Resin particles and resin composition for semiconductor member

Abstract

Provided are resin particles which can exhibit low dielectric loss tangent, can exhibit high heat resistance, and can exhibit excellent flexibility. Also provided is a resin composition for semiconductor members, which contains such resin particles. A resin particle according to an embodiment of the present invention contains a polymer P having a specific ether structure, and has a recovery rate of 4.6% or more as calculated by a load / unload test performed under the conditions of a temperature of 20 DEG C, a relative humidity of 65%, a load rate of 0.732 mN / sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN.

Description

TECHNICAL FIELD

[0001] The present application relates to a resin particle and a resin composition for semiconductor members. BACKGROUND

[0002] In order to achieve high speed of information processing using electronic devices, attempts have been made to lower the dielectric constant and the dielectric loss tangent of the insulating layer of a multilayer printed board. For example, it is being studied to achieve the lower dielectric constant and the lower dielectric loss tangent of the insulating layer by mixing resin particles in the resin forming the insulating layer.

[0003] It is required that the resin particles for semiconductor member use have high heat resistance, that is, the resin in which the resin particles are mixed does not substantially change even when heated at the time of molding processing or when a solder is used.

[0004] Further, it is required that the resin particles for semiconductor member use have excellent softness, that is, deformation or damage of the resin particles does not occur when a load based on pressing or the like is applied to the resin particles themselves or to the resin in which the resin particles are mixed.

[0005] A thermosetting resin molding material in which thermoplastic norbornene-based resin particles are compounded in a thermosetting resin raw material is reported, which has excellent electric properties such as insulation resistance, low dielectric constant, low dielectric loss tangent, and is useful as a material for a circuit board (Patent Document 1). However, the thermoplastic norbornene-based resin particles have a problem of being brittle and having poor softness. Further, the thermoplastic norbornene-based resin particles are particles obtained by pulverizing a block, a sheet, a particle, or the like of a thermoplastic norbornene-based resin, and thus are amorphous, and have a problem of having low filling property when mixed in a resin.

[0006] A hollow resin particle which can provide an organic insulating material having excellent insulation properties, a low dielectric constant, and a low dielectric loss tangent is reported (Patent Document 2). However, since it is a hollow resin particle, it has a problem of poor softness.

[0007] A resin sheet for insulating use 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 is reported (Patent Document 3). In the examples, a core-shell rubber particle is used as a particulate stress relaxation material, and a polybutadiene resin or a polycarbonate resin containing a phenolic hydroxyl group is used as a non-particulate stress relaxation material. However, the core-shell rubber particle described as a particulate stress relaxation material has a problem of high values of dielectric constant and dielectric loss tangent and insufficient heat resistance because the shell portion thereof is an acrylic resin. The non-particulate stress relaxation material is amorphous, and has a problem of low filling property when mixed in a resin.

[0008] A composition for modifying an insulating film containing a dispersion medium and a core-shell polymer having a rubbery elastic core layer is reported (Patent Literature 4). However, regarding the core-shell polymer, it is an acrylic resin as known from the composition of the polymer constituting the shell layer thereof, styrene / methyl methacrylate / acrylonitrile / glycidyl methacrylate = 60 / 50 / 30 / 40 (weight ratio) described in the examples, and thus there is a problem that the values of the dielectric constant and the dielectric loss tangent are high, and the heat resistance is insufficient.

[0009] Prior Art Documents

[0010] Patent Literature

[0011] [Patent Literature 1] Japanese Patent Application Laid-Open (JP-A) No. 6-162856

[0012] [Patent Literature 2] Japanese Patent Application Laid-Open (JP-A) No. 2000-313818

[0013] [Patent Literature 3] International Publication No. 2022-196696

[0014] [Patent Literature 4] Japanese Patent Application Laid-Open (JP-A) No. 2016-094527 SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] The present application was completed in order to solve the above-described conventional problems, and its main object is to provide resin particles capable of exhibiting a low dielectric loss tangent, capable of exhibiting a high heat resistance, and capable of exhibiting an excellent softness. A resin composition for a semiconductor member containing such resin particles is also provided.

[0017] MEANS FOR SOLVING THE PROBLEMS

[0018] [1] The resin particles of the embodiment of the present application contain a polymer P having an ether structure represented by Formula (1), and the recovery rate calculated by a load-unload test performed under conditions of a temperature of 20°C, a relative humidity of 65%, a load rate of 0.732 mN / sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN is 4.6% or more.

[0019] [Chemical Formula 1]

[0020]

[0021] [2] The resin particles according to the above-mentioned [1] can have a 3% weight loss temperature of 270°C or more when warmed at 10°C / minute in an air atmosphere.

[0022] [3] The resin particle according to any one of the above [1] or [2], wherein a dielectric loss tangent at a frequency of 10 GHz can be 0.0040 or less.

[0023] [4] The resin particle according to any one of the above [1] to [3], wherein a volume average particle diameter can be 0.1 μm to 100 μm.

[0024] [5] The resin particle according to any one of the above [1] to [4], wherein a coefficient of variation of a particle diameter can be 10% to 50%.

[0025] [6] The resin particle according to any one of the above [1] to [5], wherein an average circularity can be 0.95 to 1.00.

[0026] [7] The resin particle according to any one of the above [1] to [6], wherein the resin particle can be a solid particle.

[0027] [8] The resin particle according to any one of the above [1] to [7], wherein the polymer P can be a polymer obtained by a polymerization reaction of a monomer composition containing a compound A having an ether structure represented by the above formula (1) and a radical-reactive group, and a monomer M that reacts with the compound A.

[0028] [9] The resin particle according to the above [8], wherein the monomer M can contain an aromatic monofunctional monomer ml and an aromatic cross-linkable monomer m2.

[0029]

[10] The resin particle according to the above [8] or [9], wherein a content ratio of the compound A in the monomer composition can be 0.1% by weight or more and less than 60% by weight.

[0030]

[11] The resin particle according to the above [9] or

[10] , wherein a content ratio of the aromatic monofunctional monomer ml in the monomer component M can be 50% by weight to 99% by weight.

[0031]

[12] The resin particle according to any one of the above [9] to

[11] , wherein a content ratio of the aromatic cross-linkable monomer m2 in the monomer component M can be 1% by weight to 50% by weight.

[0032]

[13] The resin particle according to any one of the above [9] to

[12] , wherein, in the monomer composition, a content ratio of the aromatic cross-linkable monomer m2 with respect to the compound A, when the compound A is 100 parts by weight, the amount of the aromatic cross-linkable monomer m2 can be 1 part by weight to 1000 parts by weight.

[0033]

[14] The resin particle according to any one of the above-mentioned [8] to

[13] , wherein the thiol compound is contained in the monomer composition at less than 2 parts by weight per 100 parts by weight of the monomer composition.

[0034]

[15] The resin particle according to any one of the above-mentioned [1] to

[14] , which is usable for a semiconductor member.

[0035]

[16] A resin composition for a semiconductor member according to an embodiment of the present application contains the resin particle according to the above-mentioned

[15] .

[0036] Effects of the Invention

[0037] According to an embodiment of the present application, it is possible to provide a resin particle capable of exhibiting low dielectric loss tangent, capable of exhibiting high heat resistance, and capable of exhibiting excellent softness. It is also possible to provide a resin composition for a semiconductor member containing such a resin particle. DETAILED DESCRIPTION

[0038] Hereinafter, an embodiment of the present application will be described, but the present application is not limited to these embodiments.

[0039] In the present specification, when the expression "(meth)acrylic acid" appears, it means "acrylic acid and / or methacrylic acid", and when the expression "(meth)acrylate" appears, it means "acrylate and / or methacrylate".

[0040] Resin Particle

[0041] The resin particle according to an embodiment of the present application preferably has a recovery rate of 4.6% or more, more preferably 5% or more, further preferably 5.5% or more, more further preferably 6.0% or more, still further preferably 6.2% or more, particularly preferably 6.3% or more, most preferably 6.5% or more, as calculated by a load-unload test performed under conditions of a temperature of 20°C, a relative humidity of 65%, a load rate of 0.732 mN / sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN. The higher the recovery rate is, the better, but in reality, it can be 30% or less as an upper limit value. The higher the recovery rate is within the above range, the more the resin particle according to an embodiment of the present application can exhibit excellent softness. When the recovery rate exceeds the above range and is low, the softness of the resin particle becomes low, and it can cause deformation or damage of the resin particle when a load based on pressing or the like is applied to the resin particle itself or a resin in which the resin particle is mixed.

[0042] The 3% weight loss temperature of the resin particles of the embodiment of the present application when increasing the temperature at 10°C / minute in an air atmosphere is preferably 270°C or higher, more preferably 280°C or higher, further preferably 290°C or higher, still further preferably 300°C or higher, particularly preferably 310°C or higher, most preferably 320°C or higher. The higher the 3% weight loss temperature, the better, but in reality, as an upper limit, it can be 500°C or lower. The higher the 3% weight loss temperature within the above range, the more the resin particles of the embodiment of the present application can exhibit high heat resistance. When the 3% weight loss temperature exceeds the above range and is low, heating can cause the resin particles to be deformed, for example, when the resin particles are mixed with a thermosetting resin, heating for a curing reaction can cause the resin particles to be deformed, and the low dielectric loss tangent effect can be reduced. The method for measuring the 3% weight loss temperature will be described later.

[0043] The dielectric loss tangent of the resin particles of the embodiment of the present application at a frequency of 10 GHz is preferably 0.0040 or lower, more preferably 0.0030 or lower, further preferably 0.0020 or lower, particularly preferably 0.0015 or lower, most preferably 0.0010 or lower. As a lower limit of the dielectric loss tangent, it can be preferably 0 or higher. If the dielectric loss tangent is within the above range, the resin particles of the embodiment of the present application can exhibit low dielectric loss tangent of the resin itself or the resin in which the resin particles are mixed. The method for measuring the dielectric loss tangent will be described later.

[0044] The volume average particle diameter of the resin particles of the embodiment of the present application is preferably 0.1 μm to 100 μm. If the volume average particle diameter is within the above range, the resin particles of the embodiment of the present application can be used for various purposes. The method for measuring the volume average particle diameter will be described later.

[0045] In the case of the resin particles for semiconductor components, the volume average particle diameter of the resin particles of the embodiment of the present application is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 50 μm, further preferably 0.1 μm to 30 μm, particularly preferably 0.1 μm to 20 μm, most preferably 0.1 μm to 10 μm.

[0046] For purposes requiring micrometer-sized resin particles, the volume average particle diameter of the resin particles of the embodiment of the present application is preferably 0.1 μm to 100 μm, more preferably 0.3 μm to 50 μm, further preferably 0.6 μm to 30 μm, particularly preferably 0.8 μm to 20 μm, most preferably 1 μm to 10 μm.

[0047] For applications requiring resin particles of submicron size, the volume average particle diameter of the resin particles of the embodiments of the present application is preferably from 0.1 μm to 100 μm, more preferably from 0.1 μm to 50 μm, further preferably from 0.1 μm to 10 μm, particularly preferably from 0.1 μm to 5 μm, most preferably from 0.1 μm to 1 μm.

[0048] The coefficient of variation of the particle diameter of the resin particles of the embodiments of the present application is preferably from 10% to 50%, more preferably from 15% to 45%, further preferably from 18% to 42%, particularly preferably from 20% to 40%, most preferably from 22% to 38%. If the coefficient of variation of the particle diameter is within the above range, the resin particles are easily dispersed in a resin in which the resin particles are mixed, for example, and in addition, adverse effects due to an increase in the amount of coarse resin particles can be suppressed. When the coefficient of variation of the particle diameter of the resin particles is outside the above range and is too large, it can be difficult to achieve thinning or thickness variations when a resin layer is produced by mixing the resin particles in a resin, for example, due to an increase in the amount of coarse resin particles. When the coefficient of variation of the particle diameter of the resin particles is outside the above range and is too small, the resin particles are difficult to disperse in a resin in which the resin particles are mixed, for example, and thickness variations can occur when a resin layer is produced by mixing the resin particles in a resin. The method for measuring the coefficient of variation of the particle diameter will be described later.

[0049] The average circularity of the resin particles of the embodiments of the present application is preferably from 0.95 to 1.00, more preferably from 0.96 to 1.00, further preferably from 0.97 to 1.00, particularly preferably from 0.98 to 1.00, most preferably from 0.99 to 1.00. If the average circularity is within the above range, the shape of the resin particles of the embodiments of the present application is close to that of a true sphere, and therefore, the filling property when mixed in a resin, for example, is high. When the average circularity is outside the above range and is low, the shape of the resin particles deviates from that of a true sphere, and therefore, the filling property when mixed in a resin, for example, can be low.

[0050] The resin particles of the embodiments of the present application are preferably solid particles. If the resin particles of the embodiments of the present application are solid particles, more excellent softness can be exhibited.

[0051] <Polymers P>

[0052] The resin particles of the embodiments of the present application typically contain a polymer P having an ether structure represented by formula (1). By virtue of the polymer P having an ether structure represented by formula (1), the effects of the present application can be further exhibited.

[0053] [Chemical 2]

[0054]

[0055] The polymer P can be only one, or two or more.

[0056] The ether structure represented by Formula (1) that the polymer P has can be only one, or two or more.

[0057] The ether structure represented by Formula (1) that the polymer P has can be confirmed by any appropriate identification means such as NMR, IR, MS, and the like.

[0058] In terms of aspects in which the effects of the present application can be further exhibited, the content ratio of the polymer P in the resin particles of the embodiments of the present application is preferably from 60% by weight to 100% by weight, more preferably from 70% by weight to 100% by weight, further preferably from 80% by weight to 100% by weight, more further preferably from 90% by weight to 100% by weight, particularly preferably from 95% by weight to 100% by weight, most preferably from 98% by weight to 100% by weight.

[0059] A preferred embodiment of the polymer P is a polymer obtained by a polymerization reaction of a monomer composition containing a compound A having an ether structure represented by Formula (1) and a radical-reactive group, and a monomer M that reacts with the compound A. Here, the monomer composition consists of the compound A and the monomer M, and does not contain a polymerization initiator used for the polymerization reaction.

[0060] A preferred embodiment of the polymer P thus contains an ether structure represented by Formula (1) and a structural unit derived from a monomer contained in the monomer M. For example, when the monomer M contains an aromatic monofunctional monomer ml and an aromatic cross-linkable monomer m2 as described later, the preferred embodiment of the polymer P has an ether structure represented by Formula (1), a structural unit derived from the aromatic monofunctional monomer, and a structural unit derived from the aromatic cross-linkable monomer.

[0061] Here, the "structural unit derived from a monomer" refers to a structural unit of a polymer formed by cleavage of a radical-reactive group (typically, a carbon-carbon unsaturated double bond) possessed by a monomer contained in a monomer composition when the polymer is prepared by polymerization of the monomer composition. For example, the structural unit derived from a monomer of the structure of "RpRqC=CRrRs" (Rp, Rq, Rr, Rs are any appropriate groups bonded to a carbon atom through a single bond) refers to a structural unit of "-RpRqC-CRrRs-" formed by cleavage of the carbon-carbon unsaturated double bond "C=C" by polymerization.

[0062] Note that the proportion of the structural units derived from each monomer in the polymer can be known by various structural analyses of the polymer (e.g., NMR, etc.). Furthermore, even if such various structural analyses are not performed, the proportion of the structural units derived from each monomer in the polymer can be calculated based on the amount of each monomer used in the polymer production and the polymerization rate. In addition, the proportion of the structural units derived from each monomer in the polymer can be determined by any appropriate means other than these.

[0063] The compound A can be only one, or two or more.

[0064] As the radical-reactive group possessed by the compound A, any appropriate radical-reactive group can be used as long as it is a group generally known as a radical-reactive group without impairing the effects of the present application. In terms of further exhibiting the effects of the present application, as such a radical-reactive group, a group having a carbon-carbon unsaturated double bond can be preferably cited, and specifically, for example, a vinyl group, an acryloyl group, a methacryloyl group, an acrylamide group, an allyl group can be cited.

[0065] As the compound A, any appropriate compound can be used as long as it has the ether structure represented by formula (1) and the radical-reactive group without impairing the effects of the present application. In terms of further exhibiting the effects of the present application, as such a compound A, a polyphenylene ether (PPE) can be preferably cited.

[0066] As the compound A, for example, a polyphenylene ether (PPE) having a structure represented by formula (2) can be cited. Of course, the compound A is not limited to a polyphenylene ether (PPE) having a structure represented by formula (2) as long as it has the ether structure represented by formula (1) and the radical-reactive group.

[0067] [Chemical Formula 3]

[0068]

[0069] In formula (2), m, n represent the number of repeating units (the number of moles of addition) of the ether structure represented by formula (1), X 1 , X 2 is an organic group having a radical-reactive group, and Y is an organic group having no radical-reactive group. m, n are not particularly limited, and each can be, for example, 1 to 100, 2 to 70, 4 to 50, or 5 to 30.

[0070] As commercially available products of polyphenylene ether, for example, the trade name "NORYL (registered trademark)" series (NORYL (registered trademark) SA9000 and the like) (manufactured by SABIC), the trade name "Iupiace (registered trademark)" series (manufactured by Mitsubishi Chemical Corporation), the trade name "XYRON (registered trademark)" series (manufactured by Asahi Kasei Corporation), the trade name "OPE-2St" series (manufactured by Mitsubishi Gas Chemical Company, Inc.), and the trade name "DPPE-VBT50" (manufactured by DKS Co., Ltd.) can be mentioned.

[0071] In terms of aspects in which the effects of the present application can be further exhibited, the compound A can be an oligomer. In this case, the number average molecular weight Mn of the compound A is preferably 500 to 5000, more preferably 800 to 3500, further preferably 1000 to 3000, particularly preferably 1200 to 2500, most preferably 1400 to 2000.

[0072] In terms of aspects in which the effects of the present application can be further exhibited, the content ratio of the compound A in the monomer composition is preferably 0.1% by mass or more and less than 60% by mass, more preferably 0.1% by mass or more and less than 55% by mass, further preferably 0.1% by mass or more and less than 50% by mass, more further preferably 0.1% by mass or more and less than 45% by mass, still further preferably 0.1% by mass or more and less than 40% by mass, still further preferably 1% by mass to 35% by mass, still further preferably 3% by mass to 30% by mass, still further preferably 5% by mass to 25% by mass, particularly preferably 7% by mass to 22% by mass, most preferably 9% by mass to 21% by mass. When the content ratio of the compound A in the monomer composition exceeds the above range and is too low, it can be impossible to exhibit the effects of the present application, for example, it can be impossible to exhibit high heat resistance or to exhibit excellent softness. When the content ratio of the compound A in the monomer composition exceeds the above range and is too high, it can be impossible to exhibit the effects of the present application, for example, the compound A can be difficult to dissolve in the monomer composition, and thus it can be impossible to obtain resin particles.

[0073] As the monomer M, any appropriate monomer can be used as long as it is different from the compound A and reacts with the compound A, without impairing the effects of the present application. The monomer M can be only one kind, or two or more kinds.

[0074] In terms of aspects in which the effects of the present application can be further exhibited, as the monomer M, it is preferable to contain an aromatic monofunctional monomer ml and an aromatic crosslinkable monomer m2. The aromatic monofunctional monomer ml can be only one kind, or two or more kinds. The aromatic crosslinkable monomer m2 can be only one kind, or two or more kinds.

[0075] The aromatic monofunctional monomer m1 can be any appropriate aromatic monofunctional monomer, provided that it is a monofunctional aromatic monomer, without impairing the effects of the present application. In terms of further exhibiting the effects of the present application, as such an aromatic monofunctional monomer m1, for example, styrene, ethylvinylbenzene, a-methylstyrene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene can be exemplified. In terms of further exhibiting the effects of the present application, in terms of reactivity, as the aromatic monofunctional monomer m1, at least one selected from the group consisting of styrene and ethylvinylbenzene is preferred.

[0076] The aromatic crosslinkable monomer m2 can be any appropriate aromatic crosslinkable monomer, provided that it is an aromatic monomer having crosslinkability, without impairing the effects of the present application. In terms of further exhibiting the effects of the present application, as such an aromatic crosslinkable monomer m2, for example, divinylbenzene, diallyl phthalate, and divinyl naphthalene can be exemplified. In terms of further exhibiting the effects of the present application, in terms of reactivity, as the aromatic crosslinkable monomer m2, divinylbenzene is preferred.

[0077] In terms of further exhibiting the effects of the present application, the total content ratio of the aromatic monofunctional monomer m1 and the aromatic crosslinkable monomer m2 in the total amount of the monomers M is preferably 50% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, and most preferably 98% by weight or more, and 100% by weight or less.

[0078] As the monomers M, any appropriate other monomer different from the compound A, the aromatic monofunctional monomer m1, and the aromatic crosslinkable monomer m2 can be used, without impairing the effects of the present application. The other monomer can be only one, or two or more.

[0079] As other monomers, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like; maleic anhydride; (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid cyclopentyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid adamantyl ester, (meth)acrylic acid norbornyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid tricyclodecanyl ester, (meth)acrylic acid tetracyclododecanyl tetracyclododecanyl ester, (meth)acrylic acid hexadecyl ester, and the like (alkyl (meth)acrylate); dimethyl maleate, diethyl fumarate, dimethyl fumarate, diethyl fumarate, and the like (dicarboxylic acid ester monomers); 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, and the like (methacrylic acid derivative monomers having a carboxyl group and an ester bond); ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, and the like (polyfunctional (meth)acrylate); diallylamine, tetraallyloxyethane, and the like (polyfunctional allyl derivative monomers); butadiene, isoprene, and the like (conjugated diene monomers); vinyl chloride, vinylidene chloride, and the like (chlorine-containing monomers); (meth)acrylamide; N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, and the like (polyfunctional acrylamide derivative monomers); (meth)acrylonitrile; vinyl acetate; epoxy group-containing monomers; N-vinylcarbazole.

[0080] As to the aspect in which the effect of the present application can be further exhibited, the content ratio of the other monomers in the total amount of the monomers M is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 20% by mass or less, further preferably 0% by mass or more and 10% by mass or less, particularly preferably 0% by mass or more and 5% by mass or less, and most preferably 0% by mass or more and 2% by mass or less.

[0081] The content ratio of the monomer M in the monomer composition is preferably more than 40% by mass and 99.9% by mass or less, more preferably more than 45% by mass and 99.9% by mass or less, further preferably more than 50% by mass and 99.9% by mass or less, more further preferably more than 55% by mass and 99.9% by mass or less, still further preferably more than 60% by mass and 99.9% by mass or less, still further preferably 65% by mass to 99% by mass, still further preferably 70% by mass to 97% by mass, still further preferably 75% by mass to 95% by mass, particularly preferably 78% by mass to 93% by mass, most preferably 79% by mass to 91% by mass, in terms of an aspect in which the effect of the present application can be further exhibited. When the content ratio of the monomer M in the monomer composition exceeds the above range and is too low, it can be difficult to exhibit the effect of the present application, for example, the compound A can be difficult to dissolve in the monomer composition, and thus it can be difficult to obtain the resin particles. When the content ratio of the monomer M in the monomer composition exceeds the above range and is too high, it can be difficult to exhibit the effect of the present application, for example, it can be difficult to exhibit high heat resistance, or it can be difficult to exhibit excellent softness.

[0082] The content ratio of the aromatic monofunctional monomer m1 in the monomer M is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 97% by mass, further preferably 70% by mass to 95% by mass, more further preferably 80% by mass to 93% by mass, particularly preferably 85% by mass to 92% by mass, most preferably 87% by mass to 91% by mass, in terms of an aspect in which the effect of the present application can be further exhibited.

[0083] The content ratio of the aromatic crosslinkable monomer m2 in the monomer M is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, further preferably 5% by mass to 30% by mass, more further preferably 7% by mass to 20% by mass, particularly preferably 8% by mass to 15% by mass, most preferably 9% by mass to 13% by mass, in terms of an aspect in which the effect of the present application can be further exhibited.

[0084] The content ratio of the aromatic crosslinkable monomer m2 with respect to the compound A in the monomer composition is preferably 1 part by mass to 1000 parts by mass, more preferably 10 parts by mass to 500 parts by mass, further preferably 20 parts by mass to 400 parts by mass, more further preferably 25 parts by mass to 300 parts by mass, particularly preferably 30 parts by mass to 250 parts by mass, most preferably 35 parts by mass to 200 parts by mass, in terms of an aspect in which the effect of the present application can be further exhibited, when the amount of the aromatic crosslinkable monomer m2 is based on 100 parts by mass of the compound A.

[0085] The polymer P is obtained by polymerization of the monomer composition. The polymerization is preferably suspension polymerization. When suspension polymerization is performed, the polymerization is typically performed by adding the oil phase to the water phase to disperse it.

[0086] As for dispersion, any appropriate dispersion method can be used within a range not impairing the effects of the present application, provided that the oil phase can exist in the water phase in the form of droplets. As such a dispersion method, a dispersion method using a homomixer or a homogenizer can be exemplified, such as a high-speed homomixer, a Polytron homogenizer, an ultrasonic homogenizer, and a high-pressure homogenizer.

[0087] The water phase typically contains a water-based solvent. As the water-based solvent, water, a mixed solvent of water and a lower alcohol (methanol, ethanol, etc.) can be exemplified.

[0088] The water-based solvent can be used in any appropriate amount within a range not impairing the effects of the present application. As such an amount of the water-based solvent, 10 parts by weight to 5000 parts by weight, more preferably 50 parts by weight to 3000 parts by weight, and further preferably 100 parts by weight to 2000 parts by weight, relative to 100 parts by weight of the monomer composition, is preferable.

[0089] The oil phase can contain an organic solvent. As the organic solvent, an organic solvent having a boiling point of less than 100°C is typically used. As the organic solvent having a boiling point of less than 100°C, heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, butanone, chloroform, carbon tetrachloride can be exemplified. The organic solvent having a boiling point of less than 100°C can be a mixed solvent.

[0090] The organic solvent is preferably used in an amount of 20 parts by weight to 250 parts by weight, relative to 100 parts by weight of the monomer composition. However, in the case where the resin particles of the embodiment of the present application are solid particles, it is preferable that no organic solvent is used, and the organic solvent is preferably used in an amount of less than 20 parts by weight, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, particularly preferably 1 part by weight or less, and most preferably 0.1 part by weight or less, relative to 100 parts by weight of the monomer composition.

[0091] In the polymerization of the monomer composition, any appropriate additive B that is neither compound A nor monomer M can be used within a range not impairing the effects of the present application. The additive B can be only one or two or more.

[0092] As the additive B, a polymerization initiator, a surfactant, a dispersion stabilizer, a mercaptan compound, and an antioxidant can be exemplified.

[0093] As the polymerization initiator, any appropriate polymerization initiator can be used within a range not impairing the effects of the present application. The polymerization initiator can be only one, or two or more. As such a polymerization initiator, for example, organic peroxides such as lauroyl peroxide (LPO), benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butyl 2-ethylhexanoate peroxide, di-tert-butyl peroxide, and the like; azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, 2,2'-azobis(2,4-dimethylpentanenitrile), and the like can be exemplified. Among these polymerization initiators, if an organic peroxide is used, a more excellent low dielectric loss tangent of the resin particles can be exhibited.

[0094] The polymerization initiator can be added to the water phase or the oil phase, but is typically added to the oil phase.

[0095] The amount of the polymerization initiator to be added is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 5 parts by weight, relative to 100 parts by weight of the monomer composition.

[0096] As the surfactant, any appropriate surfactant can be used within a range not impairing the effects of the present application. The surfactant can be only one, or two or more. In terms of further exhibiting the effects of the present application, as the surfactant, at least one selected from the group consisting of amphoteric surfactants and anionic surfactants is preferred.

[0097] As the amphoteric surfactant, any appropriate amphoteric surfactant can be used within a range not impairing the effects of the present application. As such an amphoteric surfactant, a publicly known amphoteric surfactant that can be used in the production of the resin particles can be used. As the amphoteric surfactant, for example, lauryl dimethyl amine oxide, lauryl dimethyl amido glycine betaine, phosphate ester-based surfactants, phosphite ester-based surfactants can be exemplified. The amphoteric surfactant can be only one, or two or more.

[0098] As the anionic surfactant, any appropriate anionic surfactant can be used within a range not impairing the effects of the present application. As such anionic surfactants, for example, the following can be listed: fatty acid salts, polysulfonic acid salts, polycarboxylic acid salts, alkyl sulfate salts, alkyl aryl sulfonic acid salts, alkylnaphthalene sulfonic acid salts, dialkyl sulfonic acid salts, dialkyl sulfosuccinic acid salts, alkyl phosphate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl aryl ether sulfate salts, naphthalene sulfonic acid formaldehyde condensate salts, polyoxyethylene alkyl phosphate sulfonic acid salts, glycerin borate fatty acid esters, polyoxyethylene glycerin fatty acid esters. Specifically, for example, the following can be listed: sodium dodecylbenzenesulfonate, sodium laurylsulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonyl phenyl ether sulfate salt, sodium salt of β-naphthalene sulfonic acid formaldehyde condensate. The anionic surfactant can be only one, or two or more.

[0099] The surfactant can be added to the water phase or to the oil phase, but is typically added to the water phase.

[0100] The surfactant is preferably used in an amount of 0.001 parts by weight to 1 part by weight, more preferably 0.005 parts by weight to 0.5 parts by weight, and further preferably 0.01 parts by weight to 0.1 parts by weight, relative to 100 parts by weight of the water-based solvent contained in the water phase.

[0101] As the dispersion stabilizer, any appropriate dispersion stabilizer can be used within a range not impairing the effects of the present application. The dispersion stabilizer can be only one, or two or more. In terms of further exhibiting the effects of the present application, as the dispersion stabilizer, for example, the following can be listed: polyvinyl alcohol; polycarboxylic acid; celluloses such as hydroxyethyl cellulose, carboxymethyl cellulose; polyvinylpyrrolidone; inorganic water-soluble polymers such as sodium tripolyphosphate; phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate; water-insoluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, colloidal silica. Among these, in terms of further exhibiting the effects of the present application, magnesium pyrophosphate is preferred.

[0102] The dispersion stabilizer can be added to the water phase or to the oil phase, but is typically added to the water phase.

[0103] The dispersion stabilizer is preferably used in an amount of 0.1 parts by weight to 50 parts by weight, and more preferably 0.5 parts by weight to 10 parts by weight, relative to 100 parts by weight of the water-based solvent contained in the water phase.

[0104] As the thiol compound, any appropriate thiol compound can be used within a range not impairing the effects of the present application. The thiol compound can be only one, or two or more. As such a thiol compound, for example, multifunctional thiol compounds, monofunctional thiol compounds having an alkyl group having 1 or more and 20 or less carbon atoms in the molecule can be listed.

[0105] As the multifunctional thiol compound, any appropriate multifunctional thiol compound can be used within a range not impairing the effects of the present application, as long as it is a compound having two or more mercapto groups in the molecule. The multifunctional thiol compound can be only one, or two or more. As such a multifunctional thiol compound, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2-cyclohexanedithiol, decanedithiol, ethyleneglycol bithio glycolate, ethyleneglycol bithio propionate, ethyleneglycol bithio glycolate (EGTG), 1,4-butanediol bithio propionate (BDTG), trimethylolpropane trithio glycolate (TMTG), trimethylolpropane trithio propionate, pentaerythritol tetra thio glycolate (PETG), pentaerythritol tetra thio propionate, dipentaerythritol hexa thio propionate, tris (2-hydroxyethyl) isocyanurate trithiopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine can be listed. Among them, ethyleneglycol bithio glycolate (EGTG), 1,4-butanediol bithio propionate (BDTG), trimethylolpropane trithio glycolate (TMTG), pentaerythritol tetra thio glycolate (PETG) are preferred.

[0106] As the monofunctional thiol compound having an alkyl group having 1 or more and 20 or less carbon atoms in the molecule, any appropriate monofunctional thiol compound having an alkyl group having 1 or more and 20 or less carbon atoms in the molecule can be used within a range not impairing the effects of the present application, as long as it is a compound having one mercapto group in the molecule and having an alkyl group having 1 or more and 20 or less carbon atoms. The monofunctional thiol compound having an alkyl group having 1 or more and 20 or less carbon atoms in the molecule can be only one, or two or more. As such a monofunctional thiol compound having an alkyl group having 1 or more and 20 or less carbon atoms in the molecule, for example, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, dodecyl mercaptan, compounds having these branched structures can be listed.

[0107] The amount of the mercaptan compound to be added is preferably 5 parts by weight or less, more preferably 0.05 to 5 parts by weight, further preferably 0.1 to 3 parts by weight, particularly preferably 0.3 to 2 parts by weight, relative to 100 parts by weight of the monomer composition. That is, the mercaptan compound is preferably contained in an amount of 5 parts by weight or less, more preferably 0.05 to 5 parts by weight, further preferably 0.1 to 3 parts by weight, particularly preferably 0.3 to 2 parts by weight, relative to 100 parts by weight of the monomer composition.

[0108] The mercaptan compound can function as a chain transfer agent and can become a structural unit of the polymer P. The mercaptan compound can, in 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, a polyfunctional (meth)acrylic monomer), stop elongation of a polymer chain by capturing a radical from a growing polymer chain, at the same time, generate a new radical, and start a growth reaction of another polymer chain. Thus, the molecular weight of the resulting polymer P, and further, the resin particles of the embodiments of the present application, can be made uniform, and the particle size distribution can be made uniform.

[0109] As the antioxidant, any appropriate antioxidant can be used within a range not impairing the effects of the present application. The antioxidant can be only one kind, or two or more kinds. As such an antioxidant, for example, an antioxidant having a melting point of 30°C or higher and 105°C or lower can be exemplified. When an antioxidant having a melting point lower than 30°C is used, the external air temperature can cause the antioxidant to be liquefied when the resin particles are recovered as a dry powder. When an antioxidant having a melting point exceeding 105°C is used, the dispersion stability of the dispersion of the resin particles can be affected at the time of heat treatment.

[0110] As the antioxidant, a substance in a powder state at room temperature (25°C) can be used. In addition, a substance dispersed or dissolved in water, alcohol, or the like can also be used.

[0111] As the antioxidant, for example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant can be exemplified. From the viewpoint that the effects of the present application can be further exhibited, an antioxidant having a radical capturing ability is preferred, a phenolic antioxidant, an amine antioxidant is preferred, and a phenolic antioxidant is more preferred.

[0112] As the phenolic antioxidant, any appropriate phenolic antioxidant can be used within a range not impairing the effects of the present application. As such a phenolic antioxidant, a compound having an alkyl group or the like as a substituent in the ortho position with respect to the phenolic hydroxyl group is preferred. Further, from the viewpoint of further exhibiting the effects of the present application and the like, the use of p-methoxyphenol is preferred. As the phenolic antioxidant, for example, 3-(4'-hydroxy-3',5-di-tert-butylphenyl)propionic acid n-octadecyl ester, ethylenebis(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, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] can be exemplified.

[0113] As the phosphorus antioxidant, any appropriate phosphorus antioxidant can be used within a range not impairing the effects of the present application. As such a phosphorus antioxidant, for example, 3,9-di-octadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphospha- spiro(5.5)undecane can be exemplified.

[0114] As the sulfur antioxidant, any appropriate sulfur antioxidant can be used within a range not impairing the effects of the present application. As such a sulfur antioxidant, for example, 3,3'-thiodipropionic acid dioctadecyl ester, pentaerythritol tetrakis[3-(dodecylthio)propionate] can be exemplified.

[0115] As the amine antioxidant, any appropriate amine antioxidant can be used within a range not impairing the effects of the present application. As such an amine antioxidant, for example, sebacic acid bis(2,2,6,6-tetramethyl-4-piperidyl) ester, butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate can be exemplified.

[0116] The addition amount of the antioxidant is preferably 0.05 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 3 parts by weight, with respect to 100 parts by weight of the monomer composition.

[0117] The polymerization temperature can be any appropriate polymerization temperature within a range not impairing the effects of the present application, as long as it is a temperature suitable for suspension polymerization. As such a polymerization temperature, for example, the initial temperature of polymerization can be set to 30°C to 80°C, and then the temperature is increased, and the later-stage temperature of polymerization can be set to 70°C to 120°C.

[0118] The polymerization time can be any appropriate time for suspension polymerization, provided that the effects of the present application are not impaired. As such a polymerization time, it is preferably 1 hour to 48 hours at the initial temperature of polymerization, and preferably 1 hour to 24 hours at the later temperature of polymerization.

[0119] After the polymerization, the resin particles of the embodiment of the present application can be subjected to decomposition treatment of a dispersing stabilizer such as magnesium pyrophosphate, washing, separation, drying, and the like, as needed, to thereby obtain the resin particles of the embodiment of the present application.

[0120] "Resin particles for semiconductor members and resin composition for semiconductor members"

[0121] In terms of aspects in which the effects of the present application can be further utilized, the resin particles of the embodiment of the present application are suitable for semiconductor members. That is, the resin particles of the embodiment of the present application are preferably for semiconductor members.

[0122] The semiconductor member means a member constituting a semiconductor, and examples thereof include a semiconductor package and a semiconductor module.

[0123] The semiconductor package is constituted with at least one member selected from the group consisting of a molding resin, an underfill material, a mold underfill material, a die attach material, a prepreg for a semiconductor package substrate, a metal-clad laminate for a semiconductor package substrate, and a build-up material for a printed circuit board for a semiconductor package, as an essential constituent member.

[0124] The semiconductor module is constituted with at least one member selected from the group consisting of a prepreg for a printed circuit board, a metal-clad laminate for a printed circuit board, a build-up material for a printed circuit board, a solder resist material, a cover film, an electromagnetic wave shielding film, and an adhesive sheet for a printed circuit board, as an essential constituent member.

[0125] The resin particles of the embodiment of the present application can exhibit low dielectric loss tangent, can exhibit high heat resistance, and can exhibit excellent flexibility, and thus can be suitably used for a resin composition for semiconductor members. That is, the resin composition for semiconductor members of the embodiment of the present application contains the resin particles of the embodiment of the present application. In the present specification, the resin composition for semiconductor members means a resin composition for semiconductor members.

[0126] The resin composition for semiconductor members of the embodiment of the present application typically contains the resin particles of the embodiment of the present application and a resin component.

[0127] As the resin component, any appropriate resin component used in semiconductor members can be used.

[0128] The content ratio of the resin particle of the embodiment of the present application in the resin composition for a semiconductor member can be appropriately set according to the purpose.

[0129] Other uses of the resin particle

[0130] The resin particle of the embodiment of the present application can be applied to any appropriate other use such as a paint composition, a cosmetic, a light-diffusing composition, a light-diffusing film, and the like, in addition to a semiconductor member.

[0131] Paint composition

[0132] The resin particle of the embodiment of the present application can impart an excellent appearance to a coating film containing the same, and thus can be suitably used for a paint composition. Such a paint composition contains the resin particle of the embodiment of the present application.

[0133] The paint composition preferably contains at least one selected from the group consisting of a binder resin and a UV-curable resin. The binder resin can be only one or two or more. The UV-curable resin can be only one or two or more.

[0134] As the binder resin, any appropriate binder resin can be used within a range not impairing the effects of the present application. As such a binder resin, for example, a resin soluble in an organic solvent or water, an emulsion-type water-based resin capable of being dispersed in water can be exemplified. As the binder resin, specifically, for example, an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, a chlorinated polyolefin resin, an amorphous polyolefin resin can be exemplified.

[0135] As the UV-curable resin, any appropriate UV-curable resin can be used within a range not impairing the effects of the present application. As such a UV-curable resin, for example, a multifunctional (meth)acrylate resin, a multifunctional polyurethane acrylate resin, preferably a multifunctional (meth)acrylate resin, more preferably a multifunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule can be exemplified. As the multifunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule, specifically, for example, trimethylolpropane tri(meth)acrylate, trimethyloloethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate can be exemplified.

[0136] When the coating composition contains at least one selected from the group consisting of the binder resin and the UV-curable resin, the content ratio can be any appropriate content ratio according to the purpose. Typically, the resin particles of the embodiments of the present application are preferably 5 to 50% by weight, more preferably 10 to 50% by weight, and further preferably 20 to 40% by weight, relative to the total amount of at least one selected from the group consisting of the binder resin (in the case of an emulsion type water-based resin, the solid content is converted) and the UV-curable resin and the resin particles of the embodiments of the present application.

[0137] When the UV-curable resin is used, it is preferable to use a photopolymerization initiator in combination. As the photopolymerization initiator, any appropriate photopolymerization initiator can be used within a range not impairing the effects of the present application. As such a photopolymerization initiator, for example, acetophenone-based, benzoin-based, benzophenone-based, phosphine oxide-based, ketal-based, a-hydroxyalkylphenone-based, a- aminoalkylphenone, anthraquinone-based, thioxanthone-based, azo compound, peroxide-based (described in Japanese Patent Application Publication No. 2001-139663, etc.), 2,3-dialkyldiketone compound, disulfide, fluoramine compound, aromatic sulfonium salt, onium salt, borate, active halogen compound, a-acyloxime ester can be listed.

[0138] The coating composition can contain a solvent. The solvent can be only one, or two or more. When the coating composition contains a solvent, the content ratio can be any appropriate content ratio according to the purpose.

[0139] As the solvent, any appropriate solvent can be used within a range not impairing the effects of the present application. As such a solvent, a solvent capable of dissolving or dispersing the binder resin or the UV-curable resin is preferable. As such a solvent, in the case of an oil-based paint, for example, a hydrocarbon-based solvent such as toluene, xylene, and the like; a ketone-based solvent such as butanone, methyl isobutyl ketone, and the like; an ester-based solvent such as ethyl acetate, butyl acetate, and the like; an ether-based solvent such as dioxane, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, and the like can be listed, and in the case of a water-based paint, for example, water, an alcohol can be listed.

[0140] The coating composition can be diluted as necessary to adjust the viscosity. As the diluent, any appropriate diluent can be used according to the purpose. As such a diluent, the aforementioned solvent can be listed. The diluent can be only one, or two or more.

[0141] The coating composition can contain other components as necessary, for example, a surface adjusting agent, a flowability adjusting agent, an ultraviolet absorber, a light stabilizer, a curing catalyst, a extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, a dye.

[0142] When the coating composition is used to form a coating film, as a coating method thereof, any appropriate coating method can be employed according to the purpose. As such a coating method, for example, a spray coating method, a roll coating method, a brush coating method, a reverse roll coating method, a gravure coating method, a die coating method, a comma coating method, a spray coating method can be cited.

[0143] When the coating composition is used to form a coating film, as a forming method thereof, any appropriate forming method can be employed according to the purpose. As such a forming method, for example, a method in which a coating film is produced by coating an arbitrary coating surface of a substrate, the coating film is dried, and the coating film is cured as necessary, whereby a coating film is formed, can be cited. As the substrate, for example, a metal, a wood, a glass, a plastic (PET (polyethylene terephthalate), PC (polycarbonate), an acrylic resin, TAC (triacetyl cellulose), and the like) can be cited.

[0144] <Light-diffusing resin composition>

[0145] The resin particle of the embodiment of the present application can impart excellent light-diffusing properties to a coating film containing the same, and thus can be suitably used for a light-diffusing resin composition. Such a light-diffusing resin composition contains the resin particle of the embodiment of the present application.

[0146] The light-diffusing resin composition preferably contains at least one selected from the group consisting of a binder resin and a UV-curable resin. As for the binder resin and the UV-curable resin, the aforementioned description for the coating composition can be cited.

[0147] The light-diffusing resin composition can contain a solvent. As for the solvent, the aforementioned description for the coating composition can be cited.

[0148] The light-diffusing resin composition can be diluted as necessary to adjust the viscosity. As a diluent, the aforementioned description for the coating composition can be cited.

[0149] The light-diffusing resin composition can contain other components as necessary, such as a coating surface adjusting agent, a flowability adjusting agent, an ultraviolet absorber, a light stabilizer, a curing catalyst, a extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, a dye.

[0150] As a coating method and a forming method when a coating film is formed using the light-diffusing resin composition, the aforementioned description for the coating composition can be cited.

[0151] <Light-diffusing film>

[0152] The resin particle of the embodiment of the present application can impart excellent light-diffusing properties to a film provided with a coating film containing the same, and thus can be suitably used for a light-diffusing film. Such a light-diffusing film contains the resin particle of the embodiment of the present application.

[0153] The light diffusion film contains a light diffusion layer formed of a light diffusion resin composition and a substrate. Note that the light diffusion layer can be the outermost layer of the light diffusion film or can not be the outermost layer. The light diffusion film of the embodiments of the present application can contain any appropriate other layer as needed. As such other layer, for example, a protective layer, a hard coat layer, a planarization 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, a primer layer can be cited.

[0154] As the substrate, for example, a metal, wood, glass, a plastic film, a plastic sheet, a plastic lens, a plastic panel, a cathode ray tube, a fluorescent display tube, a liquid crystal display panel can be cited. As the plastic constituting the plastic film, the plastic sheet, the plastic lens, the plastic panel, for example, PET (polyethylene terephthalate), PC (polycarbonate), an acrylic resin, TAC (triacetyl cellulose) can be cited.

[0155] Example

[0156] Hereinafter, the present application will be specifically described by citing examples, but the present application is not limited to these examples. Note that, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

[0157] <Method for measuring volume average particle diameter and coefficient of variation of particle diameter of resin particles>

[0158] 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 Corporation). The measurement was performed using a pore size corrected according to the Multisizer (registered trademark) 3 User Manual issued by BECKMAN COULTER Corporation. Note that the pore size used in the measurement was appropriately selected according to the size of the particles to be measured, for example: a pore size having a size of 50 μm was selected when the expected volume average particle diameter of the particles to be measured was 1 μm or more and 10 μm or less; a pore size having a size of 100 μm was selected when the expected volume average particle diameter of the particles to be measured was more than 10 μm and 30 μm or less; a pore size having a size of 280 μm was selected when the expected volume average particle diameter of the particles to be measured was more than 30 μm and 90 μm or less; a pore size having a size of 400 μm was selected when the expected volume average particle diameter of the particles to be measured was more than 90 μm and 150 μm or less, and the like. When the volume average particle diameter after the measurement was different from the expected volume average particle diameter, the measurement was performed again using a pore size having an appropriate size. The Current (pore current) and Gain (gain) were appropriately set according to the size of the selected pore size. For example, if a pore size having a size of 50 μm was selected, the Current (pore current) was set to -800 and the Gain (gain) was set to 4; if a pore size having a size of 100 μm was selected, the Current (pore current) was set to -1600 and the Gain (gain) was set to 2; if a pore size having a size of 280 μm or 400 μm was selected, the Current (pore current) was set to -3200 and the Gain (gain) was set to 1.

[0159] Specifically, a dispersion liquid prepared by dispersing 0.1 g of the resin particles to be measured in 10 ml of a 0.1 mass% aqueous solution of a nonionic surfactant using a touch mixer (TOUCH MIXER MT-31, manufactured by YAMATO Scientific Co., Ltd.) and an ultrasonic cleaner (VELVO-CLEAR "ULTRASONIC CLEANER VS-150") was used. In the measurement, the liquid was slowly stirred in a beaker to the extent that no air bubbles were introduced, and the measurement was ended at the time point at which 100,000 resin particles were measured. The volume average particle diameter of the resin particles to be measured was the arithmetic average diameter of the particle size distribution based on the volume of 100,000 particles.

[0160] The coefficient of variation (CV value) of the particle diameter was calculated by the following equation.

[0161] Coefficient of variation (%) of particle size of particles = (standard deviation of particle size distribution on particle volume basis ÷ volume average particle size of particles) x 100 (%)

[0162] <Method for measuring roundness and method for calculating average roundness>

[0163] The roundness of the resin particles was measured using a flow-type particle image analyzer ("FPIA (registered trademark) -3000S" manufactured by Sysmex Corporation). As a specific measurement method, 0.05 g of sodium dodecylbenzenesulfonate as a dispersant was added to 20 mL of ion exchange water to obtain a surfactant aqueous solution. Next, 0.2 g of the resin particles to be measured was added to the obtained surfactant aqueous solution, and ultrasonic irradiation was performed for 5 minutes using an ultrasonic disperser "BRANSON SONIFIER 450" (output power 400 W, frequency 20 kHz) manufactured by BRANSON Corporation as a dispersing machine to perform dispersion treatment of the resin particles to be measured in the surfactant aqueous solution, thereby preparing a dispersion liquid for measurement.

[0164] The above flow-type particle image analyzer equipped with a standard objective lens (10 times) was used in the measurement. As a sheath liquid used in the above flow-type particle image analyzer, a Particle Sheath ("PSE-900A" manufactured by Sysmex Corporation) was used.

[0165] The dispersion liquid for measurement prepared according to the above procedure was introduced into the above flow-type particle image analyzer, and measurement was performed in accordance with the following [Measurement conditions for roundness]. At the time of measurement, before the start of measurement, a suspension of a standard polymer particle group (for example, "5200A" manufactured by Thermo Fisher Scientific Inc. (standard polystyrene particles diluted with ion exchange water)) was used to perform autofocusing of the above flow-type particle image analyzer.

[0166] The roundness refers to a value obtained by dividing the circumference calculated from the diameter of a true circle having the same projected area as the resin particle photographed image by the circumference of the resin particle photographed image. The average roundness refers to a value obtained by dividing the sum of the roundness of each resin particle by the sum of the frequency on a number basis. The proportion of the number of hollow particles having an average roundness of 0.90 or less was calculated from the data of the frequency on a number basis of the number of intervals of 0.010 (for example, 0.200 or more and less than 0.990) measured by the above measurement.

[0167] [Measurement conditions for roundness]

[0168] • Measurement mode: LPF measurement mode or HPF measurement mode

[0169] (Conversion volume average particle diameter is appropriately selected. As a standard, in the case of a conversion volume average particle diameter of 8 μm or less, the HPF measurement mode is selected, and in the case of a conversion volume average particle diameter of 8 μm or more, the LPF measurement mode is selected.)

[0170] • Number of measured resin particles: 1000

[0171] • Measurement range of conversion volume average particle diameter: 0.5 μm to 200 μm

[0172] • Measurement range of circularity of resin particles: 0.2 to 1.0

[0173] <3% weight loss temperature of resin particles>

[0174] The 3% weight loss temperature of the resin particles was measured using a differential thermal gravimetric simultaneous measurement device, "TG / DTA6200, AST-2" manufactured by SII Nano Technology Inc. The sampling method and temperature conditions were as follows.

[0175] The bottom of a platinum measurement container was filled with 10.5 ± 0.5 mg of a sample without gaps, as a sample for measurement. The 3% weight loss temperature was measured with alumina as a reference material under an air flow of 230 mL / minute. The TG / DTA curve was obtained by raising the temperature of the sample at a rate of 10°C / minute from 30°C to 500°C. Using the analysis software attached to the device, the temperature at the time of 3% weight loss was calculated from the obtained curve as the 3% weight loss temperature.

[0176] <Recovery rate of resin particles>

[0177] The measurement of the recovery rate of the resin particles was performed by a load-unload test using a micro compression tester "MCTM-200" manufactured by Shimadzu Corporation under the following measurement conditions.

[0178] Specifically, a dispersion liquid in which the resin particles were dispersed in ethanol was applied to a mirror-finished steel sample stage, and dried to prepare a sample for measurement. Next, in an environment of room temperature 20°C and relative humidity 65%, one independent fine resin particle (in a state in which no other resin particles were present within a range of 100 μm in diameter) was selected using an optical microscope of the MCTM-200, and the diameter of the selected resin particle was measured using a particle diameter measurement cursor of the MCTM-200.

[0179] The selected resin particles are microparticles having a diameter in the range of 7 μm to 9 μm, and resin particles outside this range are not used for the compression strength measurement. Next, the particle diameter A when a load is applied to the resin particles up to a maximum load of 9.81 mN, and the particle diameter B when subsequently unloaded to a minimum test force of 1.96 mN, are measured by lowering the test indenter to the apex of the selected resin particles at a loading speed as described below. From the displacement amount (recovery amount) obtained from the particle diameters A and B, the individual recovery rate is calculated using the following formula. The measurement is performed on 6 resin particles, and from the 6 recovery rates, the maximum and minimum values are removed, and the average of the remaining 4 data is taken as the recovery rate.

[0180] [Recovery rate calculation formula]

[0181] Recovery rate (%) = Recovery amount (μm) / Particle diameter under no load (μm) x 100

[0182] [Recovery rate measurement conditions]

[0183] Test temperature: Normal temperature (20°C), relative humidity 65%

[0184] Upper pressure indenter: Flat indenter (material: diamond) having a diameter of 50 μm

[0185] Lower pressure plate: SKS flat plate

[0186] Test type: Load-unload test

[0187] Maximum test force: 9.81 mN

[0188] Minimum test force: 1.96 mN

[0189] Loading speed: 0.732 mN / sec

[0190] Loading holding time: 1 second

[0191] Unloading holding time: 1 second

[0192] [Dielectric properties of resin particles]

[0193] The dielectric properties of the resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Corporation. Based on the perturbation theory using a resonator, the dielectric loss tangent of the resin particles was calculated at a frequency of 10 GHz, a measurement environment of 23°C, and a relative humidity of 51 ± 1%.

[0194] [Dielectric properties of a film to which resin particles are added]

[0195] The dielectric loss tangent of the film containing the obtained resin particles was measured by a cavity resonance method (measurement frequency: 5.8 GHz). The measurement result was set as a relative ratio (%) when the measurement value of the film not containing the resin particles was 100%.

[0196] [Example 1]

[0197] A reactive low-molecular-weight polyphenyl ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC) as a compound having an ether structure: 20 g, styrene (St): 334.4 g, divinylbenzene (DVB) (trade name "DVB-810", manufactured by Nippon Steel Chemical Co., Ltd., containing 81% of DVB, and the remaining 19% being ethylvinylbenzene (EVB)): 45.6 g, 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by FUJIFILM Wako Pure Chemical Corporation) as a polymerization initiator: 4 g, and benzoyl peroxide: 1.08 g were mixed to prepare an oil phase.

[0198] Sodium lauryl sulfate: 0.4 g was dissolved in a 2.2% by weight aqueous solution of magnesium pyrophosphate: 1075 g to prepare an aqueous phase.

[0199] The oil phase was added to the aqueous phase, and a suspension was prepared by dispersing the mixture using a TK homogenizer (manufactured by PRIMIX Corporation) at a rotation speed of 8300 rpm for 5 minutes. After the obtained suspension was heated at 55°C for 5 hours, the temperature inside the polymerization kettle was increased to 105°C (two-step temperature increase), and the polymerization reaction was completed by stirring at 105°C for 2 hours. After hydrochloric acid was added to the obtained slurry to decompose the magnesium pyrophosphate, the solid component was separated by filtration and dehydration, and the obtained resin particles (1) were refined by repeated water washing and dried at 80°C for 24 hours.

[0200] The results are shown in Table 1.

[0201] [Example 2]

[0202] Except that SA9000 was changed to 40 g, St was changed to 316.8 g, and DVB-810 was changed to 43.2 g, the same procedure as in Example 1 was performed to obtain resin particles (2).

[0203] Further, the obtained resin particles (2): 0.425 g, ethyl acetate: 8.3 g, and solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Kakohki Co., Ltd.): 1.7 g were defoamed and stirred using a planetary stirring defoaming machine (manufactured by KURABO Co., Ltd., "MAZERU STAR KK-250") to prepare a mixture for evaluation.

[0204] The resulting evaluation mixture was coated on a glass plate having a thickness of 5 mm using a coater with a wet thickness set to 250 μm, 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, and then cooled to room temperature, thereby obtaining a film containing the resin particles (2).

[0205] The results are shown in Table 1.

[0206] [Example 3]

[0207] The resin particles (3) were obtained in the same manner as in Example 1, except that SA9000 was changed to 80 g, St was changed to 279.2 g, and DVB-810 was changed to 40.8 g.

[0208] The results are shown in Table 1.

[0209] [Example 4]

[0210] The resin particles (4) were obtained in the same manner as in Example 1, except that SA9000 was changed to 120 g, St was changed to 246.4 g, and DVB-810 was changed to 33.6 g.

[0211] The results are shown in Table 1.

[0212] [Example 5]

[0213] An oil phase was prepared by mixing SA9000: 40 g, St: 320 g, DVB-810: 40 g, dodecanethiol as a thiol compound: 2 g, LPO (trade name "PEROYL L", manufactured by NOF Corporation) as a polymerization initiator: 5.2 g, and benzoyl peroxide: 1.6 g.

[0214] An aqueous phase was prepared by dissolving sodium lauryl sulfate: 1.2 g in a 2.2% by weight aqueous dispersion of magnesium pyrophosphate: 1280 g.

[0215] The oil phase was added to the water phase, and a suspension was prepared by dispersing using a TK homogenizer at 8300 rpm for 5 minutes, and then emulsification treatment was performed using a high-pressure emulsifier NVR (Yamada Seiki Industries Co., Ltd., Model "EM055-P20-0600-Exp") at an inlet pressure of 17 MPa and an outlet pressure of 1 MPa, thereby preparing a dispersion liquid in which droplets of the oil phase were dispersed in the water phase. The obtained dispersion liquid was heated at 75°C for 3 hours, and then the temperature inside the polymerization kettle was increased to 110°C (second temperature increase), and stirring was performed at 110°C for 3 hours, thereby completing the polymerization reaction. To the obtained slurry, hydrochloric acid was added to decompose the magnesium pyrophosphate, and then the solid component was separated by filtration and dehydration, and then purified by repeated water washing, and then dried at 80°C for 24 hours, thereby obtaining resin particles (5).

[0216] Further, the obtained resin particles (5): 0.425 g, ethyl acetate: 8.3 g, and solvent-soluble polyimide KPI-MX300F (KURARAY INDUSTRIES LTD.): 1.7 g were subjected to defoaming stirring using a planetary stirring defoaming machine (KURABO Co., Ltd., "MAZERUSTAR KK-250"), and an evaluation mixture was prepared.

[0217] The obtained evaluation mixture was applied to a glass plate having a thickness of 5 mm using an applicator in which the wet thickness was set to 250 μm, 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, and then cooled to room temperature, thereby obtaining a film containing the resin particles (5).

[0218] The results are shown in Table 1.

[0219] [Example 6]

[0220] The oil phase was prepared by mixing SA9000: 80 g, St: 280 g, DVB-810: 40 g, dodecanethiol as a thiol compound: 2 g, Irganox 1010 (BASF Japan Ltd.) as an antioxidant: 2 g, V-65 as a polymerization initiator: 4 g, and 2,2'-azobisisobutyronitrile (AIBN): 1.2 g.

[0221] The water phase was prepared by dissolving sodium lauryl sulfate: 1.2 g in a 2.2% by weight magnesium pyrophosphate aqueous dispersion liquid: 1280 g.

[0222] To the water phase, the oil phase was added, and a suspension was prepared by dispersing using a TK homogenizer at a rotation speed of 8300 rpm for 5 minutes. After that, a high-pressure emulsifier NVR (Yamato Kikai Co., Ltd., Model "EM055-P20-0600-Exp") was used to perform emulsification treatment under conditions of an inlet treatment pressure of 17 MPa and an outlet pressure of 1 MPa, thereby preparing a dispersion liquid in which oil phase droplets were dispersed in the water phase. The obtained dispersion liquid was heated at 60°C for 2 hours, and then the internal temperature of the polymerization kettle was raised to 90°C (second temperature rise), and stirring was performed at 90°C for 2 hours, thereby completing the polymerization reaction. To the obtained slurry, hydrochloric acid was added to decompose the magnesium pyrophosphate, and then the solid component was separated by filtration and dehydration, and purified by repeated water washing, and then dried at 80°C for 24 hours, thereby obtaining resin particles (6).

[0223] The results are shown in Table 1.

[0224] [Example 7]

[0225] An oil phase was prepared by mixing a reactive low-molecular-weight polyphenyl ether "OPE-2St" (manufactured by Mitsubishi Gas Chemical Company, Inc.) having an ether structure: 160 g, St: 196.8 g, DVB-810: 43.2 g, PEROYL L as a polymerization initiator: 4 g, and benzoyl peroxide: 1.6 g as a polymerization initiator.

[0226] An aqueous phase was prepared by dissolving sodium lauryl sulfate: 0.4 g in a 2.2% by weight aqueous dispersion of magnesium pyrophosphate: 1075 g.

[0227] To the water phase, the oil phase was added, and a suspension was prepared by dispersing using a TK homogenizer (manufactured by PRIMIX Co., Ltd.) at a rotation speed of 8300 rpm for 5 minutes. The obtained suspension was heated at 70°C for 5 hours, and then the internal temperature of the polymerization kettle was raised to 105°C (second temperature rise), and stirring was performed at 105°C for 2 hours, thereby completing the polymerization reaction. To the obtained slurry, hydrochloric acid was added to decompose the magnesium pyrophosphate, and then the solid component was separated by filtration and dehydration, and purified by repeated water washing, and then dried at 80°C for 24 hours, thereby obtaining resin particles (7).

[0228] The results are shown in Table 1.

[0229] [Example 8]

[0230] A resin particle (8) was obtained in the same manner as in Example 5, except that dodecanethiol was not used.

[0231] The results are shown in Table 1.

[0232] [Comparative Example 1]

[0233] Styrene (St): 356.8 g, divinylbenzene (DVB) (trade name "DVB-810", manufactured by Nippon Shokubai Co., Ltd., containing 81% of DVB, and the remaining 19% being ethylvinylbenzene (EVB)): 43.2 g, 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by FUJIFILM Wako Pure Chemical Corporation): 4 g, benzoyl peroxide: 1.08 g, to prepare an oil phase.

[0234] In a 2.2% by weight aqueous solution of magnesium pyrophosphate: 1075 g, sodium lauryl sulfate: 0.4 g was dissolved to prepare an aqueous phase.

[0235] The oil phase was added to the aqueous phase, and a suspension was prepared by dispersing using a TK homogenizer (manufactured by PRIMIX Corporation) at a rotation speed of 8300 rpm for 5 minutes. After heating the obtained suspension at 55°C for 5 hours, the temperature inside the polymerization kettle was raised to 105°C (two-step temperature increase), and the polymerization reaction was completed by stirring at 105°C for 2 hours. After adding hydrochloric acid to the obtained slurry to decompose the magnesium pyrophosphate, the solid component was separated by filtration and dehydration, and the product was refined by repeated water washing, and then dried at 80°C for 24 hours to obtain resin particles (C1).

[0236] Further, the obtained resin particles (C1): 0.425 g, ethyl acetate: 8.3 g, and solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Industries Co., Ltd.): 1.7 g were defoamed and stirred using a planetary stirring defoaming machine (manufactured by KURABO Co., Ltd., "MAZERU STAR KK-250") to prepare an evaluation mixture.

[0237] The obtained evaluation mixture was coated on a glass plate having a thickness of 5 mm using a coater with a wet thickness set to 250 μm, 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, and then cooled to room temperature to obtain a film containing the resin particles (C1).

[0238] The results are shown in Table 1.

[0239] [Comparative Example 2]

[0240] In the same manner as in Example 1, except that SA9000 was changed to 40 g, St was changed to 360 g, and DVB-810 was not used, resin particles (C2) were obtained.

[0241] The results are shown in Table 1.

[0242] [Table 1]

[0243]

[0244] industrial applicability

[0245] The resin particles of the embodiments of the present application are suitably used for semiconductor materials, etc.

Claims

1. A resin particle containing a polymer P having an ether structure represented by formula (1), Furthermore, the recovery rate calculated by loading and unloading tests conducted under conditions of 20℃ temperature, 65% relative humidity, 0.732 mN / s loading speed, 9.81 mN maximum load, and 1.96 mN minimum load is 4.6% or higher. [Chemistry 1] 2. The resin particles according to claim 1, wherein the 3% weight loss temperature when heated at 10°C / min in air is 270°C or higher.

3. The resin particles according to claim 1, wherein the dielectric loss tangent at a frequency of 10 GHz is 0.0040° or less.

4. The resin particles according to claim 1 have a volume average particle size of 0.1 μm to 100 μm.

5. The resin particles according to claim 1, wherein the coefficient of variation of the particle size is 10% to 50%.

6. The resin particles according to claim 1 have an average roundness of 0.95 to 1.

00.

7. The resin particles according to claim 1, wherein they are solid particles.

8. The resin particles according to claim 1, wherein, The polymer P is a polymer obtained by polymerization of a monomer composition containing a compound A having an ether structure and a free radical reactive group as represented by formula (1) and a monomer M that reacts with the compound A.

9. The resin particles according to claim 8, wherein, The monomer M contains an aromatic monofunctional monomer m1 and an aromatic crosslinking monomer m2.

10. The resin particles according to claim 8, wherein, The content of compound A in the monomer composition is 0.1% by weight or more and less than 60% by weight.

11. The resin particles according to claim 9, wherein, The aromatic monofunctional monomer m1 in the monomer component M is present in a proportion of 50% to 99% by weight.

12. The resin particles according to claim 9, wherein, The aromatic crosslinking monomer m2 in the monomer component M is present in an amount of 1% to 50% by weight.

13. The resin particles according to claim 9, wherein, In the monomer composition, the content ratio of the aromatic crosslinking monomer m2 relative to the compound A is such that, with 100 parts by weight of the compound A, the amount of the aromatic crosslinking monomer m2 is 1 part by weight to 1000 parts by weight.

14. The resin particles according to claim 8, wherein, The monomer composition contains 5 parts by weight or less of a thiol compound relative to 100 parts by weight of the monomer composition.

15. The resin particles according to claim 1, which are used for semiconductor components.

16. A resin composition for semiconductor components comprising the resin particles of claim 15.

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