Classifications

• • 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
  • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
• • 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
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
  • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
• • 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
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
  • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
  • C08F283/085—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides on to unsaturated polyphenylene oxides
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides

Definitions

• the present invention relates to resin particles and a resin composition for semiconductor components.
• Resin particles used in semiconductor component applications are required to have high heat resistance so that the resin particles do not undergo substantial change even when the resin in which they are mixed is heated during molding or soldering.
• resin particles used in semiconductor component applications are required to have excellent flexibility so that they do not deform or break when the resin particles themselves or the resin in which they are mixed are subjected to a load such as pressure.
• thermosetting resin molding material has been reported that is made by blending thermoplastic norbornene-based resin particles with a thermosetting resin raw material, and is useful as a material for circuit boards, with excellent electrical properties such as insulation resistance, low dielectric constant, and low dielectric tangent (Patent Document 1).
• thermoplastic norbornene-based resin particles have the problem of being brittle and poor in flexibility.
• thermoplastic norbornene-based resin particles are particles obtained by crushing chunks, plates, pellets, etc. of thermoplastic norbornene-based resin, they have an irregular shape, and there is a problem that the filling property is low when mixed with resin.
• Hollow resin particles have been reported that have excellent insulating properties and can provide organic insulating materials with low dielectric constant and low dielectric tangent (Patent Document 2). However, because they are hollow resin particles, they have the problem of being poor in flexibility.
• a resin sheet for insulating purposes has been reported, in which a resin composition layer containing an epoxy resin, an organic solvent, an inorganic filler, and a stress relaxation material is provided on a support (Patent Document 3).
• core-shell type rubber particles are used as the particulate stress relaxation material, and a phenolic hydroxyl group-containing polybutadiene resin or polycarbonate resin is used as the non-particulate stress relaxation material.
• the core-shell type rubber particles described as the particulate stress relaxation material have a problem that the shell portion is an acrylic resin, and therefore the dielectric constant and dielectric tangent values are high and the heat resistance is insufficient.
• Non-particulate stress relaxation materials are amorphous, and there is a problem that the filling property is low when mixed into a resin.
• a composition for modifying insulating films which contains a dispersion medium and a core-shell polymer having a rubber-like elastic core layer, has been reported (Patent Document 4).
• the present invention has been made to solve the above-mentioned problems of the prior art, and its main objective is to provide resin particles that can achieve a low dielectric tangent, high heat resistance, and excellent flexibility. It also aims to provide a resin composition for semiconductor members that contains such resin particles.
• the resin particles according to an embodiment of the present invention contain a polymer P having an ether structure represented by formula (1), and have a recovery rate of 4.6% or more calculated by a load-unloading test performed under conditions of a temperature of 20°C, a relative humidity of 65%, a loading speed of 0.732 mN/sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN.
• the resin particles described in the above [1] may have a 3% weight loss temperature of 270° C. or higher when heated at a rate of 10° C./min in an air atmosphere.
• the resin particles according to the above [1] or [2] may have a dielectric loss tangent of 0.0040 or less at a frequency of 10 GHz.
• the resin particles according to any one of the above [1] to [3] may have a volume average particle diameter of 0.1 ⁇ m to 100 ⁇ m.
• the resin particles according to any one of the above [1] to [4] may have a particle size variation coefficient of 10% to 50%.
• the resin particles according to any one of [1] to [5] above may have an average circularity of 0.95 to 1.00.
• the resin particles according to any one of the above [1] to [6] may be solid particles.
• the polymer P may be a polymer obtained by a polymerization reaction of a monomer composition containing a compound A having an ether structure and a radical reactive group represented by the above formula (1) and a monomer M that reacts with the compound A.
• the monomer M may contain an aromatic monofunctional monomer m1 and an aromatic crosslinkable monomer m2.
• the content of the compound A in the monomer composition may be 0.1% by weight or more and less than 60% by weight.
• the content of the aromatic monofunctional monomer m1 in the monomer M may be 50% by weight to 99% by weight.
• the content of the aromatic crosslinkable monomer m2 in the monomer M may be 1% by weight to 50% by weight.
• the content ratio of the aromatic crosslinkable monomer m2 to the compound A in the monomer composition may be such that the amount of the aromatic crosslinkable monomer m2 is 1 part by weight to 1,000 parts by weight when the compound A is taken as 100 parts by weight.
• the monomer composition may contain less than 2 parts by weight of a thiol compound per 100 parts by weight of the monomer composition.
• the resin particles according to any one of the above [1] to [14] may be used for a semiconductor member.
• a resin composition for a semiconductor member according to an embodiment of the present invention contains the resin particles described in [15] above.
• resin particles that can exhibit a low dielectric tangent, high heat resistance, and excellent flexibility. It is also possible to provide a resin composition for semiconductor members that contains such resin particles.
• (meth)acrylic means “acrylic and/or methacrylic
• (meth)acrylate means "acrylate and/or methacrylate”.
• the resin particles according to the embodiment of the present invention have a restoration rate calculated by a load-unloading test performed under conditions of a temperature of 20° C., a relative humidity of 65%, a load speed of 0.732 mN/sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN, which is preferably 4.6% or more, more preferably 5% or more, even more preferably 5.5% or more, even more preferably 6.0% or more, even more preferably 6.2% or more, particularly preferably 6.3% or more, and most preferably 6.5% or more.
• the higher the restoration rate within the above range the more excellent the flexibility of the resin particles according to the embodiment of the present invention. If the restoration rate is low outside the above range, the flexibility of the resin particles will be reduced, and when a load is applied to the resin particles themselves or to a resin containing the resin particles by pressing, etc., the resin particles may be deformed or destroyed.
• the measurement method for the load-unloading test will be described in detail later.
• the resin particles according to the embodiment of the present invention preferably have a 3% weight loss temperature of 270°C or higher, more preferably 280°C or higher, even more preferably 290°C or higher, even more preferably 300°C or higher, particularly preferably 310°C or higher, and most preferably 320°C or higher when heated in an air atmosphere at a rate of 10°C/min.
• the higher the 3% weight loss temperature the better, but in reality, the upper limit may be 500°C or lower.
• the higher the 3% weight loss temperature is within the above range, the higher the heat resistance of the resin particles according to the embodiment of the present invention. If the 3% weight loss temperature is lower than the above range, the resin particles will deform when heated.
• the resin particles when the resin particles are kneaded with a thermosetting resin, the resin particles will deform when heated for the curing reaction, which may reduce the effect of reducing the dielectric tangent.
• the method for measuring the 3% weight loss temperature will be described in detail later.
• the resin particles according to the embodiment of the present invention preferably have a dielectric loss tangent at a frequency of 10 GHz of 0.0040 or less, more preferably 0.0030 or less, even more preferably 0.0020 or less, particularly preferably 0.0015 or less, and most preferably 0.0010 or less.
• the lower limit of the dielectric loss tangent may preferably be 0 or more. If the dielectric loss tangent is within the above range, the resin particles according to the embodiment of the present invention themselves and the resin in which the resin particles are mixed can have a low dielectric loss tangent. The method for measuring the dielectric loss tangent will be described in detail later.
• the volume average particle diameter of the resin particles according to the embodiment of the present invention is preferably 0.1 ⁇ m to 100 ⁇ m. If the volume average particle diameter is within the above range, the resin particles according to the embodiment of the present invention can be used for various applications. The method for measuring the volume average particle diameter will be described in detail later.
• the volume average particle size of the resin particles according to the embodiment of the present invention is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 50 ⁇ m, even more preferably 0.1 ⁇ m to 30 ⁇ m, particularly preferably 0.1 ⁇ m to 20 ⁇ m, and most preferably 0.1 ⁇ m to 10 ⁇ m.
• the volume average particle size of the resin particles according to the present invention is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.3 ⁇ m to 50 ⁇ m, even more preferably 0.6 ⁇ m to 30 ⁇ m, particularly preferably 0.8 ⁇ m to 20 ⁇ m, and most preferably 1 ⁇ m to 10 ⁇ m.
• the volume average particle size of the resin particles according to the present invention is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 50 ⁇ m, even more preferably 0.1 ⁇ m to 10 ⁇ m, particularly preferably 0.1 ⁇ m to 5 ⁇ m, and most preferably 0.1 ⁇ m to 1 ⁇ m.
• the resin particles according to the embodiment of the present invention preferably have a particle diameter coefficient of variation of 10% to 50%, more preferably 15% to 45%, even more preferably 18% to 42%, particularly preferably 20% to 40%, and most preferably 22% to 38%. If the particle diameter coefficient of variation is within the above range, for example, when the resin particles are mixed into a resin, the resin particles are easily dispersed in the resin, and the adverse effects of an increase in the amount of coarse resin particles can be suppressed. If the particle diameter coefficient of variation of the resin particles is too large outside the above range, the increase in the amount of coarse resin particles may make it difficult to form a thin film or cause thickness variations when, for example, the resin particles are mixed into a resin to form a resin layer.
• the particle diameter coefficient of variation of the resin particles is too small outside the above range, the resin particles are difficult to disperse in the resin when mixed into a resin, and for example, when the resin particles are mixed into a resin to form a resin layer, may cause thickness variations.
• the method for measuring the coefficient of variation of the particle size will be described in detail later.
• the resin particles according to an embodiment of the present invention preferably have an average circularity of 0.95 to 1.00, more preferably 0.96 to 1.00, even more preferably 0.97 to 1.00, particularly preferably 0.98 to 1.00, and most preferably 0.99 to 1.00. If the average circularity is within the above range, the shape of the resin particles according to an embodiment of the present invention will be close to a perfect sphere, and therefore, for example, the filling properties will be improved when mixed into a resin. If the average circularity is low and outside the above range, the shape of the resin particles will deviate from a perfect sphere, and, for example, there is a risk that the filling properties will be reduced when mixed into a resin.
• the resin particles according to the embodiment of the present invention are preferably solid particles. If the resin particles according to the embodiment of the present invention are solid particles, they may exhibit better flexibility.
• the resin particles according to the embodiment of the present invention typically contain a polymer P having an ether structure represented by formula (1).
• the polymer P has the ether structure represented by formula (1), the effects of the present invention can be more effectively exhibited.
• the polymer P may be of only one type or of two or more types.
• the polymer P may have only one type of ether structure represented by formula (1), or two or more types.
• polymer P has the ether structure represented by formula (1) can be confirmed by any appropriate identification means, such as NMR, IR, or MS.
• the content of polymer P in the resin particles according to an embodiment of the present invention is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight, in order to further exert the effects of the present invention.
• a preferred embodiment of polymer P is a polymer obtained by a polymerization reaction of a monomer composition containing compound A having an ether structure and a radical reactive group represented by formula (1) and monomer M that reacts with compound A.
• the monomer composition is composed of compound A and monomer M, and does not contain a polymerization initiator used in the polymerization reaction.
• a preferred embodiment of polymer P therefore includes an ether structure represented by formula (1) and structural units derived from the monomers contained in monomer M.
• monomer M includes aromatic monofunctional monomer m1 and aromatic crosslinkable monomer m2 as described below
• a preferred embodiment of polymer P has an ether structure represented by formula (1), structural units derived from aromatic monofunctional monomers, and structural units derived from aromatic crosslinkable monomers.
• a "structural unit derived from a monomer” refers to a structural unit of a polymer formed when a radical reactive group (typically a carbon-carbon unsaturated double bond) of a monomer contained in a monomer composition is cleaved by a polymerization reaction when preparing a polymer by polymerization of the monomer composition.
• the content ratio of structural units derived from each monomer in a polymer can be known by various structural analyses of the polymer (e.g., NMR, etc.). Furthermore, even without performing such various structural analyses, the content ratio of structural units derived from each monomer in a polymer may be calculated based on the amount of each monomer used to prepare the polymer and the polymerization reaction rate. Furthermore, the content ratio of structural units derived from each monomer in a polymer may be determined by any other appropriate means.
• Compound A may be of only one type or of two or more types.
• radical reactive group possessed by compound A any appropriate radical reactive group may be adopted as long as it is a group generally known as a radical reactive group and does not impair the effects of the present invention.
• radical reactive groups are preferably groups having a carbon-carbon unsaturated double bond, and specific examples thereof include vinyl groups, acrylic groups, methacrylic groups, acrylamide groups, and allyl groups.
• any appropriate compound may be used as long as it has the ether structure represented by formula (1) and a radical reactive group, without impairing the effects of the present invention.
• a preferable example of such compound A is polyphenylene ether (PPE).
• compound A is polyphenylene ether (PPE) having a structure represented by formula (2).
• PPE polyphenylene ether
• compound A is not limited to polyphenylene ether (PPE) having a structure represented by formula (2) as long as it has an ether structure represented by formula (1) and a radical reactive group.
• m and n represent the number of repeating units (number of moles added) of the ether structure represented by formula (1)
• X1 and X2 represent organic groups having a radical reactive group
• Y represents an organic group not having a radical reactive group.
• m and n are not particularly limited, and may each be, for example, 1 to 100, 2 to 70, 4 to 50, or 5 to 30.
• polyphenylene ether products include, for example, the NORYL (registered trademark) series (NORYL (registered trademark) SA9000, etc.) (manufactured by SABIC), the Iupiace (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), the ZYLON (registered trademark) series (manufactured by Asahi Kasei Corporation), the OPE-2St series (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the DPPE-VBT50 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
• NORYL registered trademark
• Iupiace registered trademark
• ZYLON registered trademark
• OPE-2St series manufactured by Mitsubishi Gas Chemical Co., Ltd.
• DPPE-VBT50 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• Compound A may be an oligomer, which can further exert the effects of the present invention.
• the number average molecular weight Mn of compound A is preferably 500 to 5000, more preferably 800 to 3500, even more preferably 1000 to 3000, particularly preferably 1200 to 2500, and most preferably 1400 to 2000.
• the content of compound A in the monomer composition is preferably 0.1% by weight or more and less than 60% by weight, more preferably 0.1% by weight or more and less than 55% by weight, even more preferably 0.1% by weight or more and less than 50% by weight, even more preferably 0.1% by weight or more and less than 45% by weight, even more preferably 0.1% by weight or more and less than 40% by weight, even more preferably 1% by weight to 35% by weight, even more preferably 3% by weight to 30% by weight, even more preferably 5% by weight to 25% by weight, particularly preferably 7% by weight to 22% by weight, and most preferably 9% by weight to 21% by weight, so that the effects of the present invention can be more effectively exhibited.
• high heat resistance may not be exhibited, or excellent flexibility may not be exhibited. If the content of compound A in the monomer composition is too high and outside the above range, the effects of the present invention may not be achieved. For example, compound A may be difficult to dissolve in the monomer composition, and resin particles may not be obtained.
• any appropriate monomer may be used as long as it is different from the compound A and reacts with the compound A, as long as the effect of the present invention is not impaired.
• the monomer M may be one type only, or two or more types.
• the monomer M preferably contains an aromatic monofunctional monomer m1 and an aromatic crosslinkable monomer m2, in that the effects of the present invention can be more effectively achieved.
• the aromatic monofunctional monomer m1 may be of only one type, or of two or more types.
• the aromatic crosslinkable monomer m2 may be of only one type, or of two or more types.
• aromatic monofunctional monomer m1 Any appropriate aromatic monofunctional monomer m1 may be used as long as it is a monofunctional aromatic monomer and does not impair the effects of the present invention.
• aromatic monofunctional monomer m1 include styrene, ethylvinylbenzene, ⁇ -methylstyrene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene, which can further bring out the effects of the present invention.
• the aromatic monofunctional monomer m1 be at least one selected from the group consisting of styrene and ethylvinylbenzene.
• aromatic crosslinkable monomer m2 Any appropriate aromatic crosslinkable monomer m2 may be used as long as it is an aromatic monomer having crosslinkability and does not impair the effects of the present invention.
• aromatic crosslinkable monomer m2 include divinylbenzene, divinylnaphthalene, and diallyl phthalate, which can further express the effects of the present invention.
• Divinylbenzene is preferred as the aromatic crosslinkable monomer m2, as it can further express the effects of the present invention and has good reactivity.
• the total content of aromatic monofunctional monomer m1 and aromatic crosslinkable monomer m2 in the total amount of monomer M is preferably 50% by weight to 100% by weight, more preferably 80% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight, in order to further exert the effects of the present invention.
• any other appropriate monomer different from compound A, aromatic monofunctional monomer m1, and aromatic crosslinkable monomer m2 may be used as long as it does not impair the effects of the present invention.
• the other monomer may be one type only, or two or more types.
• monomers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; maleic anhydride; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetracyclododecyl tetracyclododecyl (meth)acrylate, and cetyl (meth)acrylate; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, and diethyl
• methacrylic acid derivative monomers having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid
• polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate
• polyfunctional allyl derivative monomers such as diallylamine and tetraallyloxyethane
• conjugated diolefin monomers such as butadiene and isoprene
• chlorine-containing monomers such as vinyl chloride and vinylidene chloride
• (meth)acrylamide polyfunctional acrylamide derivative monomers, such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylenebis(meth)acrylamide
• (meth)acrylonitrile vinyl acetate
• the content of other monomers in the total amount of monomer M is preferably 0% to 50% by weight, more preferably 0% to 20% by weight, even more preferably 0% to 10% by weight, particularly preferably 0% to 5% by weight, and most preferably 0% to 2% by weight, in order to better exhibit the effects of the present invention.
• the content of monomer M in the monomer composition is preferably more than 40% by weight and not more than 99.9% by weight, more preferably more than 45% by weight and not more than 99.9% by weight, even more preferably more than 50% by weight and not more than 99.9% by weight, even more preferably more than 55% by weight and not more than 99.9% by weight, even more preferably more than 60% by weight and not more than 99.9% by weight, even more preferably 65% to 99% by weight, even more preferably 70% to 97% by weight, even more preferably 75% to 95% by weight, particularly preferably 78% to 93% by weight, and most preferably 79% to 91% by weight.
• the effects of the present invention may not be achieved, for example, compound A may be difficult to dissolve in the monomer composition, and resin particles may not be obtained. If the content of monomer M in the monomer composition is too high and falls outside the above range, the effects of the present invention may not be achieved, for example, high heat resistance may not be achieved, or excellent flexibility may not be achieved.
• the content of aromatic monofunctional monomer m1 in monomer M is preferably 50% by weight to 99% by weight, more preferably 60% by weight to 97% by weight, even more preferably 70% by weight to 95% by weight, even more preferably 80% by weight to 93% by weight, particularly preferably 85% by weight to 92% by weight, and most preferably 87% by weight to 91% by weight, in order to better demonstrate the effects of the present invention.
• the content of aromatic crosslinkable monomer m2 in monomer M is preferably 1% by weight to 50% by weight, more preferably 3% by weight to 40% by weight, even more preferably 5% by weight to 30% by weight, even more preferably 7% by weight to 20% by weight, particularly preferably 8% by weight to 15% by weight, and most preferably 9% by weight to 13% by weight, in order to better demonstrate the effects of the present invention.
• the content ratio of aromatic crosslinkable monomer m2 to compound A is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, even more preferably 20 to 400 parts by weight, even more preferably 25 to 300 parts by weight, particularly preferably 30 to 250 parts by weight, and most preferably 35 to 200 parts by weight, when compound A is taken as 100 parts by weight, in order to more effectively exhibit the effects of the present invention.
• the polymer P is obtained by a polymerization reaction of the monomer composition.
• the polymerization reaction is preferably a suspension polymerization reaction.
• an oil phase is added to an aqueous phase and dispersed to perform the polymerization reaction.
• any suitable dispersion method can be used as long as it can cause the oil phase to exist in droplets in the aqueous phase, without impairing the effects of the present invention.
• Representative examples of such dispersion methods include dispersion methods using a homomixer or homogenizer, such as a high-speed homomixer, a polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.
• the aqueous phase typically contains an aqueous solvent.
• Typical aqueous solvents include water and mixed solvents of water and lower alcohols (methanol, ethanol, etc.).
• any appropriate amount of the aqueous solvent may be used as long as it does not impair the effects of the present invention.
• the amount of the aqueous solvent used is preferably 10 parts by weight to 5,000 parts by weight, more preferably 50 parts by weight to 3,000 parts by weight, and even more preferably 100 parts by weight to 2,000 parts by weight, relative to 100 parts by weight of the monomer composition.
• the oil phase may contain an organic solvent.
• organic solvents include organic solvents with a boiling point of less than 100°C.
• organic solvents with a boiling point of less than 100°C include heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.
• the organic solvent with a boiling point of less than 100°C may be a mixed solvent.
• the amount of organic solvent used is preferably 20 to 250 parts by weight per 100 parts by weight of the monomer composition.
• the amount of organic solvent used is preferably less than 20 parts by weight per 100 parts by weight of the monomer composition, more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, particularly preferably 1 part by weight or less, and most preferably 0.1 parts by weight or less.
• any suitable additive B that does not correspond to either compound A or monomer M may be used within a range that does not impair the effects of the present invention.
• the additive B may be of only one type, or of two or more types.
• Additive B includes, for example, a polymerization initiator, a surfactant, a dispersion stabilizer, a thiol compound, and an antioxidant.
• any suitable polymerization initiator may be used as long as it does not impair the effects of the present invention.
• the polymerization initiator may be one type only, or two or more types.
• examples of such polymerization initiators include organic peroxides such as lauroyl peroxide (LPO), benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile); and the like.
• LPO lauroyl peroxide
• benzoyl peroxide orthochlorobenzoyl peroxide
• the polymerization initiator may be added to either the aqueous phase or the oil phase, but is typically added to the oil phase.
• the amount of polymerization initiator added is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the monomer composition.
• any appropriate surfactant may be used as the surfactant as long as it does not impair the effects of the present invention.
• the surfactant may be of only one type, or of two or more types. In terms of being able to further exert the effects of the present invention, it is preferable that the surfactant be at least one type selected from the group consisting of amphoteric surfactants and anionic surfactants.
• amphoteric surfactant any appropriate amphoteric surfactant may be used as long as it does not impair the effects of the present invention.
• an amphoteric surfactant a known amphoteric surfactant that can be used in the production of resin particles may be used.
• amphoteric surfactants include lauryl dimethylamine oxide, lauryl dimethylaminoacetate betaine, phosphate surfactants, and phosphite surfactants. Only one type of amphoteric surfactant may be used, or two or more types may be used.
• anionic surfactant any suitable anionic surfactant may be used as long as it does not impair the effects of the present invention.
• anionic surfactants include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfate ester salts, alkylaryl sulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, naphthalenesulfonate-formaldehyde condensates, polyoxyethylene alkyl phosphate sulfonates, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.
• anionic surfactants include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonylphenyl ether sulfate ester salts, and sodium salts of ⁇ -naphthalenesulfonate-formaldehyde condensates.
• the anionic surfactant may be one type only, or two or more types.
• the surfactant may be added to either the aqueous phase or the oil phase, but is typically added to the aqueous phase.
• the amount of surfactant used is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, and even more preferably 0.01 to 0.1 parts by weight, per 100 parts by weight of the aqueous solvent contained in the aqueous phase.
• any appropriate dispersion stabilizer may be adopted as long as it does not impair the effects of the present invention.
• the dispersion stabilizer may be one type only, or two or more types.
• examples of the dispersion stabilizer include polyvinyl alcohol; polycarboxylic acid; celluloses such as hydroxyethyl cellulose and carboxymethyl cellulose; polyvinylpyrrolidone; inorganic water-soluble polymers such as sodium tripolyphosphate; phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; poorly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and
• the dispersion stabilizer may be added to either the water phase or the oil phase, but is typically added to the water phase.
• the amount of dispersion stabilizer used is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the aqueous solvent contained in the aqueous phase.
• Any appropriate thiol compound may be used as the thiol compound as long as it does not impair the effects of the present invention.
• the thiol compound may be of only one type, or of two or more types. Examples of such thiol compounds include polyfunctional thiol compounds and monofunctional thiol compounds having an alkyl group with 1 to 20 carbon atoms in the molecule.
• any suitable polyfunctional thiol compound may be used as long as it has two or more thiol groups in the molecule and does not impair the effects of the present invention.
• the polyfunctional thiol compound may be one type or two or more types.
• polyfunctional thiol compounds examples include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, ethylene glycol bisthioglycolate (EGTG), 1,4-butanediol bisthiopropionate (BDTG), trimethylolpropane tristhioglycolate, and the like.
• mercapto-s-triazines examples include ethylene glycol bisthioglycolate (TMTG), trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthioglycolate (PETG), pentaerythritol tetrakisthiopropionate, dipentaerythritol hexathiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.
• TMTG ethylene glycol bisthioglycolate
• PETG pentaerythritol tetrakisthioglycolate
• ethylene glycol bisthioglycolate (EGTG), 1,4-butanediol bisthiopropionate (BDTG), trimethylolpropane tristhioglycolate (TMTG), and pentaerythritol tetrakisthioglycolate (PETG) are preferred.
• EGTG ethylene glycol bisthioglycolate
• BDTG 1,4-butanediol bisthiopropionate
• TMTG trimethylolpropane tristhioglycolate
• PETG pentaerythritol tetrakisthioglycolate
• any suitable monofunctional thiol-based compound having an alkyl group with 1 to 20 carbon atoms in the molecule can be used as long as it has one thiol group and an alkyl group with 1 to 20 carbon atoms in the molecule, within a range that does not impair the effects of the present invention.
• Examples of such monofunctional thiol-based compounds having an alkyl group with 1 to 20 carbon atoms in the molecule include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, dodecanethiol, and compounds having branched chain structures of these.
• the amount of the thiol compound added is preferably 5 parts by weight or less, more preferably 0.05 to 5 parts by weight, even more preferably 0.1 to 3 parts by weight, and particularly preferably 0.3 to 2 parts by weight, relative to 100 parts by weight of the monomer composition.
• the monomer composition preferably contains 5 parts by weight or less of the thiol compound, more preferably 0.05 to 5 parts by weight of the thiol compound, even more preferably 0.1 to 3 parts by weight of the thiol compound, and particularly preferably 0.3 to 2 parts by weight of the thiol compound, relative to 100 parts by weight of the monomer composition.
• the thiol compound can function as a chain transfer agent and can be a constituent unit of the polymer P.
• a radical polymerization system for example, a radical polymerization system using a hydrolyzable silicon compound having a hydrolyzable silyl group and a group that reacts with a radically polymerizable unsaturated group, a monofunctional (meth)acrylic monomer, or a polyfunctional (meth)acrylic monomer
• the thiol compound can receive a radical from a growing polymer chain to stop the extension of the polymer chain and generate a new radical to start a growth reaction of another polymer chain. This makes it possible to uniform the molecular weight of the resulting polymer P, and in turn the molecular weight of the resin particles according to the embodiment of the present invention, and to uniform the particle size distribution.
• any appropriate antioxidant may be used as the antioxidant as long as it does not impair the effects of the present invention.
• the antioxidant may be of only one type, or of two or more types. Examples of such antioxidants include antioxidants having a melting point of 30°C or higher and 105°C or lower. If an antioxidant with a melting point of less than 30°C is used, there is a risk that the antioxidant will liquefy due to the outside air temperature when the resin particles are recovered as a dry powder. If an antioxidant with a melting point exceeding 105°C is used, there is a risk that the dispersion stability of the resin particle dispersion liquid will be affected during heat treatment.
• the antioxidant can be in a powder form at room temperature (25°C). It can also be dispersed or dissolved in water, alcohol, etc.
• antioxidants examples include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. From the viewpoint of being able to further exert the effects of the present invention, antioxidants having radical scavenging ability are preferred, phenol-based antioxidants and amine-based antioxidants are preferred, and phenol-based antioxidants are more preferred.
• any appropriate phenolic antioxidant may be used as long as it does not impair the effects of the present invention.
• a phenolic antioxidant a compound having a substituent such as an alkyl group at the ortho position relative to the phenolic hydroxyl group is preferred.
• phenol-based antioxidants include 3-(4'-hydroxy-3',5-di-tert-butylphenyl)propion-n-octadecyl, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, and 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
• Any suitable phosphorus-based antioxidant may be used as the phosphorus-based antioxidant as long as it does not impair the effects of the present invention.
• An example of such a phosphorus-based antioxidant is 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane.
• sulfur-based antioxidant Any suitable sulfur-based antioxidant may be used as the sulfur-based antioxidant as long as it does not impair the effects of the present invention.
• sulfur-based antioxidants include dioctadecyl 3,3'-thiodipropionate and pentaerythritol tetrakis[3-(dodecylthio)propionate].
• Any appropriate amine-based antioxidant may be used as the amine-based antioxidant as long as it does not impair the effects of the present invention.
• examples of such amine-based antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) butane-1,2,3,4-tetracarboxylate, and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
• the amount of antioxidant added is preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the monomer composition.
• any suitable polymerization temperature may be used as long as it is suitable for suspension polymerization and does not impair the effects of the present invention.
• the polymerization temperature may be set to 30°C to 80°C as the initial polymerization temperature, and then the temperature may be increased to 70°C to 120°C as the later polymerization temperature.
• Any suitable polymerization time may be used as long as it is suitable for suspension polymerization and does not impair the effects of the present invention.
• Such a polymerization time is preferably 1 hour to 48 hours at the initial polymerization temperature, and preferably 1 hour to 24 hours at the later polymerization temperature.
• the dispersion stabilizer such as magnesium pyrophosphate can be decomposed, washed, separated, dried, etc., to obtain resin particles according to an embodiment of the present invention.
• the resin particles according to the embodiment of the present invention are suitable for semiconductor members in that the effects of the present invention can be more effectively utilized. That is, the resin particles according to the embodiment of the present invention are preferably for use in semiconductor members.
• a conductive material refers to a material that constitutes a semiconductor, such as a semiconductor package or a semiconductor module.
• a semiconductor package is a package that is constructed using an IC chip as an essential component and at least one material selected from the group consisting of mold resin, underfill material, mold underfill material, die bond material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.
• a semiconductor module is comprised of a semiconductor package as an essential component, and at least one member selected from the group consisting of prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic shielding films, and adhesive sheets for printed circuit boards.
• the resin particles according to the embodiment of the present invention can exhibit a low dielectric tangent, high heat resistance, and excellent flexibility, and therefore can be suitably used in a resin composition for a semiconductor member. That is, the resin composition for a semiconductor member according to the embodiment of the present invention contains the resin particles according to the embodiment of the present invention.
• the resin composition for a semiconductor member means a resin composition used for a semiconductor member.
• the resin composition for semiconductor members according to an embodiment of the present invention typically contains resin particles and a resin component according to an embodiment of the present invention.
• any suitable resin component used in semiconductor components may be used.
• the content ratio of the resin particles according to the embodiment of the present invention in the resin composition for semiconductor members according to the embodiment of the present invention can be appropriately set according to the purpose.
• the resin particles according to the embodiment of the present invention may be used for any other suitable applications, such as coating compositions, cosmetics, light diffusing compositions, and light diffusing films, in addition to semiconductor members.
• the resin particles according to the embodiment of the present invention can impart an excellent appearance to a coating film containing the resin particles, and therefore can be suitably used in a coating composition.
• Such a coating composition contains the resin particles according to the embodiment of the present invention.
• the coating composition preferably contains at least one selected from a binder resin and a UV-curable resin.
• the binder resin may be of only one type or may be of two or more types.
• the UV-curable resin may be of only one type or may be of two or more types.
• binder resin Any suitable binder resin may be used as long as it does not impair the effects of the present invention.
• binder resins include resins that are soluble in organic solvents or water, and emulsion-type water-based resins that can be dispersed in water.
• binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.
• any suitable UV-curable resin may be used as long as it does not impair the effects of the present invention.
• examples of such UV-curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins. Polyfunctional (meth)acrylate resins are preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule are more preferred.
• polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.
• the content ratio may be any appropriate content ratio depending on the purpose.
• the resin particles according to the embodiment of the present invention are preferably 5% by weight to 50% by weight, more preferably 10% by weight to 50% by weight, and even more preferably 20% by weight to 40% by weight, based on the total amount of the binder resin (in solids content in the case of an emulsion-type aqueous resin) and at least one selected from a UV-curable resin, and the resin particles according to the embodiment of the present invention.
• a photopolymerization initiator is preferably used in combination. Any appropriate photopolymerization initiator may be used as long as it does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP-A No.
• 2,3-dialkyldione compounds 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and ⁇ -acyloxime esters.
• the coating composition may contain a solvent.
• the solvent may be one type only, or may be two or more types.
• the content ratio of the solvent may be any appropriate content ratio depending on the purpose.
• any suitable solvent may be used as the solvent as long as it does not impair the effects of the present invention.
• a solvent is preferably one that can dissolve or disperse the binder resin or UV-curable resin.
• solvents include, for example, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether; and for water-based paints, such as water and alcohols.
• the coating composition may be diluted to adjust the viscosity as necessary.
• Any appropriate diluent may be used depending on the purpose. Examples of such diluents include the solvents mentioned above.
• the diluent may be one type or two or more types.
• the coating composition may contain other components as necessary, such as coating surface conditioners, flowability conditioners, UV absorbers, light stabilizers, curing catalysts, extender pigments, color pigments, metal pigments, mica powder pigments, and dyes.
• coating surface conditioners such as coating surface conditioners, flowability conditioners, UV absorbers, light stabilizers, curing catalysts, extender pigments, color pigments, metal pigments, mica powder pigments, and dyes.
• any appropriate coating method may be used depending on the purpose. Examples of such coating methods include spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.
• any suitable formation method includes a method in which a coating film is formed by applying the composition to any coating surface of a substrate, drying the coating film, and then curing the coating film as necessary to form a coating film.
• substrates include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).
• the resin particles according to the embodiment of the present invention can impart excellent light diffusibility to a coating film containing the resin particles, and therefore can be suitably used in a light diffusing resin composition.
• a light diffusing resin composition contains the resin particles according to the embodiment of the present invention.
• the light-diffusing resin composition preferably contains at least one selected from a binder resin and a UV-curable resin.
• the above-mentioned explanation of the coating composition may be applied to the binder resin and the UV-curable resin.
• the light-diffusing resin composition may contain a solvent.
• the above-mentioned explanation of the coating composition may be used for the solvent.
• the light-diffusing resin composition may be diluted to adjust the viscosity as necessary.
• the above-mentioned explanation of the coating composition may be used as the diluent.
• the light-diffusing resin composition may contain other components, such as coating surface conditioners, flowability conditioners, UV absorbers, light stabilizers, curing catalysts, extender pigments, color pigments, metal pigments, mica powder pigments, and dyes, as necessary.
• coating surface conditioners such as coating surface conditioners, flowability conditioners, UV absorbers, light stabilizers, curing catalysts, extender pigments, color pigments, metal pigments, mica powder pigments, and dyes, as necessary.
• the above explanation of the coating composition can be used for the coating method and formation method.
• the resin particles according to the embodiment of the present invention can impart excellent light diffusibility to a film having a coating film containing the resin particles, and therefore can be suitably used in a light diffusion film.
• a light diffusion film contains the resin particles according to the embodiment of the present invention.
• the light diffusion film includes a light diffusion layer formed from a light diffusing resin composition and a substrate.
• the light diffusion layer may or may not be the outermost layer of the light diffusion film.
• the light diffusion film according to the embodiment of the present invention may include any other appropriate layers depending on the purpose. Examples of such other layers include a protective layer, a hard coat layer, a planarizing layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal fine particle layer, a conductive metal oxide fine particle layer, and a primer layer.
• substrates include metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display panel.
• plastics that make up the plastic film, plastic sheet, plastic lens, and plastic panel include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetyl cellulose).
• ⁇ Method of measuring volume average particle size and coefficient of variation of particle size of resin particles The spherical equivalent volume average particle diameter of the resin particles was measured using a precision particle size distribution measuring device (product name "Coulter Multisizer (registered trademark) 3", manufactured by Beckman Coulter, Inc.). The measurement was performed using an aperture calibrated according to the Multisizer (registered trademark) 3 user's manual issued by Beckman Coulter, Inc.
• the aperture used for the measurement was appropriately selected depending on the size of the particles to be measured, such as selecting an aperture having a size of 50 ⁇ m when the assumed volume average particle diameter of the particles to be measured is 1 ⁇ m or more and 10 ⁇ m or less, selecting an aperture having a size of 100 ⁇ m when the assumed volume average particle diameter of the particles to be measured is greater than 10 ⁇ m and less than 30 ⁇ m, selecting an aperture having a size of 280 ⁇ m when the assumed volume average particle diameter of the particles is greater than 30 ⁇ m and 90 ⁇ m or less, and selecting an aperture having a size of 400 ⁇ m when the assumed volume average particle diameter of the particles is greater than 90 ⁇ m and 150 ⁇ m or less.
• the aperture was changed to one having an appropriate size and the measurement was performed again.
• Current (aperture current) and Gain (gain) were appropriately set according to the size of the selected aperture. For example, when an aperture having a size of 50 ⁇ m was selected, Current (aperture current) was set to ⁇ 800 and Gain (gain) was set to 4, when an aperture having a size of 100 ⁇ m was selected, Current (aperture current) was set to ⁇ 1600 and Gain (gain) was set to 2, and when apertures having sizes of 280 ⁇ m and 400 ⁇ m were selected, Current (aperture current) was set to ⁇ 3200 and Gain (gain) was set to 1.
• the sheath liquid used in the above-mentioned flow type particle image analyzer a particle sheath ("PSE-900A” manufactured by Sysmex Corporation) was used.
• the dispersion liquid for measurement prepared according to the above procedure was introduced into the flow type particle image analyzer, and the circularity was measured according to the following [Measurement conditions for circularity].
• the flow type particle image analyzer was automatically focused using a suspension of standard polymer particles (e.g., Thermo Fisher Scientific's "5200A” (standard polystyrene particles diluted with ion-exchanged water)).
• the circularity is the value obtained by dividing the perimeter calculated from the diameter of a perfect circle having the same projected area as an image of the resin particle by the perimeter of the image of the resin particle.
• the average circularity is the value obtained by dividing the sum of the circularities of the individual resin particles by the sum of the frequency based on the number.
• the proportion of hollow particles having an average circularity of 0.90 or less was calculated from the data of the frequency based on the number in intervals of 0.010 (e.g., 0.200 or more and less than 0.990) measured by the above measurement.
• Measurement mode LPF measurement mode or HPF measurement mode (selected appropriately depending on the spherical equivalent volume average particle diameter.
• the HPF measurement mode was selected when the spherical equivalent volume average particle diameter was 8 ⁇ m or less, and the LPF measurement mode was selected when the spherical equivalent volume average particle diameter was 8 ⁇ m or more.
• the 3% weight loss temperature of the resin particles was measured using a simultaneous thermogravimetry and differential thermal analyzer "TG/DTA6200, AST-2" manufactured by SII Nano Technology Co., Ltd.
• the sampling method and temperature conditions were as follows. The sample was filled to the bottom of a platinum measuring container with 10.5 ⁇ 0.5 mg of sample without leaving any gaps, and used as a sample for measurement.
• the 3% weight loss temperature was measured using alumina as a reference material under an air flow rate of 230 mL/min.
• the TG/DTA curve was obtained by heating the sample from 30°C to 500°C at a heating rate of 10°C/min. From the obtained curve, the temperature at 3% weight loss was calculated using the analysis software attached to the device, and was determined as the 3% weight loss temperature.
• MCTM-200 micro-compression tester
• the selected resin particles are fine particles with diameters in the range of 7 ⁇ m to 9 ⁇ m, and resin particles outside this range are not used for the measurement of compressive strength.
• the test indenter is lowered to the apex of the selected resin particle at the following loading rate to measure the particle diameter A when the resin particle is loaded to a maximum load of 9.81 mN, and the particle diameter B when the load is then removed to a minimum test force of 1.96 mN. From the displacement (restoration amount) obtained from the particle diameter A and the particle diameter B, the individual restoration rates were calculated by the following formula. Measurements were performed on six resin particles, and the maximum and minimum values were excluded from the six restoration rates, and the average value of the remaining four data was taken as the restoration rate.
• Recovery rate (%) recovery amount ( ⁇ m) / particle diameter under no load ( ⁇ m) ⁇ 100 [Conditions for measuring restoration rate]
• ⁇ Dielectric properties of resin particles The dielectric properties of the resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Co., Ltd.
• the dielectric loss tangent of the resin particles was calculated based on the perturbation theory using a resonator at a frequency of 10 GHz, in a measurement environment of 23°C and a relative humidity of 51 ⁇ 1%.
• Example 1 An oil phase was prepared by mixing 20 g of a reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure, 334.4 g of styrene (St), 45.6 g of divinylbenzene (DVB) (trade name "DVB-810", manufactured by Nippon Steel Chemical & Material Co., Ltd., a product containing 81% DVB, the remaining 19% being ethylvinylbenzene (EVB)), 4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 1.08 g of benzoyl peroxide.
• a reactive low-molecular-weight polyphenylene ether trade name "Noryl (registered trademark) SA9000-
• 0.4 g of sodium lauryl sulfate was dissolved in 1,075 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate to prepare an aqueous phase.
• the oil phase was added to the aqueous phase, and dispersed for 5 minutes at 8300 rpm using a TK homomixer (manufactured by Primix Corporation) to prepare a suspension.
• the resulting suspension was heated at 55°C for 5 hours, and then the internal temperature of the polymerization vessel was raised to 105°C (secondary heating), and the mixture was stirred at 105°C for 2 hours to complete the polymerization reaction.
• Resin particles (2) were obtained in the same manner as in Example 1, except that the amounts of SA9000, St, and DVB-810 were changed to 40 g, 316.8 g, and 43.2 g, respectively. Furthermore, 0.425 g of the obtained resin particles (2), 8.3 g of ethyl acetate, and 1.7 g of a solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were defoamed and stirred using a planetary stirring defoamer (manufactured by KURABO CORPORATION, "Mazerustar KK-250”) to prepare a mixture for evaluation.
• a solvent-soluble polyimide KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd.
• the obtained mixture for evaluation was applied to a glass plate having a thickness of 5 mm using an applicator set to a wet thickness of 250 ⁇ m, and then heated at 60° C. for 30 minutes, at 90° C. for 10 minutes, at 150° C. for 30 minutes, and at 200° C. for 30 minutes to remove ethyl acetate. Thereafter, the mixture was cooled to room temperature to obtain a film containing resin particles (2).
• Table 1 The results are shown in Table 1.
• Example 3 Resin particles (3) were obtained in the same manner as in Example 1, except that the amounts of SA9000, St, and DVB-810 were changed to 80 g, 279.2 g, and 40.8 g, respectively. The results are shown in Table 1.
• Example 4 Resin particles (4) were obtained in the same manner as in Example 1, except that the amounts of SA9000, St, and DVB-810 were changed to 120 g, 246.4 g, and 33.6 g, respectively. The results are shown in Table 1.
• Example 5 An oil phase was prepared by mixing 40 g of SA9000, 320 g of St, 40 g of DVB-810, 2 g of dodecanethiol as a thiol compound, 5.2 g of LPO (product name "Perloyl L", manufactured by NOF Corporation) as a polymerization initiator, and 1.6 g of benzoyl peroxide.
• 1.2 g of sodium lauryl sulfate was dissolved in 1,280 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate to prepare an aqueous phase.
• the oil phase was added to the aqueous phase, and dispersed for 5 minutes at a rotation speed of 8300 rpm using a TK homomixer to prepare a suspension, and then emulsified using a high-pressure emulsifier NVR (manufactured by Yoshida Kikai Kogyo Co., Ltd., model number "EM055-P20-0600-Exp") under conditions of an inlet treatment pressure of 17 MPa and an outlet pressure of 1 MPa to prepare a dispersion in which droplets of the oil phase were dispersed in the aqueous phase.
• NVR manufactured by Yoshida Kikai Kogyo Co., Ltd., model number "EM055-P20-0600-Exp
• the obtained dispersion was heated at 75°C for 3 hours, and then the internal temperature of the polymerization vessel was raised to 110°C (secondary heating), and the mixture was stirred at 110°C for 3 hours to complete the polymerization reaction.
• Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and the solid content was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain resin particles (5).
• An oil phase was prepared by mixing 80 g of SA9000, 280 g of St, 40 g of DVB-810, 2 g of dodecanethiol as a thiol compound, 2 g of Irganox 1010 (manufactured by BASF Japan Ltd.) as an antioxidant, 4 g of V-65 as a polymerization initiator, and 1.2 g of 2,2′-azobisisobutyronitrile (AIBN).
• 1.2 g of sodium lauryl sulfate was dissolved in 1,280 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate to prepare an aqueous phase.
• the oil phase was added to the aqueous phase, and dispersed for 5 minutes at a rotation speed of 8300 rpm using a TK homomixer to prepare a suspension, and then emulsified using a high-pressure emulsifier NVR (manufactured by Yoshida Kikai Kogyo Co., Ltd., model number "EM055-P20-0600-Exp") under conditions of an inlet treatment pressure of 17 MPa and an outlet pressure of 1 MPa to prepare a dispersion in which droplets of the oil phase were dispersed in the aqueous phase.
• NVR manufactured by Yoshida Kikai Kogyo Co., Ltd., model number "EM055-P20-0600-Exp
• the obtained dispersion was heated at 60°C for 2 hours, and then the internal temperature of the polymerization vessel was raised to 90°C (secondary heating), and the mixture was stirred at 90°C for 2 hours to complete the polymerization reaction.
• Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and the solid content was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain resin particles (6).
• the results are shown in Table 1.
• Example 7 An oil phase was prepared by mixing 160 g of a reactive low molecular weight polyphenylene ether "OPE-2St" (manufactured by Mitsubishi Gas Chemical Co., Inc.) as a compound having an ether structure, 196.8 g of St, 43.2 g of DVB-810, 4 g of Perloyl L as a polymerization initiator, and 1.6 g of benzoyl peroxide.
• 0.4 g of sodium lauryl sulfate was dissolved in 1,075 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate to prepare an aqueous phase.
• the oil phase was added to the aqueous phase, and dispersed for 5 minutes at 8300 rpm using a TK homomixer (manufactured by Primix Corporation) to prepare a suspension.
• the obtained suspension was heated at 70°C for 5 hours, and then the internal temperature of the polymerization vessel was raised to 105°C (secondary heating), and the mixture was stirred at 105°C for 2 hours to complete the polymerization reaction.
• Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and the solid content was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain resin particles (7).
• Table 1 The results are shown in Table 1.
• Example 8 Resin particles (8) were obtained in the same manner as in Example 5, except that dodecanethiol was not used. The results are shown in Table 1.
• 0.4 g of sodium lauryl sulfate was dissolved in 1,075 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate to prepare an aqueous phase.
• the oil phase was added to the aqueous phase, and dispersed for 5 minutes at 8300 rpm using a TK homomixer (manufactured by Primix Corporation) to prepare a suspension.
• the obtained suspension was heated at 55°C for 5 hours, and then the internal temperature of the polymerization vessel was raised to 105°C (secondary heating), and the mixture was stirred at 105°C for 2 hours to complete the polymerization reaction.
• the obtained mixture for evaluation was applied to a glass plate having a thickness of 5 mm using an applicator set to a wet thickness of 250 ⁇ m, and then heated at 60° C. for 30 minutes, at 90° C. for 10 minutes, at 150° C. for 30 minutes, and at 200° C. for 30 minutes to remove ethyl acetate. The mixture was then cooled to room temperature to obtain a film containing resin particles (C1). The results are shown in Table 1.
• the resin particles according to the embodiment of the present invention can be suitably used for semiconductor materials and the like.

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