoxy group-containing structural unit
• the epoxy group-containing structural unit in the graft part is It is contained in an amount of 3.3% to 26.7% by weight based on 100% by weight of the graft portion in the rubber-containing graft copolymer, and the stress reducing agent is in the form of powder.
• a resin composition comprising (i) a stress reducing agent with excellent dispersibility in a matrix resin, and (ii) a stress reducing agent and a matrix resin is cured.
• a stress reducing agent that can provide a cured product with a good coefficient of linear expansion.
• a stress reducing agent added to the encapsulant (resin composition) to ensure long-term reliability may be required to have a function of lowering the elastic modulus of the encapsulant.
• a decrease in the elastic modulus of the encapsulant due to the stress reducing agent often causes deterioration in the linear expansion coefficient of the encapsulant. That is, conventionally, there has been a trade-off relationship between reducing the elastic modulus of the encapsulant and maintaining the linear expansion coefficient of the encapsulant (reducing the deterioration of the linear expansion coefficient) by using a stress reducing agent. It was difficult to achieve both. Note that here, when the linear expansion coefficient deteriorates, it is intended that the sealing material expands due to temperature rise, in other words, the linear expansion coefficient increases.
• the present inventor has developed a low-stress method that can provide a cured product that has a low elastic modulus and reduced deterioration of the linear expansion coefficient (in other words, has a good linear expansion coefficient).
• a chemical agent We conducted extensive research to provide a chemical agent.
• diene rubber has been used as the elastic body of the rubber-containing graft copolymer contained in the stress reducing agent.
• the stress reducing agent containing a rubber-containing graft copolymer containing an elastic body containing a diene rubber the effect of reducing the deterioration of the linear expansion coefficient of the cured product due to the epoxy group-containing structural unit in the graft portion was small.
• the effect of reducing the deterioration of the coefficient of linear expansion of the cured product due to the epoxy group-containing structural unit in the graft portion was first observed by the present inventors when an elastic body containing organosiloxane rubber was employed in the process of intensive study. This was a unique effect that could not be easily imagined based on conventional technical common sense.
• the present inventor surprisingly found that when the amount of the epoxy group-containing structural unit contained in the graft portion exceeds a certain amount, the dispersibility of the stress reducing agent in the matrix resin decreases.
• the stress reducing agent may also be required to have dispersibility in the matrix resin. Therefore, the inventors of the present invention have conducted further intensive studies in order to provide a stress-lowering agent that can provide a cured product that has excellent dispersibility in matrix resins, a low modulus of elasticity, and a good coefficient of linear expansion. went.
• an elastic body containing an organosiloxane rubber and an epoxy group-containing structural unit grafted to the elastic body Surprisingly, a stress reducing agent containing fine polymer particles containing a rubber-containing graft copolymer having a graft moiety containing a specific amount of (i) has excellent dispersibility in matrix resin, and ( ii) It is possible to provide a resin composition that can provide a cured product that has a low modulus of elasticity and a good linear expansion coefficient.
• the stress reducing agent is in the form of powder and contains polymer fine particles (A).
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.
• the proportion of the elastic body in the polymer fine particles (A) is more than 70% by weight and 97% by weight or less based on 100% by weight of the polymer fine particles (A), and the elastic body is organosiloxane rubber.
• the graft portion includes an epoxy group-containing structural unit.
• the epoxy group-containing structural unit in the graft portion is contained in an amount of 0.5% to 4.0% by weight based on 100% by weight of the rubber-containing graft copolymer.
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body;
• the proportion of the elastic body in the combined fine particles (A) is more than 70% by weight and 97% by weight or less with respect to 100% by weight of the polymer fine particles (A), and the elastic body contains organosiloxane rubber.
• the graft part contains an epoxy group-containing structural unit, and the epoxy group-containing structural unit in the graft part is 3.3% by weight to 26.7% by weight based on 100% by weight of the graft part in the rubber-containing graft copolymer. Contains % by weight.
• the stress reducing agent according to one embodiment of the present invention may be referred to as “the present stress reducing agent”. Since the present stress reducing agent has the above-mentioned structure, it has the advantage of excellent dispersibility of the polymer fine particles (A) into the matrix resin. In other words, since the present stress reducing agent has the above-mentioned structure, by mixing the stress reducing agent and the matrix resin, it is possible to create a resin composition in which the polymer fine particles (A) are uniformly dispersed in the matrix resin.
• the present stress reducing agent can provide a cured product having a low elastic modulus and a good linear expansion coefficient by curing a resin composition containing the stress reducing agent and a matrix resin.
• the advantage of In this specification “the deterioration of the linear expansion coefficient of the cured product is reduced” may be expressed as "the linear expansion coefficient of the cured product is good.”
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.
• the elastic body includes organosiloxane rubber.
• the stress reducing agent can provide a cured product having a low elastic modulus and a good linear expansion coefficient.
• the resin composition can provide a cured product having sufficient heat resistance and excellent impact resistance at low temperatures.
• the elastic body can also be referred to as an elastic part or rubber particles.
• the organosiloxane rubber is, for example, (a) composed of an alkyl or aryl di-substituted silyloxy unit such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy, etc. (b) organosiloxane polymers composed of alkyl or aryl monosubstituted silyloxy units, such as organohydrogensilyloxy in which some of the alkyls in the side chains are substituted with hydrogen atoms; can be mentioned. These organosiloxane polymers may be used alone or in combination of two or more.
• a cyclic siloxane composed of a plurality of dimethylsilyloxy units may be used as a raw material for organosiloxane rubber.
• the cyclic siloxane include octamethylcyclotetrasiloxane (also known as "D4") having 4 dimethylsilyloxy units, decamethylcyclopentasiloxane (also known as "D5") having 5 dimethylsilyloxy units, and 6 dodecamethylcyclohexasiloxane (also known as "D6”) having two dimethylsilyloxy units, and the like.
• a polymer composed of dimethylsilyloxy units is referred to as dimethylsilyloxy rubber
• a polymer composed of methylphenylsilyloxy units is referred to as methylphenylsilyloxy rubber
• a polymer composed of dimethylsilyloxy units is referred to as methylphenylsilyloxy rubber
• a polymer composed of diphenylsilyloxy units is called dimethylsilyloxy-diphenylsilyloxy rubber.
• organosiloxane rubber (a) dimethylsilyloxy rubber, methyl It is more preferable to use one or more selected from the group consisting of phenylsilyloxy rubber and dimethylsilyloxy-diphenylsilyloxy rubber, and (b) dimethylsilyloxy rubber because it is easily available and economical. It is even more preferable that there be.
• the raw materials include (a) one or more hydrolyzable silyl groups in the molecule, and (b) one or more ethylenically unsaturated groups and/or mercapto groups.
• a monomer hereinafter also referred to as “monomer M”
• the organosiloxane rubber may contain a structural unit derived from monomer M (hereinafter also referred to as “constituent unit M").
• the hydrolyzable silyl group contained in monomer M is not particularly limited.
• the hydrolyzable silyl group include a halogenosilyl group, an acyloxysilyl group, an amidosilyl group, an aminosilyl group, an alkenyloxysilyl group, an aminoxysilyl group, an oximesilyl group, an alkoxysilyl group, a thioalkoxysilyl group, and a silanol group. etc.
• an alkoxysilyl group is more preferable because it has high polymerization reactivity and is easy to handle.
• the monomer M contains two or more hydrolyzable silyl groups in the molecule, the plurality of hydrolyzable silyl groups may be the same or different.
• the monomer M include vinylsilanes such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and tetramethyltetravinylcyclotetrasiloxane; ⁇ -methacryloyloxyethyldimethoxymethylsilane, 3- (meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, 3-(meth)acryloyloxypropylmethoxydimethylsilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, ) Acryloyloxypropyldiethoxymethylsilane, 3-(meth)acryloyloxypropyldiethoxyethylsilane, 3-(meth)acryloyloxypropylethoxyd
• Examples include mercaptoalkylsilanes such as ethoxysilane, 3-mercaptopropyldiethoxymethylsilane, and 3-mercaptopropyldiethoxyethylsilane.
• the monomer M p-vinylphenylmethyldimethoxysilane, 2-(m-vinylphenyl)ethylmethyldimethoxysilane, 1-(m-vinylphenyl)methyldimethylisopropoxysilane, 2-(p-vinylphenyl)ethylmethyldimethoxysilane, -vinylphenyl)ethylmethyldimethoxysilane, 3-(p-vinylphenoxy)propylmethyldiethoxysilane, 3-(p-vinylbenzoyloxy)propylmethyldimethoxysilane, 1-(o-vinylphenyl)-1,1 , 2-trimethyl-2,2-dimethoxydisilane
• the compounds mentioned above as specific examples of (meth)acryloyloxyalkylsilanes are more preferable, such as 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyldimethoxymethyl.
• Silane is more preferred. This configuration has the advantage that the graft portion-forming monomer mixture can be efficiently polymerized in the presence of the organosiloxane rubber.
• the organosiloxane rubber preferably contains 0.001% to 10.0% by weight, and preferably 0.001% to 5.0% by weight of the structural unit M based on 100% by weight of the organosiloxane rubber. More preferably, it is contained in an amount of 0.01% to 5.0% by weight, and particularly preferably 1.0% to 5.0% by weight.
• This configuration has the advantage that the graft portion-forming monomer mixture can be efficiently polymerized in the presence of the organosiloxane rubber.
• the organosiloxane rubber contained in the elastic body may be composed of only one type of polyorganosiloxane rubber having the same composition of constituent units, or two types of polyorganosiloxane rubber having different compositions (types and content ratios) of constituent units. It may be composed of the above polyorganosiloxane.
• the polymer fine particles (A) more preferably contain organosiloxane rubber in an amount of 60% to 100% by weight, and more preferably 70% to 100% by weight, based on 100% by weight of the elastic body contained in the polymeric particles (A). It is more preferable to contain % by weight, more preferably 80 % to 100 % by weight, even more preferably 90 % to 100 % by weight, particularly preferably 95 % to 100 % by weight. According to this configuration, the present stress reducing agent can provide a cured product having a better coefficient of linear expansion.
• the polymer fine particles (A) may contain 100% by weight of organosiloxane rubber in the elastic body contained in the polymer fine particles (A), that is, the elastic body may be composed only of organosiloxane rubber. It's okay.
• the elastic body may contain one or more other rubbers in addition to the organosiloxane rubber described above, as long as the effects of the embodiment of the present invention are not impaired.
• the other rubbers include diene rubber, (meth)acrylate rubber, and natural rubber.
• the total content of the other rubbers is less than 40% by weight, more preferably less than 30% by weight, and more preferably 20% by weight based on 100% by weight of the elastic body contained in the polymer fine particles (A). %, more preferably less than 10% by weight, particularly preferably less than 5% by weight.
• diene rubber examples include butadiene rubber (also referred to as polybutadiene rubber) consisting of structural units derived from 1,3-butadiene, or butadiene-styrene rubber (also referred to as polybutadiene rubber), which is a copolymer of 1,3-butadiene and styrene. Also referred to as polystyrene-butadiene), etc.
• polybutadiene rubber also referred to as polybutadiene rubber
• butadiene-styrene rubber also referred to as polybutadiene rubber
• Examples of the (meth)acrylate rubber include ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber.
• a crosslinked structure can be introduced into the organosiloxane rubber by using a polyfunctional alkoxysilane compound and/or a polyfunctional monomer during the preparation (polymerization) of the organosiloxane rubber. Therefore, the polyfunctional alkoxysilane compound and polyfunctional monomer used in the preparation of organosiloxane rubber can also be said to be a crosslinking agent in organosiloxane rubber.
• polyfunctional alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane (TEOS), tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyl.
• TEOS tetraethoxysilane
• tetraisopropoxysilane tetrabutoxysilane
• tetraoctylsilane methyltrimethoxysilane
• methyltriethoxysilane methyltriethoxysilane
• ethyltriethoxysilane methyl.
• examples include triisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane and dimethyldimethoxysilane.
• a polyfunctional monomer can also be said to be a monomer that has two or more radically polymerizable reactive groups within the same molecule.
• the radically polymerizable reactive group is preferably a carbon-carbon double bond.
• Examples of polyfunctional monomers include (meth)acrylates having ethylenically unsaturated double bonds, such as allyl alkyl (meth) acrylates and allyloxyalkyl (meth) acrylates, but do not include butadiene. 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 cyclohexane. Examples include dimethanol di(meth)acrylate and polyethylene glycol di(meth)acrylates. 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, etc. is exemplified.
• monomers having three (meth)acrylic groups include alkoxylated trimethylolpropane tri(meth)acrylates, glycerolpropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxy Examples include ethyl)isocyanurate tri(meth)acrylate.
• alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, and the like.
• examples of the monomer having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, examples of the monomer having five (meth)acrylic groups include dipentaerythritol penta(meth)acrylate. Furthermore, examples of the monomer having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Examples of the polyfunctional monomer include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.
• 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, It is more preferably 20°C or less, more preferably 10°C or less, more preferably 0°C or less, more preferably -20°C or less, more preferably -40°C or less, more preferably -45°C or less, and more preferably -50°C or less.
• the resulting resin composition containing the stress reducing agent can provide a cured product having excellent toughness.
• the viscosity of the resulting resin composition containing the stress reducing agent can be lowered.
• the Tg of the elastic body can be obtained by measuring viscoelasticity using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) A flat plate made of polymer fine particles (A) is measured using a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Keizai Control Co., Ltd.).
• the peak temperature of tan ⁇ is taken as the glass transition temperature.
• the lowest peak temperature is taken as the glass transition temperature of the elastic body.
• the Tg of the elastic body is lower than 0°C. It is preferably large, more preferably 20°C or higher, even more preferably 50°C or higher, particularly preferably 80°C or higher, and most preferably 120°C or higher.
• the Tg of the elastic body can be determined by the composition of the structural units included in the elastic body. In other words, by changing the composition of the monomers used when producing (polymerizing) the elastic body, the Tg of the resulting elastic body can be adjusted.
• the group of monomers that provides a homopolymer having a Tg larger than 0°C is defined as monomer group a.
• a group of monomers that provides a homopolymer having a Tg of less than 0° C. is referred to as monomer group b. 50 to 100% by weight (more preferably 65 to 99% by weight) of structural units derived from at least one monomer selected from monomer group a, and at least one selected from monomer group b.
• elastic body X 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 is referred to as elastic body X.
• the elastic body X has a Tg greater than 0°C.
• the resulting resin composition containing the stress reducing agent can provide a cured product having sufficient rigidity.
• a crosslinked structure is introduced into the elastic body.
• Examples of the method for introducing the crosslinked structure include the methods described above.
• Examples of monomers that can be included in the monomer group a include, but are not limited to, unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; vinyl substituted compounds such as ⁇ -methylstyrene; Aromatic compounds; ring alkylated vinyl such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, etc.
• Aromatic compounds Ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; Ring halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; 4-acetoxystyrene, etc.
• ring ester substituted vinyl aromatic compounds ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; acenaphthalene , aromatic monomers such as indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; Examples include methacrylic monomers including methacrylic acid derivatives; certain acrylic esters such as isobornyl acrylate and tert-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile; 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- Examples include monomers that can provide a homopolymer having a Tg of 120° C. or higher, such as adamantyl acrylate and 1-adamantyl methacrylate. These monomers a may be used alone or in combination of two or more.
• Examples of the monomer b include ethyl acrylate, butyl acrylate (also known as butyl acrylate), 2-ethylhexyl acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl. Examples include acrylate. 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 more preferably 0.10 ⁇ m to 1.00 ⁇ m. It is more preferably 0.10 ⁇ m to 0.80 ⁇ m, even more preferably 0.10 ⁇ m to 0.50 ⁇ m.
• the volume average particle size of the elastic body is (a) 0.03 ⁇ m or more, an elastic body having a desired volume average particle size can be stably obtained; (b) when it is 50.00 ⁇ m or less, the elastic body can be obtained stably.
• the resulting cured product has good heat resistance and impact resistance.
• the volume average particle diameter of the elastic body can be measured using a dynamic light scattering particle size distribution measuring device or the like using an aqueous latex containing the elastic body as a sample.
• the method for measuring the volume average particle diameter of the elastic body will be described in detail in the Examples below.
• the proportion of the elastic body in the polymer fine particles (A) is preferably more than 70% by weight and not more than 97% by weight, more preferably more than 70% by weight and not more than 95% by weight, with the whole fine polymer particles (A) being 100% by weight. Preferably, more than 70% by weight and 93% by weight or less is more preferable.
• the proportion of the elastic body is more than 70% by weight, the resulting resin composition containing the stress reducing agent can provide a cured product with excellent toughness and impact resistance.
• the proportion of the elastic body is 97% by weight or less, the polymer fine particles (A) do not easily aggregate (do not easily aggregate), so the resulting resin composition containing the stress reducing agent has a high viscosity.
• the resin composition can be easily handled.
• the proportion of the elastic body in the polymer fine particles (A) is more than 70% by weight, the elastic modulus of the cured product can be effectively lowered due to the large proportion of the elastic body, while the graft Due to the small proportion of the powder, the dispersibility of the powder into the matrix resin tended to deteriorate.
• the proportion of the elastic body in the polymer fine particles (A) is more than 70% by weight, the dispersibility in the matrix resin is good and low. It is possible to realize low stress in a cured product of a resin composition containing a stress agent and a matrix resin.
• the elastic body is preferably one that can swell in a suitable solvent but does not substantially dissolve in it.
• the elastic body is preferably insoluble in the matrix resin used.
• the gel content of the elastic body is preferably 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, particularly preferably 95% by weight or more.
• the resulting resin composition containing the stress reducing agent can provide a cured product with excellent toughness.
• the method for calculating gel content is as follows. First, an aqueous latex containing the polymer fine particles (A) is obtained, and then a granular material of the polymer fine particles (A) is obtained from the aqueous latex.
• the method for obtaining powdery particles of polymer fine particles (A) from aqueous latex is not particularly limited, but includes, for example, (i) agglomerating polymer fine particles (A) in the aqueous latex, and (ii) resulting Examples include a method of obtaining granular material of the polymer fine particles (A) by dehydrating the material and (iii) further drying the aggregate.
• MEK methyl ethyl ketone
• the obtained MEK melt is separated into a component soluble in MEK (MEK soluble component) and a component insoluble in MEK (MEK insoluble component).
• MEK soluble component component soluble in MEK
• MEK insoluble component component insoluble in MEK
• the obtained MEK lysate was subjected to centrifugation using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E) at a rotation speed of 30,000 rpm for 1 hour, and the lysate was then Separate into soluble and MEK-insoluble components.
• a centrifuge manufactured by Hitachi Koki Co., Ltd., CP60E
• the weight of the obtained MEK soluble content and MEK insoluble content is measured, and the gel content is calculated from the following formula.
• Gel content (%) (Weight of methyl ethyl ketone insoluble matter)/ ⁇ (Weight of methyl ethyl ketone insoluble matter)+(Weight of methyl ethyl ketone soluble matter) ⁇ 100.
• the "elastic body" of the polymer fine particles (A) may consist of only one type of elastic body having the same constituent unit composition.
• the "elastic body” of the polymer fine particles (A) is one type selected from organosiloxane rubbers.
• the "elastic body" of the polymer fine particles (A) may be composed of multiple types of elastic bodies each having a different composition of constituent units.
• the "elastic body" of the polymer fine particles (A) may be two or more types selected from organosiloxane rubbers, or one type selected from organosiloxane rubbers, diene rubber, and It may also be a mixture with one or more types selected from the other rubbers mentioned above, such as (meth)acrylate rubber.
• the "elastic body" of the polymer fine particles (A) is composed of a plurality of types of elastic bodies each having a different composition of constituent units.
• the plurality of types of elastic bodies are respectively referred to as elastic body 1 , elastic body 2 , . . . , and elastic body n .
• n is an integer of 2 or more.
• the "elastic body” of the polymer fine particles (A) may include a composite of separately polymerized elastic body 1 , elastic body 2 , . . . , and elastic body n .
• the "elastic body" of the polymer fine particles (A) may include one elastic body obtained by polymerizing each of elastic body 1 , elastic body 2 , . . . , and elastic body n in order.
• the process of sequentially polymerizing a plurality of elastic bodies (polymers) in this manner is also referred to as multistage polymerization.
• One elastic body obtained by multistage polymerization of multiple types of elastic bodies is also referred to as a multistage polymerized elastic body. The method for producing the multistage polymerized elastic body will be described in detail later.
• a multistage polymerized elastic body consisting of elastic body 1 , elastic body 2 , . . . , and elastic body n will be explained.
• the elastic body n may cover at least a portion of the elastic body n-1 , or may cover the entire elastic body n-1 .
• a part of the elastic body n may enter inside the elastic body n-1 .
• each of the plurality of elastic bodies may form a layered structure.
• elastic body 1 forms the innermost layer
• a layer of elastic body 2 is formed outside of elastic body 1
• An aspect in which the layer of elastic body 3 is formed as the outermost layer of the elastic body outside the layer of elastic body 2 is also one aspect of the present invention.
• a multistage polymerized elastic body in which each of a plurality of elastic bodies forms a layered structure can also be called a multilayer elastic body.
• the "elastic body" of the polymer fine particles (A) is (a) a composite of multiple types of elastic bodies, (b) a multistage polymerized elastic body, and/or (c) a multilayer elastic body. May include the body.
• the polymer grafted to the elastic body is referred to as a graft portion.
• the polymer fine particles (A) include a rubber-containing graft copolymer having the elastic body and a graft portion grafted to the elastic body.
• the graft portion can play various roles. "Various roles" include, for example, (a) improving the compatibility between the matrix resin and the polymer fine particles (A), and (b) improving the dispersibility of the polymer fine particles (A) in the matrix resin. and (c) enabling the polymer fine particles (A) to be dispersed in the state of primary particles in the resulting resin composition containing the stress reducing agent or in the cured product.
• the graft portion includes, as a structural unit, an epoxy group-containing structural unit, in other words, a structural unit having an epoxy group.
• an epoxy group-containing structural unit such as glycidyl methacrylate
• the stress-lowering agent has the advantage of being able to provide a cured product with a better coefficient of linear expansion.
• a graft part containing an epoxy group-containing structural unit can be obtained by using (polymerizing) a mixture containing a monomer having an epoxy group (monomer mixture for forming a graft part). .
• monomers having epoxy groups include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether. These may be used alone or in combination of two or more. Glycidyl methacrylate is more preferred as the monomer having an epoxy group because it is easily available and economical.
• the graft portion preferably contains 0.5% to 4.0% by weight, and 0.6% to 3.8% by weight of the epoxy group-containing structural unit based on 100% by weight of the rubber-containing graft copolymer. It is more preferable to contain 0.7 wt % to 3.5 wt %, more preferably 0.8 wt % to 3.3 wt %, and 0.8 wt % or more.3. The content is more preferably less than 2% by weight, even more preferably 0.9% to 3.0% by weight, and particularly preferably 1.0% to less than 3.0% by weight.
• the coefficient of linear expansion of the cured product is significantly reduced, that is, the stress-lowering agent has the advantage of being able to provide a cured product with a better coefficient of linear expansion.
• the stressing agent has the advantage that it has excellent dispersibility in the matrix resin. There is.
• the graft portion contains 3.3% to 26.7% by weight of an epoxy group-containing structural unit as a structural unit based on 100% by weight of all the structural units of the grafted portion in the rubber-containing graft copolymer. preferably 4.0% to 25.0% by weight, even more preferably 5.0% to 22.0% by weight, and even more preferably 6.0% to 20.0% by weight. It is particularly preferable.
• the stress-lowering agent has the advantage of being able to provide a cured product with a better coefficient of linear expansion.
• the stressing agent has the advantage that it has excellent dispersibility in the matrix resin. There is.
• the graft portion contains an epoxy group-containing structural unit within the above range based on 100% by weight of the rubber-containing graft copolymer, and contains 100% by weight of the total structural units of the graft portion in the rubber-containing graft copolymer.
• the graft portion contains, as a structural unit, an aromatic vinyl monomer that does not contain an epoxy group, a vinyl cyan monomer that does not contain an epoxy group, and a (meta) monomer that does not contain an epoxy group, as a structural unit that does not contain an epoxy group. It may contain a structural unit derived from one or more monomers selected from the group consisting of acrylate monomers.
• the above-mentioned one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers may be used alone; You may use combinations of more than one species.
• the graft portion contains, as a structural unit, a structural unit derived from an aromatic vinyl monomer that does not contain an epoxy group, a structural unit that originates from a vinyl cyan monomer that does not contain an epoxy group, and a (meta) that does not contain an epoxy group.
• the total content of structural units derived from acrylate monomers is preferably 10 to 97% by weight, more preferably 30 to 96% by weight, and more preferably 50 to 95% by weight, based on 100% by weight of all structural units of the graft portion. It is more preferable to contain it by weight%, particularly preferably from 60 to 94% by weight, and most preferably from 70 to 94% by weight.
• the graft portion may contain, as a structural unit, a structural unit derived from a monomer having a reactive group other than an epoxy group.
• monomers having reactive groups other than epoxy groups include oxetane groups, hydroxyl groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic esters, cyclic amides, benzoxazine groups, and cyanogen groups. Examples include monomers having acid ester groups and the like.
• the graft portion may include a structural unit derived from a polyfunctional monomer as a structural unit.
• a structural unit derived from a polyfunctional monomer swelling of the polymer fine particles (A) can be prevented in the resulting resin composition containing the stress reducing agent;
• the resulting stress-lowering agent is included, compared to when the graft part contains a structural unit derived from a polyfunctional monomer.
• the resin composition can provide a cured product with better toughness and impact resistance.
• polyfunctional monomer are the same as those explained in the section (Crosslinked structure of elastic body) above, so the description is incorporated and the explanation is omitted here.
• the graft portion may contain structural units derived from other monomers.
• 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 or lower.
• °C or less more preferably 50 °C or less, more preferably 40 °C or less, more preferably 30 °C or less, more preferably 20 °C or less, more preferably 10 °C or less, more preferably 0 °C or less, -20 °C or less °C or less, more preferably -40°C or less, more preferably -45°C or less, more preferably -50°C or less, more preferably -55°C or less, more preferably -60°C or less, -65°C or less is more preferable, -70°C or below is more preferable, -75°C or below is more preferable, -80°C or below is more preferable, -85°C or below is more preferable, -90°C or below is more preferable, -95°C or below is more preferable.
• the temperature is preferably -100°C or lower, more preferably -105°C or lower, more preferably -110°C or lower, more preferably -115°C or lower, even more preferably -120°C or lower, particularly preferably -125°C or lower.
• the glass transition temperature of the graft portion is preferably 0°C or higher, more preferably 30°C or higher, more preferably 50°C or higher, even more preferably 70°C or higher, even more preferably 90°C or higher, and particularly preferably 110°C or lower. preferable.
• the Tg of the graft portion can be determined by the composition of the structural units contained in the graft portion. In other words, by changing the composition of the monomers used when producing (polymerizing) the graft part, the Tg of the resulting graft part can be adjusted.
• the highest peak temperature is determined by selecting the highest peak temperature of the graft portion. Glass transition temperature.
• the polymer fine particles (A) are polymers having the same structure as the graft portion, and may include a polymer that is not grafted to the elastic body.
• a polymer having the same structure as the graft portion and not grafted to the elastic body is also referred to as a non-grafted polymer.
• the non-grafted 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 grafted to the elastic body that is, the proportion of the graft part, among the polymers produced in the graft part preparation step, is referred to as the graft ratio.
• the graft ratio can also be said to be a value expressed by (weight of grafted part)/ ⁇ (weight of grafted part)+(weight of non-grafted polymer) ⁇ 100.
• soluble components may also be present in addition to the graft portion and the non-grafted polymer.
• This soluble content is intended to be auxiliary raw materials such as unpolymerized monomers and initiators.
• Examples of methods for determining whether it is a graft copolymer (A), a non-graft polymer, or a soluble component include a method of determining whether it is soluble or insoluble in a solvent. For example, (i) graft copolymer (A) if insoluble in MEK, (ii) non-graft copolymer (A) if soluble in MEK and insoluble in methanol, (iii) non-graft copolymer (A) if soluble in MEK. , and if it is soluble in methanol, it is determined to be a soluble content.
• 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 resulting resin composition containing the stress reducing agent does not become too high.
• the polymer fine particles (A) and the non-grafted polymer can be separated using a solvent, but in this specification, the non-grafted polymer is also referred to as the polymer according to an embodiment of the present invention. It constitutes a part of the fine particles (A).
• the "weight of the polymer fine particles (A)” refers to the weight of the polymer fine particles (A), which is the MEK-insoluble content, The total weight of the MEK soluble portion and the methanol insoluble portion of the non-grafted polymer is intended.
• the weight of the polymer in the graft section is the amount of monomers that constitute the polymer in the graft section.
• the method of coagulating the polymer fine particles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous latex, etc. may be used.
• the graft portion may consist of only one type of graft portion having constitutional units of the same composition.
• the graft portion may be composed of multiple types of graft portions each having a different composition of structural units.
• the graft portion is composed of multiple types of graft portions.
• each of the plurality of types of graft parts is referred to as graft part 1 , graft part 2 , . . . , graft part n (n is an integer of 2 or more).
• the graft portion may include a composite of graft portion 1 , graft portion 2 , . . . , and graft portion n , each of which is polymerized separately.
• the graft part may include one polymer obtained by multistage polymerization of graft part 1 , graft part 2 , . . . , and graft part n .
• a polymer obtained by multistage polymerization of multiple types of graft parts is also referred to as a multistage polymerization graft part.
• the method for producing the multistage polymerization graft portion will be described in detail later.
• the graft portion is composed of multiple types of graft portions, all of these multiple types of graft portions do not need to be grafted to the elastic body. It is sufficient that at least a part of at least one type of graft part is grafted to the elastic body, and the other types of graft parts (other types) are graft parts grafted to the elastic body. may be grafted to.
• the graft portion is composed of multiple types of graft portions, it is a polymer having the same structure as the multiple types of graft portions, and is not grafted to the elastic body (multiple types of non-polymer types). (graft polymer).
• a multistage polymerization graft section consisting of graft section 1 , graft section 2 , . . . , and graft section n will be explained.
• the graft section n may cover at least a portion of the graft section n-1 or may cover the entire graft section n-1 .
• a part of the graft section n may enter inside the graft section n-1 .
• each of the plurality of graft sections may form a layered structure.
• graft section 1 forms the innermost layer in the graft section
• a layer of graft section 2 is formed outside graft section 1 .
• the layer of the graft section 3 is formed as the outermost layer outside the layer of the graft section 2 is also an embodiment of the present invention.
• a multistage polymerization graft section in which each of the plurality of graft sections forms a layered structure can also be called a multilayer graft section.
• the graft portion may include (a) a mixture of multiple types of graft portions, (b) a multistage polymerization graft portion, and/or (c) a multilayer graft portion.
• the elastic body and the graft portion are polymerized in this order in the production of the polymer fine particles (A)
• at least a portion of the graft portion can cover at least a portion of the elastic body in the obtained polymer fine particles (A).
• the polymer fine particles (A) obtained by multistage polymerization of an elastic body and a graft portion can also be called a multistage polymer.
• the graft portion may cover at least a portion of the elastic body or may cover the entire elastic body.
• the polymer fine particles (A) are a multistage polymer, a part of the graft portion may enter inside the elastic body.
• 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 a 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 the elastic body is the core layer and the graft portion is the shell layer can also be called a core-shell structure.
• the polymer particles (A) in which the elastic body and the graft portion form a layered structure (core-shell structure) can also be said to be a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particles (A) may be a multistage polymer, and/or a multilayer polymer or a core-shell polymer. However, as long as the graft portion is graft-bonded to the elastic body, the polymer fine particles (A) are not limited to the above configuration.
• At least a portion of the graft portion covers at least a portion of the elastic body.
• at least a portion of the graft portion is preferably present on the outermost side of the polymer fine particles (A).
• the rubber-containing graft copolymer may further include a surface crosslinked polymer.
• the rubber-containing graft copolymer further contains a surface crosslinked polymer, blocking resistance can be improved in the production of polymer fine particles (A), and (b) the resulting stress-lowering agent-containing resin In the composition, there is an advantage that the dispersibility of the polymer fine particles (A) in the matrix resin becomes better.
• the rubber-containing graft copolymer when the rubber-containing graft copolymer further contains a surface crosslinked polymer, it may also have the following effects: (a) the effect of reducing the viscosity of the resulting resin composition containing the stress-lowering agent; (b) the elasticity (c) the effect of increasing the crosslink density in the body; and (c) the effect of increasing the grafting efficiency of the graft section.
• the crosslinking density in an elastic body means the number of crosslinked structures in the entire elastic body.
• the surface crosslinked polymer contains, as structural units, 30% to 100% by weight of structural units derived from polyfunctional monomers and 0% to 70% by weight of structural units derived from other vinyl monomers. %, total 100% by weight.
• polyfunctional monomer are the same as those explained in the section (Crosslinked structure of elastic body) above, so the description is incorporated and the explanation is omitted here.
• the volume average particle diameter (Mv) of the polymer fine particles (A) is preferably 0.03 ⁇ m to 50.00 ⁇ m, and 0.03 ⁇ m to 50.00 ⁇ m, since it is possible to obtain a highly stable resin composition having a desired viscosity. More preferably 05 ⁇ m to 10.00 ⁇ m, more preferably 0.08 ⁇ m to 2.00 ⁇ m, even more preferably 0.10 ⁇ m to 1.00 ⁇ m, even more preferably 0.10 ⁇ m to 0.80 ⁇ m, and even more preferably 0.10 ⁇ m to 0.50 ⁇ m. is particularly preferred.
• the volume average particle diameter (Mv) of the polymer fine particles (A) is intended to mean the volume average particle diameter of the primary particles of the polymer fine particles (A), unless otherwise specified. do.
• the volume average particle diameter of the polymer fine particles (A) can be measured using a dynamic light scattering particle size distribution measuring device or the like using an aqueous latex containing the polymer fine particles (A) as a sample.
• the volume average particle diameter of the polymer fine particles (A) will be described in detail in the Examples below.
• the volume average particle diameter of the polymer fine particles (A) is measured by cutting the cured product of the resin composition, imaging the cut surface using an electron microscope, etc., and using the obtained imaging data (imaged image). You can also do that.
• the number distribution of the volume average particle size of the polymer fine particles (A) in the matrix resin is set to be 0.5 times or more and 1 time or less of the volume average particle size, since a resin composition with low viscosity and easy to handle is obtained. It is preferable to have a price range.
• the polymer fine particles (A) can be produced by polymerizing an elastic body and then graft-polymerizing a polymer constituting the graft portion to the elastic body in the presence of the elastic body.
• the polymer fine particles (A) can be produced by a known method, for example, an emulsion polymerization method, a suspension polymerization method, a microsuspension polymerization method, or the like.
• the polymerization of the elastic body, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface crosslinked polymer in the polymer fine particles (A) can be carried out using known methods such as emulsion polymerization, suspension polymerization, This can be carried out by a method such as a microsuspension polymerization method.
• the emulsion polymerization method is particularly preferred as a method for producing the polymer fine particles (A).
• compositional design of the polymer fine particles (A) is easy
• industrial production of the polymer fine particles (A) is easy
• the resin composition described below It has the advantage that an aqueous latex of polymer fine particles (A) that can be suitably used for the production of is easily obtained.
• a method for producing an elastic body, a graft portion, and a surface crosslinked polymer having an arbitrary structure that may be included in the polymer fine particles (A) will be described.
• the method for preparing the organosiloxane rubber is not particularly limited, and any known emulsion polymerization method can be used.
• a specific example of a method for preparing an organosiloxane rubber is a method in which an organosiloxane and the monomer M are subjected to emulsion polymerization in the presence of an acidic emulsifier.
• raw organosiloxanes used in the preparation of organosiloxane rubber include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Various organosiloxane-based cyclic bodies having three or more members such as dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetradecamethylcycloheptasiloxane, and dimethylcyclics (mixture of dimethylsiloxane cyclic oligomers 3-7mers) are used. preferable.
• the acidic emulsifier is not particularly limited, but when an organosiloxane cyclic body is used, it is preferably one that can open the organosiloxane cyclic body.
• Preferred examples of acidic emulsifiers include dodecylbenzenesulfonic acid.
• the amount of the acidic emulsifier used is not particularly limited, and depends on (a) the desired volume average particle diameter of the organosiloxane rubber and polymer fine particles (A), and (b) the solid content (monomer mixture) concentration in the reaction solution. , (c) polymerization conditions such as polymerization temperature, and (d) whether or not additives such as surfactants are used and the amount used.
• the volume average particle diameter of the resulting organosiloxane rubber can be controlled by (a) the degree of preliminary dispersion of the raw materials, (b) the amount of emulsifier used, (c) the polymerization temperature, and (d) the method of supplying the raw materials.
• organosiloxane rubber When organosiloxane rubber is obtained by emulsion polymerization carried out in the presence of an acidic emulsifier, the resulting aqueous latex is strongly acidic, so it is preferable to neutralize it after the polymerization reaction is completed.
• the basic compound used for neutralization is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, ammonia, triethylamine, and the like.
• the aqueous latex can be neutralized by adding these basic compounds directly or in the form of an aqueous solution to the aqueous latex containing the organosiloxane rubber.
• organosiloxane rubber for example, the method described in WO2006/070664 can also be used.
• the elastic body contains at least one member selected from the group consisting of diene rubber and (meth)acrylate rubber
• these elastic bodies can be subjected to emulsion polymerization, suspension polymerization, microsuspension polymerization, etc.
• the manufacturing method for example, the method described in WO2005/028546 can be used.
• the graft portion can be formed, for example, by polymerizing monomers used for forming the graft portion by known radical polymerization.
• the polymerization of the graft portion is preferably carried out by an emulsion polymerization method.
• the graft portion can be manufactured, for example, according to the method described in WO2005/028546.
• the graft portion having multiple types of graft portions may be polymerized, and then the graft portions may be graft-polymerized to an elastic body to produce the polymer fine particles (A).
• Polymer fine particles (A) may be produced by successively performing multi-stage graft polymerization of a plurality of types of polymers constituting the graft portion onto the elastic body in the presence of the elastic body.
• a known emulsifier (dispersant) can be used.
• emulsifiers include anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, polyacrylic acid derivatives, and the like.
• anionic emulsifier include sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosic acid-based emulsifiers, and carboxylic acid-based emulsifiers.
• sulfur emulsifier include sodium dodecylbenzenesulfonate (abbreviation: SDBS).
• examples of the phosphorus emulsifier include polyoxyethylene lauryl ether sodium phosphate.
• thermal decomposition type initiator When employing an emulsion polymerization method as a method for preparing diene rubber and (meth)acrylate rubber and/or a method for preparing a graft portion, a thermal decomposition type initiator can be used.
• the thermal decomposition type initiator may be a known initiator such as (a) 2,2'-azobisisobutyronitrile, and (b) peroxides such as organic peroxides and inorganic peroxides. Agents can be mentioned.
• the organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-butyl peroxide. Examples include hexyl peroxide. Examples of the inorganic peroxide include hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like.
• a redox type initiator When employing an emulsion polymerization method as a method for preparing diene rubber and (meth)acrylate rubber and/or a method for preparing a graft portion, a redox type initiator can also be used.
• the redox type initiator includes (a) peroxides such as organic peroxides and inorganic peroxides, and (b) transition metal salts such as iron (II) sulfate, sodium formaldehyde sulfoxylate, glucose, etc. This is an initiator used in combination with a reducing agent. Further, if necessary, a chelating agent such as disodium ethylenediaminetetraacetate, and a phosphorus-containing compound such as sodium pyrophosphate may be used in combination.
• a redox type initiator When a redox type 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 within a wide range. Therefore, it is preferable to use a redox type initiator.
• redox type 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 when a redox type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent, etc. used can be within known ranges.
• a known chain transfer agent can be used in a known amount.
• a chain transfer agent By using a chain transfer agent, the molecular weight and/or degree of crosslinking of the resulting elastic body, graft portion, or surface crosslinked polymer can be easily adjusted.
• a surfactant can be used in the production of the polymer fine particles (A).
• the type and amount of the surfactant used are within known ranges.
• the present stress reducing agent may further contain a resin (B) in addition to the polymer fine particles (A). Since the present stress reducing agent contains the resin (B), it has the advantage that the dispersibility of the polymer fine particles (A) in the matrix resin is better.
• the resin (B) may be, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin.
• thermosetting resin in resin (B) is not particularly limited, but includes resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenol resins, polyol resins, and amino-formaldehyde resins. It is preferable to include at least one selected from the group.
• examples of the thermosetting resin in the resin (B) include resins containing polymers obtained by polymerizing aromatic polyester raw materials. In the resin (B), only one type of thermosetting resin may be used, or two or more types may be used in combination.
• Epoxy resin The epoxy resin is not particularly limited as long as it has at least one epoxy group in its molecule.
• epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, and novolak epoxy resin. , glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, rubber modified epoxy resin containing polybutadiene or NBR, glycidyl ether of tetrabromobisphenol A, etc.
• flame-retardant epoxy resins examples include glycidyl ethers of alcohols, hydantoin-type epoxy resins, epoxidized products of unsaturated polymers such as petroleum resins, and aminoglycidyl ether-containing resins.
• Examples of the polyhydric alcohol include N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, and glycerin.
• Examples of the epoxy resin include epoxy compounds obtained by adding bisphenols A (or F) or polybasic acids to the epoxy resin described above. The epoxy resin is not limited to these, and commonly used epoxy resins may be used. These epoxy resins may be used alone or in combination of two or more.
• epoxy resins those having at least two epoxy groups in one molecule are preferred because they have high reactivity in curing the resin composition and the resulting cured product can easily form a three-dimensional network.
• epoxy resins having at least two epoxy groups in one molecule epoxy resins containing bisphenol type epoxy resins as a main component are preferred because they are economical and easily available.
• thermoplastic resin in the resin (B) examples include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes, and polyvinyl acetates. These may be used alone or in combination of two or more.
• the resin (B) may be the same resin (resin having the same composition) as the matrix resin to be mixed, which will be described later, or may be a resin different from the matrix resin. In the resin composition, it is preferable that the matrix resin and the resin (B) do not undergo phase separation.
• the resin (B) is preferably a resin that is compatible with the matrix resin.
• the resin (B) is the same resin as the matrix resin to be mixed which will be described later, the resin (B) does not affect various physical properties of the resulting resin composition or cured product containing the stress reducing agent. It has the advantage of not being
• the resulting resin composition containing the stress reducing agent appears to contain only the resin (B) or only the matrix resin in addition to the polymer fine particles (A).
• the resin (B) is a different type of resin from the matrix resin.
• the matrix resin and the resin (B) can be distinguished.
• the finally obtained resin composition containing the stress reducing agent may contain, in addition to the polymer fine particles (A), the resin (B) as a resin other than the matrix resin.
• oils and oils and fatty acid esters are also included in resin (B).
• oils and fats that can be suitably used as the resin (B) include epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil.
• epoxidized soybean oil commercially available products can be used, such as ADEKAISER O-130P manufactured by ADEKA.
• fatty acid esters that can be suitably used as the resin (B) include epoxidized fatty acid esters such as epoxidized butyl fatty acid, epoxidized fatty acid 2-ethylhexyl, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester. It will be done.
• Epoxidized fats and oils and epoxidized fatty acid esters are sometimes referred to as epoxy plasticizers. That is, in this specification, an epoxy plasticizer is also included in the resin (B).
• epoxy plasticizers other than epoxidized fats and oils and epoxidized fatty acid esters include diepoxystearyl epoxyhexahydrophthalate and di2-ethylhexyl epoxyhexahydrophthalate.
• thermosetting resins thermoplastic resins, mixtures of thermosetting resins and thermoplastic resins, oils and fats, and fatty acid esters can be used in combination with an antioxidant.
• the antioxidant is considered to be part of the resin (B) only when used in combination with each of the above-mentioned substances. When only an antioxidant is used, the antioxidant is not considered resin (B). A case where only an antioxidant is used instead of resin (B) will be explained.
• the antioxidant is a component that does not contribute to crosslinking
• the final product i.e., the final product; for example, if the matrix resin is a thermosetting resin
• the physical properties of the cured product tend to be poor.
• the Tg of the final product may be lowered or the impact resistance may be poor.
• the antioxidant is not particularly limited.
• examples of antioxidants include (a) primary antioxidants such as phenolic antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants, and (b) sulfur antioxidants. and secondary antioxidants such as phosphorus-based antioxidants.
• antioxidant other conventionally known substances may be used.
• antioxidants include the "Antioxidant Handbook” published by Taiseisha (first edition published October 25, 1976), and the “Polymer Additives Handbook” published by CMC Publishing (edited and written by Toru Haruna, November 2010). You may use various substances described in, for example, the 1st edition published on the 7th.
• Resin (B) is a thermosetting resin, a mixture of a thermosetting resin and an antioxidant, a thermoplastic resin, a mixture of a thermoplastic resin and an antioxidant, an oil or fat, a mixture of an oil or fat and an antioxidant, or a fatty acid. It is preferably one or more selected from the group consisting of esters, mixtures of fatty acid esters and antioxidants, epoxy hardeners, and mixtures of epoxy hardeners and antioxidants, and epoxy resins, acrylic heavy one or more selected from the group consisting of a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy plasticizer and an antioxidant.
• the resulting resin composition containing the stress reducing agent can provide a cured product with excellent heat resistance, and (b) improves the dispersibility of the polymer fine particles (A) in the matrix resin. It has the advantage of being able to
• resin (B) Other properties of the resin (B) are not particularly limited as long as it is a liquid, semi-solid, or solid having a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25°C.
• the resin (B) has a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25°C means "the resin (B) has a viscosity of 100 mPa ⁇ s at 25°C It is intended to have a viscosity of ⁇ 1,000,000 mPa ⁇ s.
• the viscosity of the resin (B) is preferably 750,000 mPa ⁇ s or less at 25°C. According to the above configuration, the stress reducing agent has an advantage of excellent fluidity.
• the viscosity of the resin (B) at 25° C. is more preferably 200 mPa ⁇ s or more, and more preferably 300 mPa ⁇ s or more. According to this configuration, the resin (B) is not impregnated into the polymer fine particles (A), but can enter between the plurality of polymer fine particles (A) and remain near the surface of the polymer fine particles (A). As a result, the resin (B) can prevent the polymer particles (A) from fusing together.
• the viscosity of the resin (B) at 25° C. is more preferably 100 mPa ⁇ s to 750,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 700,000 mPa ⁇ s, and more preferably 100 mPa ⁇ s to 350,000 mPa ⁇ s. , more preferably from 100 mPa ⁇ s to 300,000 mPa ⁇ s, more preferably from 100 mPa ⁇ s to 50,000 mPa ⁇ s, even more preferably from 100 mPa ⁇ s to 30,000 mPa ⁇ s, and from 100 mPa ⁇ s to 15,000 mPa ⁇ s. Particularly preferred.
• the resin (B) is semi-solid at 25°C, it can also be said that the resin (B) is semi-liquid at 25°C, and the resin (B) has a viscosity greater than 1,000,000 mPa ⁇ s at 25°C. It can be said that they are doing so.
• the resin (B) is semi-solid or solid at 25° C., the resulting resin composition containing the stress reducing agent has the advantage of being less sticky and easier to handle.
• the content of the resin (B) in the stress reducing agent is such that the content of the polymer fine particles (A) is 50 to 99% when the total of the polymer fine particles (A) and the resin (B) is 100% by weight.
• the amount of the resin (B) is 1 to 50% by weight.
• the content of the resin (B) should be determined depending on the type of resin (B) and the physical properties of the resin (B) (solid, semi-solid, liquid , viscosity, etc.).
• the stress reducing agent may not be obtained.
• the resin (B) is a liquid at 25° C. and the content of the resin (B) in the stress reducing agent is large, there is a possibility that the fluidity (smooth feel) of the stress reducing agent may be deteriorated.
• the content of the resin (B) in the stress reducing agent will be explained from the viewpoint of excellent blocking resistance.
• the polymer fine particles (A) account for 55 to 99 weight%
• the resin (B) accounts for 1 to 45 weight%.
• the polymer fine particles (A) be 60 to 99 weight %, and the resin (B) be 1 to 40 weight %, and the polymer fine particles (A) be 65 to 99 weight %, and the resin ( B) is more preferably 1 to 35% by weight, polymer fine particles (A) is 70 to 99% by weight, resin (B) is 1 to 30% by weight, and polymer fine particles (A) are more preferably 1 to 35% by weight.
• ) is more preferably 75 to 99% by weight, resin (B) is more preferably 1 to 25% by weight, polymer fine particles (A) is 80 to 99% by weight, and resin (B) is 1 to 20% by weight.
• the polymer fine particles (A) be 85 to 99 weight %, and the resin (B) be 1 to 15 weight %, and the polymer fine particles (A) be 90 to 99 weight %, and the resin ( It is even more preferable that B) be 1 to 10% by weight, particularly preferably 95 to 99% by weight of polymer fine particles (A), and 1 to 5% by weight of resin (B).
• the content of the resin (B) in the stress reducing agent will be explained from the viewpoint that the dispersibility of the polymer fine particles (A) in the matrix resin is improved.
• the polymer particles (A) should be 50 to 97% by weight and the resin (B) should be 3 to 50% by weight.
• the polymer fine particles (A) is 50 to 95% by weight, and the resin (B) is more preferably 50 to 50% by weight, and the polymer fine particles (A) is 50 to 92% by weight, and the resin (B) is 50 to 92% by weight.
• the polymer fine particles (A) are 50 to 82 weight %, and the resin (B) is more preferably 18 to 50 weight %, and the polymer fine particles (A) are 50 to 80 weight %, and the resin (B) is 50 to 82 weight %. It is even more preferably 20 to 50% by weight, and particularly preferably 60 to 80% by weight of the polymer fine particles (A) and 20 to 40% by weight of the resin (B).
• the stress reducing agent further includes an antiblocking agent. According to this configuration, the stress reducing agent obtained has (a) excellent blocking resistance, and (b) excellent dispersibility of the polymer fine particles (A) in the matrix resin.
• the antiblocking agent is not particularly limited as long as it exhibits the effects of one embodiment of the present invention.
• antiblocking agents include blocking agents made of inorganic fine particles such as silicon dioxide, titanium oxide, aluminum oxide, zirconium oxide, aluminum silicate, diatomaceous earth, zeolite, kaolin, talc, calcium carbonate, calcium phosphate, barium sulfate, and magnesium hydrosilicate.
• Inhibitor Antiblocking agent made of organic fine particles; Examples include oil-based antiblocking agents such as polyethylene wax, higher fatty acid amide, metal soap, and silicone oil. Among these, antiblocking agents made of fine particles are preferred, and antiblocking agents made of organic fine particles are more preferred.
• the antiblocking agent made of organic fine particles has a structure derived from one or more monomers selected from aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers as structural units. Particularly preferred is an antiblocking agent made of organic fine particles of a polymer containing units.
• the antiblocking agent made of fine particles is generally one in which fine particles are dispersed in a liquid or in the form of a colloid.
• the fine particles in the antiblocking agent have a volume average particle diameter (Mv) of usually 10 ⁇ m or less, preferably 0.05 ⁇ m to 10.00 ⁇ m.
• Mv volume average particle diameter
• the content of the anti-blocking agent is preferably 0.01% to 5.00% by weight, and 0.50% to 3.00% by weight based on the total weight (100% by weight) of the stress reducing agent. More preferred.
• the stress reducing agent may contain other optional components other than the above-mentioned components, if necessary.
• Other optional components include various components described in the section (4-4. Other optional components) below.
• the antiblocking agent and other optional components can be added as appropriate during any step in the method for producing the stress reducing agent.
• the antiblocking agent and other optional components may be added to an aqueous suspension (aqueous latex) of the polymer fine particles (A) or the polymer fine particles (A) and the resin (B) before or after coagulation. Can be added.
• a stress reducing agent containing polymer fine particles (A), resin (B), or polymer fine particles (A) and resin (B) can also be added.
• the method for producing the stress reducing agent is not particularly limited.
• an example of a method for producing a stress reducing agent will be described, taking as an example a case where the stress reducing agent contains polymer fine particles (A) and a resin (B).
• resin (B) is not used in the following manufacturing method, it is possible to obtain a stress reducing agent that contains polymer fine particles (A) and does not contain resin (B).
• a method for producing a stress reducing agent includes a resin (B) addition step of adding resin (B) to aqueous latex containing polymer fine particles (A), and using the obtained aqueous latex.
• the method includes an aggregation step of preparing an aggregate containing the polymer fine particles (A) and the resin (B), and a recovery step of recovering the aggregate.
• aggregation “coagulation” and “coagulation” each have the same meaning and are interchangeable.
• the resin (B) addition step is a step of obtaining an aqueous latex containing polymer fine particles (A) and resin (B).
• the resin (B) addition step can also be said to be a step of mixing the polymer particles (A) and the resin (B).
• the specific method of adding the resin (B) to the aqueous latex containing the polymer fine particles (A) is not particularly limited, and the resin (B) is directly added to the aqueous latex containing the polymer fine particles (A). Examples include a method of adding in an aqueous emulsion state and a method of adding in a solution state.
• the resin (B) is preferably added in the form of an aqueous emulsion to the aqueous latex containing the polymer fine particles (A).
• the aggregation step is a step for aggregating the polymer particles (A) in the aqueous latex together with the resin (B).
• an aggregate containing the polymer fine particles (A) and the resin (B) can be obtained.
• the method of coagulating the polymer fine particles (A) with the resin (B) is not particularly limited, but includes, for example, a method using a solvent, a method using a flocculant (also referred to as a coagulant and a coagulant), a method using a coagulant (also referred to as a coagulant and a coagulant), and a method using a polymer fine particle.
• a method such as spraying an aqueous latex containing (A) and resin (B) may be used.
• the aggregation step preferably includes a step of preparing an agglomerate containing the polymer fine particles (A) and the resin (B) using a coagulant.
• a step of preparing an agglomerate containing the polymer fine particles (A) and the resin (B) using a coagulant since there is no need to use a solvent, it is possible to obtain a powder or granular material for a thermosetting resin that has a small environmental load. Moreover, according to the configuration, a special facility for spraying is not required, and therefore powder for thermosetting resin can be easily obtained.
• the recovery step is a step in which water in the aqueous latex is removed to obtain aggregates containing polymer fine particles (A) and resin (B).
• the recovery step can also be referred to as a step of separating aggregates containing the polymer particles (A) and resin (B) from the water component from the aqueous latex.
• the water component is a mixture that has water as its main component, but also contains an emulsifier, non-agglomerated polymer fine particles (A), resin (B), and the like.
• the method for collecting the aggregate containing the polymer fine particles (A) and the resin (B) is not particularly limited, and examples thereof include methods such as filtration and centrifugation.
• the aggregate obtained through the resin (B) addition step, aggregation step, and recovery step described above can be used as a stress reducing agent.
• the method for producing a stress reducing agent may further include a washing step.
• the washing step is a step of washing the aggregate containing the polymer fine particles (A) and the resin (B) obtained in the recovery step.
• a powder or granular material for a thermosetting resin with a low content of impurities etc. can be obtained.
• the washing step may be any step of washing the aggregates, and the specific method is not particularly limited.
• a method of mixing aggregates and water and stirring with a stirrer a method of kneading the aggregates and water using a kneader, a method of mixing aggregates and water with a rotation-revolution mixer, a method of mixing water into aggregates, Methods such as a method of spraying and a method of washing the cake with a pressure filter can be mentioned.
• Various types of kneaders can be used, such as batch kneaders, continuous kneaders, extrusion kneaders, and extruders.
• the object to be cleaned is intended to be all impurities contained in the aggregate, and is not particularly limited.
• impurities derived from emulsifiers e.g., phosphorus emulsifiers, sulfonic acid emulsifiers
• a flocculant described below impurities derived from the flocculant, etc. can be mentioned.
• emulsifiers include (a) anionic emulsifiers such as acids, alkali metal salts of the acids, or ammonium salts of the acids listed below, and (b) nonionic emulsifiers such as alkyl- or aryl-substituted polyethylene glycols. Examples include emulsifiers, (c) polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, polyacrylic acid derivatives, and the like.
• acids examples include (a1) alkyl or aryl sulfonic acids such as dioctyl sulfosuccinic acid and dodecylbenzenesulfonic acid, or alkyl or aryl ether sulfonic acids, and (a2) alkyl or aryl sulfuric acids such as dodecyl sulfuric acid.
• alkyl or aryl ether sulfuric acid (a3) alkyl or aryl substituted phosphoric acid, or alkyl or aryl ether substituted phosphoric acid, (a4) N-alkyl or aryl sarcosinic acid represented by dodecyl sarcosinic acid, (a5) Examples include alkyl or aryl carboxylic acids such as oleic acid and stearic acid, or alkyl or aryl ether carboxylic acids.
• the anionic emulsifier formed from the acids described in (a1) and (a2) above is referred to as a sulfur-based emulsifier
• the anionic emulsifier formed from the acids described in (a3) above is referred to as a phosphorus-based emulsifier
• An anionic emulsifier formed from the acids described in (a4) above is referred to as a sarcosic acid emulsifier
• an anionic emulsifier formed from the acids described in (a5) above is referred to as a carboxylic acid emulsifier.
• These emulsifiers may be used alone or in combination of two or more.
• the method for producing a stress reducing agent may further include a drying step.
• a stress reducing agent in the form of powder or granules can be obtained.
• the drying step is a step of drying the aggregate containing the polymer fine particles (A) and the resin (B) obtained in the collection step or the washing step to obtain powder.
• the method of drying the aggregates is not particularly limited, and examples include a method of drying the aggregates using a dryer, a method of placing the aggregates in a container and heating and depressurizing the inside of the container, and a method of preparing the aggregates in a container. Examples include a method of bringing the dry gas and the aggregate into countercurrent contact within the container.
• Resin composition A resin composition containing the above-described stress reducing agent and matrix resin is also an embodiment of the present invention. "The resin composition according to one embodiment of the present invention” may be hereinafter referred to as “the present resin composition.” According to the present stress reducing agent, by adding it to the matrix resin, it is possible to lower the elastic modulus of the matrix resin and to reduce deterioration of the coefficient of linear expansion.
• the matrix resin is not particularly limited, and includes, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin.
• thermosetting resins such as epoxy resins, phenol resins, polyimide resins, oxetane resins, and thermoplastic resins such as polycarbonate resins are more preferred.
• the thermosetting resin and thermoplastic resin may be the same as the thermosetting resin and thermoplastic resin described in the section (2-2. Resin (B)).
• the matrix resin is preferably an epoxy resin.
• the epoxy resin may be the same as the epoxy resin described in section (2-2. Resin (B)).
• As the epoxy resin an epoxy resin may be used alone, or an epoxy resin and one or more matrix resins other than the epoxy resin may be used in combination.
• the properties of the matrix resin are not particularly limited.
• the matrix resin preferably has a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25°C.
• the viscosity of the matrix resin at 25° C. is more preferably 50,000 mPa ⁇ s or less, even more preferably 30,000 mPa ⁇ s or less, and particularly preferably 15,000 mPa ⁇ s or less.
• the matrix resin has an advantage of excellent fluidity.
• a matrix resin having a viscosity of 100 mPa ⁇ s to 1,000,000 mPa ⁇ s at 25° C. can also be said to be a liquid.
• the polymer fine particles (A) having the above-mentioned structure are well dispersed in a matrix resin having a viscosity of 1,000,000 mPa ⁇ s or less at 25°C. It has the advantage of being
• the viscosity of the matrix resin is 100 mPa ⁇ s or more at 25° C. because the matrix resin enters into the polymer particles (A) and can prevent the polymer particles (A) from fusing with each other. It is more preferable that it is 500 mPa ⁇ s or more, even more preferably that it is 1000 mPa ⁇ s or more, and it is particularly preferable that it is 1500 mPa ⁇ s or more.
• the viscosity of the matrix resin at 25°C is more preferably 100 mPa ⁇ s to 750,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 700,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 350,000 mPa ⁇ s, and 100 mPa ⁇ s to 750,000 mPa ⁇ s. ⁇ s ⁇ 300,000 mPa s is more preferred, 100 mPa s ⁇ 50,000 mPa s is more preferred, 100 mPa s ⁇ 30,000 mPa s is even more preferred, and 100 mPa s ⁇ 15,000 mPa s is particularly preferred .
• the matrix resin may have a viscosity greater than 1,000,000 mPa ⁇ s.
• the matrix resin may be semi-solid (semi-liquid) or solid.
• the resulting resin composition containing powder has the advantage of being less sticky and easier to handle.
• the matrix resin preferably has an endothermic peak of 25°C or less in a differential scanning calorimetry (DSC) thermogram, and more preferably has an endothermic peak of 0°C or less. According to the above configuration, the matrix resin has an advantage of excellent fluidity.
• the blending ratio of the stress reducing agent and matrix resin is usually 0.5 to 50% by weight for the stress reducing agent and 50% by weight for the matrix resin when the total of the stress reducing agent and matrix resin is 100% by weight. It is preferable that the stress reducing agent is 1 to 40 weight %, and the matrix resin is 60 to 99 weight %, and the stress reducing agent is 1 to 25 weight %, and the matrix resin is 1 to 25 weight %. More preferably, the resin content is 75 to 99% by weight, the stress reducing agent is 2.5 to 20% by weight, and the matrix resin is particularly preferably 80 to 97.5% by weight.
• the blending ratio of the stress reducing agent and the matrix resin is determined by adjusting the blending ratio of the (a) powder to the matrix resin in order to set the content ratio of the polymer fine particles (A) and the matrix resin in the resulting resin composition to a desired value. It can be appropriately set depending on the content and moisture content of components other than the polymer fine particles (A) contained in the granules, the method of mixing the (b) stress reducing agent and the matrix resin, and the like.
• the content ratio of the polymer fine particles (A) and the matrix resin in the resin composition is usually determined when the total of the polymer fine particles (A) and the matrix resin is 100% by weight.
• ) is preferably 0.5 to 50% by weight
• the matrix resin is preferably 50 to 99.5% by weight
• the polymer fine particles (A) is preferably 1 to 40% by weight
• the matrix resin is 60 to 99% by weight.
• the polymer fine particles (A) are 1 to 25% by weight
• the matrix resin is 75 to 99% by weight
• the polymer fine particles (A) are 2.5 to 20% by weight
• the matrix resin is 2.5 to 20% by weight.
• Particularly preferred is 80 to 97.5% by weight.
• the state of the matrix resin is not particularly limited as long as it flows when mixed with the stress reducing agent, and it may be solid at room temperature, but from the viewpoint of workability, it may be in a liquid state. preferable.
• the temperature at which the stress reducing agent and matrix resin are mixed is generally set to a temperature at which the matrix resin can flow.
• a temperature at which the matrix resin can flow Regarding the temperature, if the resin (B) in the powder can flow at a temperature at which the matrix resin can flow, it becomes easy to uniformly mix the resin (B) and the matrix resin.
• the present resin composition contains a thermosetting resin as a matrix resin
• a cured product can be obtained by curing the resin composition.
• the present resin composition contains a thermoplastic resin as a matrix resin
• a molded article can be obtained by molding the resin composition.
• a cured product obtained by curing the present resin composition and a molded article obtained by molding the present resin composition are also embodiments of the present invention.
• the present resin composition may further contain a known thermosetting resin other than the matrix resin, or may further contain a known thermoplastic resin.
• the resin composition may contain other optional components other than the components described above, as necessary.
• the present resin composition preferably contains silica as an inorganic filler.
• silica may be used alone, or silica and one or more other arbitrary components other than silica may be used in combination.
• Other optional components include, for example, curing agents, coloring agents such as pigments and dyes, extender pigments, pigment dispersants, ultraviolet absorbers, the above-mentioned antioxidants, heat stabilizers (gelling inhibitors), and plasticizers.
• leveling agent leveling agent, antifoaming agent, silane coupling agent, antistatic agent, flame retardant, lubricant, thinner, viscosity modifier, thixotropic agent, low shrinkage agent, inorganic filler, organic filler, thermoplastic resin , desiccants, dispersants, thermal conductivity improvers, water binders, anti-sagging agents, anti-color separation agents, anti-settling agents, coating wear control agents, surface conditioners, monobasic organic acids, camphor, castor oil, etc. Can be mentioned.
• a method for producing a resin composition according to an embodiment of the present invention includes a step of mixing a stress reducing agent containing polymer fine particles (A), a thermosetting resin, and an inorganic filler. This is a method for producing a composition.
• the stress reducing agent containing the polymer fine particles (A) is as described in [3. It can be manufactured by the manufacturing method described in the section ⁇ Method for manufacturing stress reducing agent''.
• the method for producing the resin composition is particularly limited as long as it includes a step of mixing a stress reducing agent containing polymer fine particles (A), a thermosetting resin, and an inorganic filler.
• a stress reducing agent containing polymer fine particles (A) a thermosetting resin
• an inorganic filler and, if necessary, other optional components mentioned above may be added to the resulting mixture and mixed using a mixer or the like.
• the order in which the stress reducing agent, thermosetting resin, inorganic filler, and other optional components are added is not limited to the above-mentioned order, and may be in any order.
• the method for producing a resin composition according to an embodiment of the present invention more preferably includes a step of mixing a stress reducing agent containing polymer fine particles (A), an epoxy resin, and silica.
• This is a method for producing a resin composition.
• the production method which includes a step of mixing a stress reducing agent containing polymer fine particles (A), an epoxy resin, and silica
• the stress reducing agent, epoxy resin, silica, and other optional components are mixed.
• the addition order may be any order, but for example, after mixing the stress reducing agent and the epoxy resin, silica and, if necessary, the other mentioned above are added to the resulting mixture.
• a method of adding optional components and mixing them using a mixer or the like can be mentioned.
• the sealing material according to one embodiment of the present invention is made using the stress reducing agent or resin composition described above. Since the sealing material according to one embodiment of the present invention has the above configuration, it has the advantage of being excellent in toughness and impact resistance.
• the sealing material according to one embodiment of the present invention is also simply referred to as the main sealing material.
• Apps of the present encapsulant include, but are not particularly limited to, encapsulants for various electrical devices such as semiconductors and power devices.
• the present sealing material can be manufactured using a stress reducing agent or a resin composition.
• the method for manufacturing the present sealing material is not particularly limited, and any known method can be used.
• One embodiment of the present invention includes the following configuration.
• the proportion of the elastic body containing the graft copolymer in the polymer fine particles (A) is more than 70% by weight and 97% by weight or less based on 100% by weight of the polymer fine particles (A), and
• the elastic body includes an organosiloxane rubber, the graft portion includes an epoxy group-containing structural unit, and the epoxy group-containing structural unit in the graft portion is 0.0% by weight based on 100% by weight of the rubber-containing graft copolymer.
• the epoxy group-containing structural unit in the graft portion is contained in an amount of 3.3% to 26.7% by weight based on 100% by weight of the grafted portion in the rubber-containing graft copolymer, according to [1].
• Low stress agent Low stress agent.
• the proportion of the elastic body containing the graft copolymer in the polymer fine particles (A) is more than 70% by weight and 97% by weight or less based on 100% by weight of the polymer fine particles (A), and
• the elastic body contains an organosiloxane rubber, the graft part contains an epoxy group-containing structural unit, and the epoxy group-containing structural unit in the graft part is based on 100% by weight of the graft part in the rubber-containing graft copolymer. , 3.3% to 26.7% by weight, and the stress reducing agent is in the form of powder or granules.
• a resin composition comprising the stress reducing agent according to any one of [1] to [5], a thermosetting resin, and an inorganic filler.
• thermosetting resin is an epoxy resin
• inorganic filler is silica
• a sealing material comprising the resin composition according to [6].
• a sealing material comprising the resin composition according to [7].
• a method for producing a resin composition comprising a step of mixing a stress reducing agent containing polymer fine particles (A), a thermosetting resin, and an inorganic filler, the method comprising: (A) includes a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, and the proportion of the elastic body in the polymer fine particles (A) is , with respect to 100% by weight of the polymer fine particles (A), more than 70% by weight and not more than 97% by weight, the elastic body contains an organosiloxane rubber, and the graft portion contains an epoxy group-containing structural unit, The epoxy group-containing structural unit in the graft portion is contained in an amount of 0.5% to 4.0% by weight based on 100% by weight of the rubber-containing graft copolymer, and the stress reducing agent is in the form of powder.
• a method for producing a resin composition comprising a step of mixing a stress reducing agent containing polymer fine particles (A), a thermo
• the epoxy group-containing structural unit in the graft portion is contained in an amount of 3.3% to 26.7% by weight based on 100% by weight of the grafted portion in the rubber-containing graft copolymer, according to [10].
• a method for producing a resin composition is produced.
• a method for producing a resin composition comprising a step of mixing a stress reducing agent containing polymer fine particles (A), a thermosetting resin, and an inorganic filler, the method comprising: (A) includes a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, and the proportion of the elastic body in the polymer fine particles (A) is , with respect to 100% by weight of the polymer fine particles (A), more than 70% by weight and not more than 97% by weight, the elastic body contains an organosiloxane rubber, and the graft portion contains an epoxy group-containing structural unit, The epoxy group-containing structural unit in the graft portion is contained in an amount of 3.3% to 26.7% by weight based on 100% by weight of the grafted portion in the rubber-containing graft copolymer, and the stress reducing agent is contained in a powder or granule.
• a method for producing a resin composition comprising a step of mixing a stress reducing agent
• thermosetting resin is an epoxy resin and the inorganic filler is silica.
• the volume average particle diameter (Mv) of the elastic body (elastic core layer) and polymer fine particles (A) dispersed in the aqueous latex was measured using Nanotrac Wave II-EX150 (manufactured by Microtrac Bell Co., Ltd.). Aqueous latex diluted with deionized water was used as a measurement sample. The measurement was performed by inputting the refractive index of water, each elastic body, and the polymer fine particles, measuring time 120 seconds, and adjusting the sample concentration so that the loading index was within the range of 1 to 10.
• the resin composition was placed on a grind meter (grind gauge), the resin composition on the gauge was scraped off with a metal scraper, and the dispersion state was visually confirmed.
• the scale was read at the position where 5 to 10 points of granular marks produced by the movement of the scraper were generated in a 3 mm wide band, and the time until the scale reached 0 ⁇ m was measured. The results are shown in Table 1.
• the obtained liquid mixture was stirred for 5 minutes at 10,000 rpm using a homomixer to prepare an emulsion.
• the obtained emulsion was charged all at once into a 5-necked glass container.
• the glass vessel had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and addition ports for monomers and emulsifiers.
• DSA dodecylbenzenesulfonic acid
• aqueous latex (R-1) containing an elastic body mainly composed of organosiloxane rubber was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the elastic body containing organosiloxane rubber as a main component contained in the obtained aqueous latex was 280 nm.
• aqueous latex (R-1) of organosiloxane rubber including 85 parts by weight of an elastic material whose main component is polyorganosiloxane rubber
• deionized water Into a glass reactor, 180 parts by weight of aqueous latex (R-1) of organosiloxane rubber (including 85 parts by weight of an elastic material whose main component is polyorganosiloxane rubber) and 43 parts by weight of deionized water were charged.
• the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. While replacing the gas in the glass reactor with nitrogen, the raw materials introduced were stirred at 60°C.
• 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.11 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes.
• MMA methyl methacrylate
• BA butyl acrylate
• BHP t-butyl hydroperoxide
• Production Example 1-2 Preparation of aqueous latex (L-2) containing polymer fine particles (A)
• Production Example 1-1 instead of the mixture of 14.25 parts by weight of MMA, 0.75 parts by weight of BA and 0.04 parts by weight of t-butyl hydroperoxide (BHP), 13.5 parts by weight of MMA and 0.75 parts by weight of BA were used.
• Polymer fine particles (A) were prepared in the same manner as in Production Example 1-1, except that a mixture of 0.75 parts by weight of glycidyl methacrylate (GMA) and 0.04 parts by weight of t-butyl hydroperoxide (BHP) was used.
• An aqueous latex (L-2) was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer particles (A) contained in the obtained aqueous latex was 292 nm.
• Production Example 1-3 Preparation of aqueous latex (L-3) containing polymer fine particles (A)
• Production Example 1-1 instead of the mixture of 14.25 parts by weight of MMA, 0.75 parts by weight of BA and 0.04 parts by weight of t-butyl hydroperoxide (BHP), 12.75 parts by weight of MMA and 0.75 parts by weight of BA were used.
• An aqueous latex (L -3) was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 290 nm.
• Production Example 1-4 Preparation of aqueous latex (L-4) containing polymer fine particles (A)
• Production Example 1-1 instead of the mixture of 14.25 parts by weight of MMA, 0.75 parts by weight of BA and 0.04 parts by weight of t-butyl hydroperoxide (BHP), 10.75 parts by weight of MMA and 0.75 parts by weight of BA were used.
• An aqueous latex (L -4) was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 291 nm.
• Production Example 1-5 Preparation of aqueous latex (L-5) containing polymer fine particles (A)
• Production Example 1-1 instead of the mixture of 14.25 parts by weight of MMA, 0.75 parts by weight of BA and 0.04 parts by weight of t-butyl hydroperoxide (BHP), 9.75 parts by weight of MMA and 0.75 parts by weight of BA were used.
• An aqueous latex (L -5) was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer particles (A) contained in the obtained aqueous latex was 292 nm.
• each of PHP, EDTA, and ferrous sulfate heptahydrate was added in arbitrary amounts and at arbitrary times into the pressure-resistant polymerization vessel.
• an aqueous latex (R-2) containing an elastic body (core layer) containing polybutadiene rubber as a main component was obtained.
• the volume average particle diameter of the elastic body (core layer) contained in the obtained aqueous latex was 90 nm.
• a pressure-resistant polymerization vessel 7 parts by weight of the solid content of the polybutadiene rubber latex (R-2) obtained above, 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 part by weight of ferrous sulfate heptahydrate was added.
• the gas inside the pressure polymerization vessel was replaced with nitrogen to sufficiently remove oxygen from the inside of the pressure polymerization vessel.
• 93 parts by weight of Bd was charged into a pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C.
• a glass reactor was charged with 260 parts by weight of the polybutadiene rubber latex (R-3) (including 85 parts by weight of an elastic material whose main component is polybutadiene rubber) and 50 parts by weight of deionized water.
• the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. While replacing the gas in the glass reactor with nitrogen, the raw materials introduced were stirred at 60°C.
• 1.8 parts by weight of 1,3-butylene glycol dimethacrylate and 0.07 parts by weight of t-butyl hydroperoxide (BHP) were added into the glass reactor and stirred for 10 minutes.
• an aqueous latex (L-6) containing polymer fine particles (A) was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 200 nm.
• Production Example 1-7 Preparation of aqueous latex (L-7) containing polymer fine particles (A)
• Production Example 1-6 instead of the mixture of 14.25 parts by weight of MMA, 0.75 parts by weight of BA, and 0.05 parts by weight of BHP, 12.75 parts by weight of MMA, 0.75 parts by weight of BA, 1.5 parts by weight of GMA, and 0.05 parts by weight of BHP were used.
• An aqueous latex (L-7) containing polymer fine particles (A) was obtained in the same manner as in Production Example 1-6, except that the mixture was 0.5 parts by weight.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 200 nm.
• Production Example 1-8 Preparation of aqueous latex (L-8) containing polymer fine particles (A)
• Production Example 1-6 instead of the mixture of 14.25 parts by weight of MMA, 0.75 parts by weight of BA, and 0.05 parts by weight of BHP, 9.75 parts by weight of MMA, 0.75 parts by weight of BA, 4.5 parts by weight of GMA, and 0.05 parts by weight of BHP were used.
• An aqueous latex (L-8) containing polymer fine particles (A) was obtained in the same manner as in Production Example 1-6, except that the mixture was 0.5 parts by weight.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 200 nm.
• Example 1 Preparation of powder (P-2)
• aqueous latex (L-2) which is equivalent to 100 parts by weight of the polymer fine particles (A), and 22.2 parts by weight of the aqueous emulsion (S-1) (11.1 parts by weight of the resin (B)) were added.
• (equivalent) was poured into 600 parts by weight of the above ion-exchanged water to obtain a slurry containing a coagulated material containing polymer fine particles (A) and resin (B).
• the slurry was centrifugally dehydrated to obtain the above-mentioned coagulated wet powder.
• a resin composition was prepared using the powder (P-2) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• Example 2 Preparation of powder (P-3)
• Powder (P-3) was obtained in the same manner as in Example 1, except that aqueous latex (L-3) was used instead of aqueous latex (L-2).
• the dispersibility of the obtained powder in the matrix resin was measured by the method described in the above section (Dispersibility of powder in matrix resin). The results are shown in Table 1.
• a resin composition was prepared using the powder (P-3) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• Example 3 Preparation of powder (P-4)
• a powder (P-4) was obtained in the same manner as in Example 1, except that aqueous latex (L-4) was used instead of aqueous latex (L-2). .
• the dispersibility of the obtained powder in the matrix resin was measured by the method described in the above section (Dispersibility of powder in matrix resin). The results are shown in Table 1.
• a resin composition was prepared using the powder (P-4) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• a resin composition was prepared using the powder (P-1) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• Powder (P-5) was obtained in the same manner as in Example 1, except that aqueous latex (L-5) was used instead of aqueous latex (L-2).
• the dispersibility of the obtained powder in the matrix resin was measured by the method described in the above section (Dispersibility of powder in matrix resin). The results are shown in Table 1.
• a resin composition was prepared using the powder (P-5) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• Example 1 22.2 parts by weight of aqueous emulsion (S-2) was used instead of 22.2 parts by weight of aqueous emulsion (S-1), and aqueous latex (L-2) was used instead of aqueous latex (L-2).
• Powder (P-6) was obtained in the same manner as in Example 1, except that L-6) was used.
• the dispersibility of the obtained powder in the matrix resin was measured by the method described in the above section (Dispersibility of powder in matrix resin). The results are shown in Table 1.
• a resin composition was prepared using the powder (P-6) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• a resin composition was prepared using the powder (P-7) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• a resin composition was prepared using the powder (P-8) according to the method described in the above section (Measurement of physical properties of cured product of epoxy + silica blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• Comparative example 6 In Comparative Example 6, no stress reducing agent (powder) was used. The same procedure as described above (epoxy + silica A resin composition was prepared by the same method as in the section (Measurement of Physical Properties of Cured Blend). Furthermore, using this resin composition, a cured product was prepared according to the method described in the above-mentioned section (Measurement of physical properties of cured product of epoxy + silica blend). The elastic modulus and linear expansion coefficient of the obtained cured product were measured by the method described above. The results are shown in Table 1.
• One embodiment of the present invention provides a stress reducing agent that (i) is a stress reducing agent with excellent dispersibility in a matrix resin, and (ii) can provide a cured product having a good coefficient of linear expansion. be able to. Therefore, the resin composition containing the stress reducing agent according to one embodiment of the present invention can be suitably used as a sealing material for electronic materials and the like.

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