Resin particles and resin composition for semiconductor members

Abstract

The present invention provides resin particles with which it is possible to achieve preferred dielectric loss tangent, high heat resistance and excellent flexibility. The present invention also provides a resin composition for semiconductor members, the resin composition containing the resin particles.　Resin particles according to an embodiment of the present invention contain a polymer P that has a specific ether structure, and have a recovery ratio of 4.6% or more as calculated by a loading-unloading test that is performed under the conditions of a temperature of 20°C, a relative humidity of 65%, a loading rate of 0.732 mN / second, a maximum load of 9.81 mN, and a minimum load of 1.96 mN.

Description

Resin particles and resin composition for semiconductor members

[0001] The present invention relates to resin particles and a resin composition for a semiconductor member.

[0002] In order to increase the speed of information processing using electronic devices, attempts have been made to lower the dielectric constant and dielectric loss tangent of the insulating layer of a multilayer printed circuit board. For example, studies have been conducted to lower the dielectric constant and dielectric loss tangent of the insulating layer by mixing resin particles into the resin that forms the insulating layer.

[0003] 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 containing the resin particles is heated during molding or soldering.

[0004] Furthermore, resin particles used for semiconductor component applications are required to have excellent flexibility so that the resin particles will not deform or break when a load such as pressure is applied to the resin particles themselves or to the resin in which the resin particles are mixed.

[0005] A thermosetting resin molding material has been reported that is useful as a material for circuit boards and has excellent electrical properties such as insulation resistance, low dielectric constant, and low dielectric loss tangent. The thermosetting resin molding material is made by blending thermoplastic norbornene-based resin particles with a thermosetting resin raw material (Patent Document 1). However, the thermoplastic norbornene-based resin particles have problems such as brittleness and poor flexibility. Furthermore, because the thermoplastic norbornene-based resin particles are particles obtained by crushing chunks, plates, pellets, etc. of the thermoplastic norbornene-based resin, they have an irregular shape, which results in poor filling properties when mixed into a resin.

[0006] Hollow resin particles have been reported that can provide organic insulating materials with excellent insulating properties, low dielectric constants, and low dielectric loss tangents (Patent Document 2). However, because they are hollow resin particles, they have the problem of being poor in flexibility.

[0007] A resin sheet for insulating applications 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). In the examples, core-shell 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. However, the core-shell rubber particles described as the particulate stress relaxation material have a shell made of an acrylic resin, which results in problems such as high dielectric constant and dielectric loss tangent values ​​and insufficient heat resistance. Non-particulate stress relaxation materials are amorphous, which results in problems such as poor filling properties when mixed into a resin.

[0008] A composition for modifying an insulating film containing a dispersion medium and a core-shell polymer having a rubber-like elastic core layer has been reported (Patent Document 4). However, the core-shell polymer has a problem in that the polymer constituting the shell layer is an acrylic resin, as can be seen from the composition of styrene / methyl methacrylate / acrylonitrile / glycidyl methacrylate = 60 / 50 / 30 / 40 (weight ratio) described in the examples, and therefore has high values ​​of dielectric constant and dielectric loss tangent, and insufficient heat resistance.

[0009] Japanese Patent Laid-Open No. 6-162856 Japanese Patent Laid-Open No. 2000-313818 International Publication No. 2022-196696 Japanese Patent Laid-Open No. 2016-094527

[0010] The present invention has been made to solve the above-mentioned conventional problems, and a main object of the present invention is to provide resin particles that can exhibit a low dielectric loss tangent, high heat resistance, and excellent flexibility, and to provide a resin composition for a semiconductor member containing such resin particles.

[0011] [1] 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 as calculated by a load-unloading test conducted under the conditions of a temperature of 20°C, a relative humidity of 65%, a loading rate of 0.732 mN / sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN. [2] The resin particles described in [1] above 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. [3] The resin particles described in [1] or [2] above may have a dielectric loss tangent of 0.0040 or lower at a frequency of 10 GHz. [4] The resin particles described in any of [1] to [3] above may have a volume average particle diameter of 0.1 μm to 100 μm. [5] The resin particles described in any of [1] to [4] above may have a particle diameter coefficient of variation of 10% to 50%. [6] The resin particles described in any of [1] to [5] above may have an average circularity of 0.95 to 1.00. [7] The resin particles described in any of [1] to [6] above may be solid particles. [8] In the resin particle according to any one of [1] to [7] above, 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 formula (1) above and a monomer M reactive with the compound A. [9] In the resin particle according to [8] above, the monomer M may contain an aromatic monofunctional monomer m1 and an aromatic crosslinkable monomer m2.

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

[11] In the resin particle according to [9] or

[10] above, the content of the aromatic monofunctional monomer m1 in the monomer M may be 50% by weight to 99% by weight.

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

[11] above, the content of the aromatic crosslinkable monomer m2 in the monomer M may be 1% by weight to 50% by weight.

[13] In the resin particles according to any one of [9] to

[12] above, 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 1000 parts by weight when the compound A is taken as 100 parts by weight.

[14] In the resin particles according to any one of [8] to

[13] above, the monomer composition may contain less than 2 parts by weight of a thiol compound per 100 parts by weight of the monomer composition.

[15] The resin particles according to any one of [1] to

[14] above may be used for semiconductor members.

[16] A resin composition for semiconductor members according to an embodiment of the present invention contains the resin particles according to

[15] above.

[0012] According to an embodiment of the present invention, it is possible to provide resin particles that can exhibit low dielectric tangent, high heat resistance, and excellent flexibility. Also, it is possible to provide a resin composition for a semiconductor member containing such resin particles.

[0013] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0014] In this specification, the expression "(meth)acrylic" means "acrylic and / or methacrylic", and the expression "(meth)acrylate" means "acrylate and / or methacrylate".

[0015] Resin Particles The resin particles according to an embodiment of the present invention have a recovery rate calculated by a load-unloading test performed under conditions of a temperature of 20°C, a relative humidity of 65%, a loading rate of 0.732 mN / sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN. The recovery rate 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 recovery rate, the better, but in reality, the upper limit may be 30% or less. The higher the recovery rate within the above range, the more excellent the flexibility of the resin particles according to an embodiment of the present invention. If the recovery rate is lower than the above range, the flexibility of the resin particles will be reduced, and when a load such as pressure is applied to the resin particles themselves or to a resin containing the resin particles, the resin particles may deform or break. The measurement method for the load-unloading test will be described in detail later.

[0016] The resin particles according to an 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 at a rate of 10°C / min in an air atmosphere. 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 within the above range, the higher the heat resistance of the resin particles according to an embodiment of the present invention. If the 3% weight loss temperature is lower than the above range, the resin particles may deform upon heating. For example, when the resin particles are kneaded with a thermosetting resin, the resin particles may deform upon heating due to the curing reaction, which may reduce the dielectric loss tangent reduction effect. The method for measuring the 3% weight loss temperature will be described in detail later.

[0017] The resin particles according to an 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 is preferably 0 or more. If the dielectric loss tangent is within the above range, the resin particles according to an embodiment of the present invention themselves and resins containing the resin particles can exhibit a low dielectric loss tangent. The method for measuring the dielectric loss tangent will be described in detail later.

[0018] The volume average particle diameter of the resin particles according to the embodiment of the present invention is preferably 0.1 μm to 100 μm. As long as 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.

[0019] When used as resin particles for semiconductor components, the volume average particle diameter of the resin particles according to an embodiment of the present invention is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 50 μm, even more preferably 0.1 μm to 30 μm, particularly preferably 0.1 μm to 20 μm, and most preferably 0.1 μm to 10 μm.

[0020] For applications requiring micron-sized resin particles, the volume average particle size of the resin particles according to embodiments of the present invention is preferably 0.1 μm to 100 μm, more preferably 0.3 μm to 50 μm, even more preferably 0.6 μm to 30 μm, particularly preferably 0.8 μm to 20 μm, and most preferably 1 μm to 10 μm.

[0021] For applications requiring submicron-sized resin particles, the volume average particle size of the resin particles according to embodiments of the present invention is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 50 μm, even more preferably 0.1 μm to 10 μm, particularly preferably 0.1 μm to 5 μm, and most preferably 0.1 μm to 1 μm.

[0022] The resin particles according to an embodiment of the present invention preferably have a particle size 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 size 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 increased amount of coarse resin particles can be suppressed. If the particle size coefficient of variation of the resin particles is too large outside the above range, the increased amount of coarse resin particles may result in difficulty in forming a thin film or in uneven thickness, for example, when the resin particles are mixed into a resin to form a resin layer. If the particle size 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 may result in uneven thickness, for example, when the resin particles are mixed into a resin to form a resin layer. The method for measuring the coefficient of variation of the particle size will be described in detail later.

[0023] 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, thereby improving the packing properties when mixed into a resin, for example. If the average circularity is low and outside the above range, the shape of the resin particles will deviate from a perfect sphere, which may result in reduced packing properties when mixed into a resin, for example.

[0024] The resin particles according to the embodiment of the present invention are preferably solid particles, which can exhibit better flexibility.

[0025] <Polymer P> The resin particles according to an embodiment of the present invention typically contain a polymer P having an ether structure represented by formula (1). When the polymer P has the ether structure represented by formula (1), the effects of the present invention can be more effectively exhibited.

[0026] The polymer P may be of one kind or of two or more kinds.

[0027] The polymer P may have only one type of ether structure represented by formula (1), or two or more types.

[0028] The fact that polymer P has the ether structure represented by formula (1) can be confirmed by any appropriate identification means such as NMR, IR, MS, etc.

[0029] 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, still 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 terms of being able to further exhibit the effects of the present invention.

[0030] 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. Here, the monomer composition consists of compound A and monomer M, but does not contain a polymerization initiator used in the polymerization reaction.

[0031] A preferred embodiment of polymer P therefore comprises an ether structure represented by formula (1) and structural units derived from the monomers contained in monomer M. For example, when monomer M comprises 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 the aromatic monofunctional monomer, and structural units derived from the aromatic crosslinkable monomer.

[0032] Here, a "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) of a monomer contained in a monomer composition through a polymerization reaction when the monomer composition is polymerized to prepare a polymer. For example, a structural unit derived from a monomer having a structure of "RpRqC=CRrRs" (Rp, Rq, Rr, and 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 a carbon-carbon unsaturated double bond "C=C" through a polymerization reaction.

[0033] The content ratio of the structural units derived from each monomer in the polymer can be determined by various structural analyses of the polymer (e.g., NMR, etc.). Alternatively, without performing such various structural analyses, the content ratio of the structural units derived from each monomer in the polymer may be calculated based on the amount of each monomer used in preparing the polymer and the polymerization reaction rate. Alternatively, the content ratio of the structural units derived from each monomer in the polymer may be determined by any other appropriate means.

[0034] The compound A may be one kind or two or more kinds.

[0035] As the 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. In terms of being able to further exhibit the effects of the present invention, such a radical reactive group is preferably a group having a carbon-carbon unsaturated double bond, and specific examples thereof include a vinyl group, an acryl group, a methacryl group, an acrylamide group, and an allyl group.

[0036] Any appropriate compound having the ether structure represented by formula (1) and a radical-reactive group may be used as the compound A, as long as it does not impair the effects of the present invention. In terms of being able to further exhibit the effects of the present invention, such compound A is preferably polyphenylene ether (PPE).

[0037] An example of compound A is polyphenylene ether (PPE) having a structure represented by formula (2). Of course, 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.

[0038]

[0039] In formula (2), m and n represent the number of repeating units (number of moles added) of the ether structure represented by formula (1), and X 1 , X 2 is an organic group having a radical reactive group, and Y is 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.

[0040] Commercially available polyphenylene ether products include, for example, the "NORYL (registered trademark)" series (such as NORYL (registered trademark) SA9000) (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 Company, Inc.), and the "DPPE-VBT50" series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0041] Compound A may be an oligomer, which can further enhance the effects of the present invention. In this case, the number-average molecular weight Mn of compound A is preferably 500 to 5,000, more preferably 800 to 3,500, even more preferably 1,000 to 3,000, particularly preferably 1,200 to 2,500, and most preferably 1,400 to 2,000.

[0042] The content of compound A in the monomer composition is preferably 0.1 wt % or more and less than 60 wt %, more preferably 0.1 wt % or more and less than 55 wt %, even more preferably 0.1 wt % or more and less than 50 wt %, even more preferably 0.1 wt % or more and less than 45 wt %, even more preferably 0.1 wt % or more and less than 40 wt %, even more preferably 1 wt % to 35 wt %, even more preferably 3 wt % to 30 wt %, even more preferably 5 wt % to 25 wt %, particularly preferably 7 wt % to 22 wt %, and most preferably 9 wt % to 21 wt %. If the content of compound A in the monomer composition is too low 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. 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 exhibited, for example, compound A may become difficult to dissolve in the monomer composition, and resin particles may not be obtained.

[0043] As the monomer M, any appropriate monomer can be adopted as long as it is different from the compound A and reacts with the compound A, within a range that does not impair the effects of the present invention. The monomer M may be one type only, or two or more types.

[0044] The monomer M preferably contains an aromatic monofunctional monomer m1 and an aromatic crosslinkable monomer m2, in order to further enhance the effects of the present invention. The aromatic monofunctional monomer m1 may be of only one type or may contain two or more types. The aromatic crosslinkable monomer m2 may be of only one type or may contain two or more types.

[0045] As the aromatic monofunctional monomer m1, any appropriate aromatic monofunctional monomer can be used as long as it is a monofunctional aromatic monomer and does not impair the effects of the present invention. Examples of such aromatic monofunctional monomer m1 include styrene, ethylvinylbenzene, α-methylstyrene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene, from the viewpoint of being able to further exhibit the effects of the present invention. From the viewpoint of being able to further exhibit the effects of the present invention and from the viewpoint of reactivity, the aromatic monofunctional monomer m1 is preferably at least one selected from the group consisting of styrene and ethylvinylbenzene.

[0046] As the aromatic crosslinkable monomer m2, any appropriate aromatic crosslinkable monomer may be used as long as it is an aromatic monomer having crosslinkability and does not impair the effects of the present invention. Examples of such aromatic crosslinkable monomer m2 include divinylbenzene, divinylnaphthalene, and diallyl phthalate, which can further enhance the effects of the present invention. Divinylbenzene is preferred as the aromatic crosslinkable monomer m2 in terms of further enhancing the effects of the present invention and reactivity.

[0047] The total content of the aromatic monofunctional monomer m1 and the aromatic crosslinkable monomer m2 in the total amount of monomers 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 exhibit the effects of the present invention.

[0048] As the monomer M, any appropriate other monomer different from the compound A, the aromatic monofunctional monomer m1, and the aromatic crosslinkable monomer m2 can be used as long as the effects of the present invention are not impaired. The other monomer may be one type only, or two or more types.

[0049] Other 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 fumarate; 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl methacrylic acid derivative monomers having a carboxy group and an ester bond, such as maleic 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; epoxy group-containing monomers; and N-vinylcarbazole.

[0050] The content of the other monomers in the total amount of monomer M is preferably 0% by weight to 50% by weight, more preferably 0% by weight to 20% by weight, even more preferably 0% by weight to 10% by weight, particularly preferably 0% by weight to 5% by weight, and most preferably 0% by weight to 2% by weight, in terms of being able to further exhibit the effects of the present invention.

[0051] The content of monomer M in the monomer composition is preferably more than 40% by weight but not more than 99.9% by weight, more preferably more than 45% by weight but not more than 99.9% by weight, even more preferably more than 50% by weight but not more than 99.9% by weight, even more preferably more than 55% by weight but not more than 99.9% by weight, even more preferably more than 60% by weight but not more than 99.9% by weight, even more preferably 65% ​​by weight to 99% by weight, even more preferably 70% by weight to 97% by weight, even more preferably 75% by weight to 95% by weight, particularly preferably 78% by weight to 93% by weight, and most preferably 79% by weight to 91% by weight. If the content of monomer M in the monomer composition is too low outside the above range, the effects of the present invention may not be exhibited, for example, compound A may be less soluble in the monomer composition, and resin particles may not be obtained. If the content of the monomer M in the monomer composition is too high and outside the above range, the effects of the present invention may not be exhibited, for example, high heat resistance may not be exhibited or excellent flexibility may not be exhibited.

[0052] The content of the aromatic monofunctional monomer m1 in the 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, still 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 terms of being able to further exhibit the effects of the present invention.

[0053] The content of the aromatic crosslinkable monomer m2 in the 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, still 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 terms of being able to further exhibit the effects of the present invention.

[0054] In the monomer composition, the content ratio of the aromatic crosslinkable monomer m2 to the compound A is, from the viewpoint of further exhibiting the effects of the present invention, preferably 1 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, even more preferably 20 to 400 parts by weight, still 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 the compound A is taken as 100 parts by weight.

[0055] The polymer P is obtained by a polymerization reaction of a monomer composition. The polymerization reaction is preferably a suspension polymerization reaction. When performing the suspension polymerization reaction, the polymerization reaction is typically performed by adding an oil phase to an aqueous phase and dispersing them.

[0056] Any suitable dispersion method can be used for the dispersion, as long as it allows the oil phase to exist in droplet form in the aqueous phase, without impairing the effects of the present invention. Typical 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.

[0057] The aqueous phase typically contains an aqueous solvent, such as water or a mixed solvent of water and a lower alcohol (e.g., methanol or ethanol).

[0058] The amount of the aqueous solvent used may be any appropriate amount as long as it does not impair the effects of the present invention, and is preferably 10 to 5,000 parts by weight, more preferably 50 to 3,000 parts by weight, and even more preferably 100 to 2,000 parts by weight, relative to 100 parts by weight of the monomer composition.

[0059] The oil phase may contain an organic solvent. Typical examples of the organic solvent include organic solvents having a boiling point of less than 100°C. Examples of organic solvents having 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 having a boiling point of less than 100°C may be a mixed solvent.

[0060] The amount of organic solvent used is preferably 20 to 250 parts by weight relative to 100 parts by weight of the monomer composition. However, when the resin particles in an embodiment of the present invention are solid particles, it is preferable to use no organic solvent, and the amount of organic solvent used is preferably less than 20 parts by weight relative to 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.

[0061] When carrying out the polymerization reaction of the monomer composition, any appropriate additive B that does not fall under either the compound A or the monomer M may be used within a range that does not impair the effects of the present invention. The additive B may be one type only, or two or more types may be used.

[0062] Examples of additive B include a polymerization initiator, a surfactant, a dispersion stabilizer, a thiol compound, and an antioxidant.

[0063] Any appropriate polymerization initiator may be used as the polymerization initiator as long as it does not impair the effects of the present invention. The polymerization initiator may be a single type 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; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile). Among these polymerization initiators, the use of organic peroxides can result in resin particles with a more excellently low dielectric tangent.

[0064] The polymerization initiator may be added to the aqueous phase or the oil phase, but is typically added to the oil phase.

[0065] The amount of the polymerization initiator added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer composition.

[0066] As the surfactant, any appropriate surfactant may be used as long as it does not impair the effects of the present invention. The surfactant may be one type or two or more types. In terms of being able to further exhibit the effects of the present invention, the surfactant is preferably at least one type selected from the group consisting of amphoteric surfactants and anionic surfactants.

[0067] As the amphoteric surfactant, any appropriate amphoteric surfactant can be used as long as it does not impair the effects of the present invention. As such an amphoteric surfactant, a known amphoteric surfactant that can be used in the production of resin particles can be used. Examples of amphoteric surfactants include lauryl dimethylamine oxide, lauryl dimethylaminoacetic acid betaine, phosphate surfactants, and phosphite surfactants. Only one type of amphoteric surfactant may be used, or two or more types may be used.

[0068] Any appropriate anionic surfactant can be used as the anionic surfactant as long as it does not impair the effects of the present invention. Examples of such 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-formalin condensates, polyoxyethylene alkyl phosphate sulfonates, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters. Specific examples include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene nonylphenyl ether sulfate ester salts, and the sodium salt of β-naphthalenesulfonate-formalin condensates. The anionic surfactant may be used alone or in combination of two or more types.

[0069] The surfactant may be added to either the aqueous phase or the oil phase, but is typically added to the aqueous phase.

[0070] The amount of the 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, relative to 100 parts by weight of the aqueous solvent contained in the aqueous phase.

[0071] As the dispersion stabilizer, any appropriate dispersion stabilizer can be used 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 may be used. In terms of being able to further demonstrate the effects of the present invention, examples of dispersion stabilizers include polyvinyl alcohol; polycarboxylic acids; 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 colloidal silica. Among these, magnesium pyrophosphate is preferred in terms of being able to further demonstrate the effects of the present invention.

[0072] The dispersion stabilizer may be added to either the aqueous phase or the oil phase, but is typically added to the aqueous phase.

[0073] The amount of the dispersion stabilizer used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the aqueous solvent contained in the aqueous phase.

[0074] As the thiol compound, any appropriate thiol compound can be adopted as long as it does not impair the effects of the present invention. The thiol compound may be one type only or two or more types. Examples of such thiol compounds include polyfunctional thiol compounds and monofunctional thiol compounds having an alkyl group having 1 to 20 carbon atoms in the molecule.

[0075] As the polyfunctional thiol compound, any appropriate polyfunctional thiol compound can 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. Examples of such polyfunctional thiol compounds 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. Examples of suitable mercapto-s-triazines 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. Among these, ethylene glycol bisthioglycolate (EGTG), 1,4-butanediol bisthiopropionate (BDTG), trimethylolpropane tristhioglycolate (TMTG), and pentaerythritol tetrakisthioglycolate (PETG) are preferred.

[0076] As the monofunctional thiol compound having an alkyl group having 1 to 20 carbon atoms in the molecule, any suitable monofunctional thiol compound having an alkyl group having 1 to 20 carbon atoms in the molecule can be used as long as it has one thiol group and an alkyl group having 1 to 20 carbon atoms in the molecule, as long as the effects of the present invention are not impaired. The monofunctional thiol compound having an alkyl group having 1 to 20 carbon atoms in the molecule may be one type or two or more types. Examples of such monofunctional thiol compounds having an alkyl group having 1 to 20 carbon atoms in the molecule include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, dodecanethiol, and compounds having branched chain structures thereof.

[0077] 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. That is, the monomer composition contains preferably 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.

[0078] The thiol compound can function as a chain transfer agent and can be a structural unit of the polymer P. In a radical polymerization system (e.g., a radical polymerization system using a hydrolyzable silicon compound having a hydrolyzable silyl group and a group reactive with a radically polymerizable unsaturated group, a monofunctional (meth)acrylic monomer, or a polyfunctional (meth)acrylic monomer), the thiol compound can accept radicals from a growing polymer chain to terminate the elongation of the polymer chain and generate new radicals to initiate the growth reaction of another polymer chain. This makes it possible to uniform the molecular weight of the resulting polymer P, and ultimately the molecular weight of the resin particles according to an embodiment of the present invention, and to uniform the particle size distribution.

[0079] Any appropriate antioxidant may be used as the antioxidant as long as it does not impair the effects of the present invention. Only one type of antioxidant may be used, or two or more types may be used. Examples of such antioxidants include antioxidants having a melting point of 30°C or higher and 105°C or lower. When an antioxidant with a melting point lower than 30°C is used, there is a risk that the antioxidant will liquefy due to the ambient temperature when the resin particles are recovered as a dry powder. When an antioxidant with a melting point higher than 105°C is used, there is a risk that the dispersion stability of the resin particle dispersion will be affected during heat treatment.

[0080] The antioxidant may be in a powder form at room temperature (25° C.), or may be dispersed or dissolved in water, alcohol, or the like.

[0081] Examples of antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. From the viewpoint of further exhibiting 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.

[0082] Any appropriate phenolic antioxidant may be used as the phenolic antioxidant as long as it does not impair the effects of the present invention. As such 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. Furthermore, from the viewpoint of further exerting the effects of the present invention, it is preferable not to use p-methoxyphenol. Examples of phenolic 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].

[0083] Any suitable phosphorus-based antioxidant may be used as long as it does not impair the effects of the present invention, such as 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane.

[0084] Any appropriate sulfur-based antioxidant may be used as long as it does not impair the effects of the present invention, such as dioctadecyl 3,3'-thiodipropionate and pentaerythritol tetrakis[3-(dodecylthio)propionate].

[0085] Any appropriate amine-based antioxidant may be used as long as it does not impair the effects of the present invention, such as 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.

[0086] The amount of the antioxidant added is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer composition.

[0087] The polymerization temperature may be any suitable temperature suitable for suspension polymerization as long as it does not impair the effects of the present invention. For example, the polymerization temperature may be 30°C to 80°C as the initial temperature of the polymerization, and then the temperature may be increased to 70°C to 120°C as the later temperature of the polymerization.

[0088] The polymerization time may be any suitable time suitable for suspension polymerization as long as it does not impair the effects of the present invention. The polymerization time is preferably 1 hour to 48 hours at the temperature in the initial stage of polymerization, and preferably 1 hour to 24 hours at the temperature in the later stage of polymerization.

[0089] After the polymerization, if necessary, decomposition treatment of the dispersion stabilizer such as magnesium pyrophosphate, washing, separation, drying, etc. can be carried out to obtain the resin particles according to an embodiment of the present invention.

[0090] Resin particles for semiconductor members and resin composition for semiconductor members The resin particles according to an embodiment of the present invention are suitable for semiconductor members because they can further utilize the effects of the present invention. That is, the resin particles according to an embodiment of the present invention are preferably for use in semiconductor members.

[0091] The conductive member means a member that constitutes a semiconductor, and examples thereof include a semiconductor package and a semiconductor module.

[0092] A semiconductor package is constructed using an IC chip as an essential component and at least one member selected from a mold resin, an underfill material, a mold underfill material, a die bond 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.

[0093] A semiconductor module is constructed using a semiconductor package as an essential component and at least one member selected from a prepreg for printed circuit boards, a metal-clad laminate for printed circuit boards, a build-up material for printed circuit boards, a solder resist material, a coverlay film, an electromagnetic wave shielding film, and an adhesive sheet for printed circuit boards.

[0094] The resin particles according to an embodiment of the present invention can exhibit a low dielectric loss 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 an embodiment of the present invention contains the resin particles according to an embodiment of the present invention. In this specification, the resin composition for a semiconductor member means a resin composition used for a semiconductor member.

[0095] The resin composition for a semiconductor member according to an embodiment of the present invention typically contains resin particles according to an embodiment of the present invention and a resin component.

[0096] As the resin component, any appropriate resin component that is used in semiconductor members can be used.

[0097] The content of the resin particles according to an embodiment of the present invention in the resin composition for a semiconductor member according to an embodiment of the present invention can be appropriately set depending on the purpose.

[0098] <<Other Uses of Resin Particles>> The resin particles according to the embodiment of the present invention may be used in any other appropriate applications, such as coating compositions, cosmetics, light-diffusing compositions, and light-diffusing films, in addition to semiconductor components.

[0099] <Coating Composition> The resin particles according to an 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 an embodiment of the present invention.

[0100] 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 contain two or more types. The UV-curable resin may be of only one type or may contain two or more types.

[0101] Any suitable binder resin can be used as long as it does not impair the effects of the present invention. Examples of such binder resins include resins soluble in organic solvents or water, and emulsion-type aqueous resins that can be dispersed in water. Specific examples of binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0102] As the UV-curable resin, any appropriate UV-curable resin can 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. Specific examples of 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.

[0103] When the coating composition contains at least one selected from a binder resin and a UV-curable resin, any appropriate content ratio can be adopted depending on the purpose. Typically, 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 terms of solids content in the case of an emulsion-type aqueous resin), the at least one selected from the UV-curable resin, and the resin particles according to the embodiment of the present invention.

[0104] When a UV-curable resin is used, a photopolymerization initiator is preferably used in combination. Any appropriate photopolymerization initiator can 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, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP 2001-139663 A, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and α-acyloxime esters.

[0105] The coating composition may contain a solvent. The solvent may be one type only, or two or more types. When the coating composition contains a solvent, any appropriate content ratio can be adopted depending on the purpose.

[0106] As the solvent, any appropriate solvent can be used as long as it does not impair the effects of the present invention. Such a solvent is preferably a solvent that can dissolve or disperse a binder resin or a UV-curable resin. Examples of such solvents include, for oil-based paints, 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. For water-based paints, examples of such solvents include water and alcohols.

[0107] The coating composition may be diluted to adjust the viscosity as needed. 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.

[0108] The coating composition may contain other components, as needed, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye.

[0109] When forming a coating film using a coating composition, any appropriate coating method can be adopted depending on the purpose, such as spray coating, roll coating, brush coating, reverse roll coating, gravure coating, die coating, comma coating, and spray coating.

[0110] When forming a coating film using a coating composition, any suitable formation method can be adopted depending on the purpose. Such a formation method includes, for example, applying the composition to any coating surface of a substrate to form a coating film, drying the coating film, and then curing the coating film as needed to form a coating film. Examples of substrates include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).

[0111] <Light-diffusing resin composition> The resin particles according to an 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. Such a light-diffusing resin composition includes the resin particles according to an embodiment of the present invention.

[0112] The light-diffusing resin composition preferably contains at least one selected from a binder resin and a UV-curable resin. The binder resin and the UV-curable resin may be the same as those described above for the coating composition.

[0113] The light-diffusing resin composition may contain a solvent. The above-mentioned explanation of the coating composition may be applied to the solvent.

[0114] The light-diffusing resin composition may be diluted to adjust the viscosity as needed. The above-mentioned explanation of the coating composition can be applied to the diluent.

[0115] The light-diffusing resin composition may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye, as needed.

[0116] When a coating film is formed using the light-diffusing resin composition, the coating method and formation method can be the same as those described above for the coating composition.

[0117] <Light Diffusion Film> The resin particles according to an 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 diffusing film. Such a light diffusing film contains the resin particles according to an embodiment of the present invention.

[0118] 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 an embodiment of the present invention may include any appropriate other layer 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.

[0119] Examples of the substrate include metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display panel. Examples of the plastic that constitutes the plastic film, plastic sheet, plastic lens, and plastic panel include polyethylene terephthalate (PET), polycarbonate (PC), acrylic resin, and triacetyl cellulose (TAC).

[0120] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight."

[0121] <Method for measuring volume average particle diameter and coefficient of variation of particle diameter of resin particles> The spherical equivalent volume average particle diameter of 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 carried out using an aperture calibrated in accordance with the Multisizer (registered trademark) 3 user's manual published by Beckman Coulter, Inc. The aperture used for measurement was appropriately selected depending on the size of the particles to be measured. For example, if the assumed volume average particle diameter of the particles to be measured was 1 μm or more and 10 μm or less, an aperture having a size of 50 μm was selected; if the assumed volume average particle diameter of the particles to be measured was more than 10 μm and 30 μm or less, an aperture having a size of 100 μm was selected; if the assumed volume average particle diameter of the particles to be measured was more than 30 μm and 90 μm or less, an aperture having a size of 280 μm was selected; and if the assumed volume average particle diameter of the particles was more than 90 μm and 150 μm or less, an aperture having a size of 400 μm was selected. If the volume average particle diameter after measurement differed from the assumed volume average particle diameter, the aperture was changed to one having an appropriate size and the measurement was performed again. The Current (aperture current) and Gain (gain) were appropriately set depending on the size of the selected aperture. For example, when an aperture having a size of 50 μm was selected, Current (aperture current) was set to −800 and Gain was set to 4; when an aperture having a size of 100 μm was selected, Current (aperture current) was set to −1600 and Gain was set to 2; when apertures having sizes of 280 μm and 400 μm were selected, Current (aperture current) was set to −3200 and Gain was set to 1. Specifically, 0.1 g of resin particles to be measured was dispersed in 10 ml of a 0.1% by mass aqueous solution of a nonionic surfactant using a touch mixer ("TOUCHMIXER MT-31" manufactured by Yamato Scientific Co., Ltd.) and an ultrasonic cleaner ("ULTRASONIC CLEANER VS-150" manufactured by Vervoclear Co., Ltd.) to prepare a dispersion. During the measurement, the contents of the beaker were gently stirred to an extent that no air bubbles were introduced, and the measurement was terminated when 100,000 resin particles were measured.The volume-average particle diameter of the resin particles to be measured was the arithmetic mean diameter in the volume-based particle size distribution of 100,000 particles. The coefficient of variation (CV value) of the particle diameter of the particles was calculated using the following formula: Coefficient of variation of particle diameter of particles (%) = (standard deviation of volume-based particle size distribution of particles ÷ volume-average particle diameter of particles) × 100 (%).

[0122] <Method for Measuring Circularity and Method for Calculating Average Circularity> The circularity of resin particles was measured using a flow particle image analyzer (Sysmex Corporation's "FPIA (registered trademark)-3000S"). Specifically, 0.05 g of sodium dodecylbenzenesulfonate was added as a dispersant to 20 mL of ion-exchanged 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 waves were applied for 5 minutes using a BRANSON ultrasonic disperser "BRANSON SONIFIER 450" (output 400 W, frequency 20 kHz) manufactured by BRANSON. This dispersion treatment dispersed the resin particles to be measured in the surfactant aqueous solution, thereby preparing a dispersion for measurement. The measurement was performed using the flow particle image analyzer equipped with a standard objective lens (10x magnification). A particle sheath (Sysmex Corporation's "PSE-900A") was used as the sheath liquid for the flow particle image analyzer. The measurement dispersion prepared according to the above procedure was introduced into the flow particle image analyzer, and measurement was performed according to the following [Circularity Measurement Conditions]. Prior to the start of the measurement, the flow 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-exchange water)). Circularity is the circumferential length calculated from the diameter of a perfect circle having the same projected area as an image of the resin particles, divided by the circumferential length of the image of the resin particles. Average circularity is the sum of the circularities of individual resin particles divided by the sum of the number-based frequency. The proportion of hollow particles with an average circularity of 0.90 or less was calculated from the number-based frequency data measured in intervals of 0.010 (e.g., 0.200 or more and less than 0.990) by the above measurement. [Circularity measurement conditions] Measurement mode: LPF measurement mode or HPF measurement mode (selected appropriately depending on the spherical equivalent volume average particle diameter. As a guideline, the HPF measurement mode was selected when the spherical equivalent volume average particle diameter was 8 μm or less, and the LPF measurement mode was selected when the spherical equivalent volume average particle diameter was 8 μm or more.) - Number of resin particles measured: 1,000 - Measurement range of spherical equivalent volume average particle diameter: 0.5 μm to 200 μm - Measurement range of resin particle circularity: 0.2 to 1.0.

[0123] <3% Weight Loss Temperature of Resin Particles> The 3% weight loss temperature of resin particles was measured using a "TG / DTA6200, AST-2" differential thermal thermogravimetric simultaneous measurement device manufactured by SII Nanotechnology Inc. The sampling method and temperature conditions were as follows. 10.5±0.5 mg of sample was packed tightly into the bottom of a platinum measurement container to prepare a measurement sample. The 3% weight loss temperature was measured using alumina as the reference material at 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. The temperature at which 3% weight loss occurred was calculated from the obtained curve using the analysis software provided with the device, and this was taken as the 3% weight loss temperature.

[0124] <Resin Particle Recovery Rate> The recovery rate of resin particles was measured by a load-unload test using a Shimadzu Corporation microcompression tester "MCTM-200" under the following measurement conditions. Specifically, a dispersion of resin particles in ethanol was applied to a mirror-finished steel sample stage and dried to prepare a measurement sample. Next, at room temperature of 20°C and a relative humidity of 65%, an individual fine resin particle (with no other resin particles present within a diameter range of at least 100 μm) was selected using the MCTM-200 optical microscope, and the diameter of the selected resin particle was measured using the MCTM-200 particle size measurement cursor. The selected resin particles were fine particles with a diameter ranging from 7 μm to 9 μm, and resin particles outside this range were not used in the compression strength measurement. Next, the test indenter was lowered onto the apex of the selected resin particle at the following loading rate, and the particle diameter A was measured when a load of 9.81 mN was applied to the resin particle, and the particle diameter B was measured when the load was then removed to a minimum test force of 1.96 mN. From the displacement (restored amount) obtained from particle diameter A and particle diameter B, the individual restoration rates were calculated using 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 of the remaining four data was taken as the restoration rate. [Formula for calculating the recovery rate] Recovery rate (%) = recovery amount (μm) / particle diameter under no load (μm) × 100 [Conditions for measuring the recovery rate] Test temperature: room temperature (20°C), relative humidity 65% ​​Upper pressure indenter: flat indenter with a diameter of 50 μm (material: diamond) Lower pressure plate: SKS flat plate Test type: load-unload test Maximum test force: 9.81 mN Minimum test force: 1.96 mN Load rate: 0.732 mN / sec Load holding time: 1 sec Unload holding time: 1 sec

[0125] <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 perturbation theory using a resonator at a frequency of 10 GHz under the measurement environment of 23°C and a relative humidity of 51±1%.

[0126] <Dielectric Properties of Resin Particle-Added Film> The dielectric loss tangent of the obtained film containing resin particles was measured by a cavity resonance method (measurement frequency: 5.8 GHz). The measurement results were expressed as a relative percentage (%), with the measurement value of the film not containing resin particles being 100%.

[0127] 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., containing 81% DVB, with 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. An aqueous phase was prepared by dissolving 0.4 g of sodium lauryl sulfate in 1,075 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate. The oil phase was added to the aqueous phase, and the mixture was dispersed for 5 minutes at 8,300 rpm using a TK Homomixer (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 increased 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 resulting slurry to decompose the magnesium pyrophosphate, and the solids were separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain resin particles (1). The results are shown in Table 1.

[0128] Example 2 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 solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were degassed and stirred using a planetary stirring defoamer (manufactured by KURABO Corporation, "Mazerustar KK-250") to prepare a mixture for evaluation. The obtained mixture for evaluation was applied to a 5 mm thick glass plate using an applicator set to a wet thickness of 250 μm, and then heated at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes to remove ethyl acetate. The mixture was then cooled to room temperature to obtain a film containing resin particles (2). The results are shown in Table 1.

[0129] 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.

[0130] 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.

[0131] 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 (trade name "Perloyl L" manufactured by NOF Corporation) as a polymerization initiator, and 1.6 g of benzoyl peroxide. An aqueous phase was prepared by dissolving 1.2 g of sodium lauryl sulfate in 1,280 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate. The oil phase was added to the aqueous phase, and the mixture was dispersed using a TK homomixer at a rotation speed of 8,300 rpm for 5 minutes to prepare a suspension. The mixture was then emulsified using a high-pressure emulsifier NVR (manufactured by Yoshida Kikai Kogyo Co., Ltd., model "EM055-P20-0600-Exp") at an inlet treatment pressure of 17 MPa and an outlet pressure of 1 MPa, producing a dispersion in which droplets of the oil phase were dispersed in the aqueous phase. The resulting dispersion was heated at 75°C for 3 hours, and then the internal temperature of the polymerization vessel was increased to 110°C (secondary temperature increase). The polymerization reaction was completed by stirring at 110°C for 3 hours. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate, and the solids were separated by dehydration through filtration. The solids were purified by repeated washing with water and then dried at 80°C for 24 hours to obtain resin particles (5). Furthermore, 0.425 g of the resulting resin particles (5), 8.3 g of ethyl acetate, and 1.7 g of 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. The obtained mixture for evaluation was applied to a 5 mm thick glass plate using an applicator set to a wet thickness of 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. Thereafter, the mixture was cooled to room temperature to obtain a film containing resin particles (5). The results are shown in Table 1.

[0132] Example 6 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). An aqueous phase was prepared by dissolving 1.2 g of sodium lauryl sulfate in 1,280 g of a 2.2 wt% aqueous dispersion of magnesium pyrophosphate. The oil phase was added to the aqueous phase and dispersed using a TK Homomixer at 8,300 rpm for 5 minutes to prepare a suspension. The resulting mixture was then emulsified using a high-pressure emulsifier NVR (Yoshida Kikai Kogyo Co., Ltd., model "EM055-P20-0600-Exp") at 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. The resulting 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 resulting slurry to decompose the magnesium pyrophosphate. The solids were then separated by dehydration through filtration, purified by repeated water washing, and dried at 80°C for 24 hours to obtain resin particles (6). The results are shown in Table 1.

[0133] 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. An aqueous phase was prepared by dissolving 0.4 g of sodium lauryl sulfate in 1,075 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate. The oil phase was added to the aqueous phase, and the mixture was dispersed at 8,300 rpm for 5 minutes using a TK Homomixer (manufactured by Primix Corporation) to prepare a suspension. The resulting suspension was heated at 70°C for 5 hours, and then the internal temperature of the polymerization vessel was increased 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 the 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). The results are shown in Table 1.

[0134] [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.

[0135] Comparative Example 1 An oil phase was prepared by mixing 356.8 g of styrene (St), 43.2 g of divinylbenzene (DVB) (trade name "DVB-810", manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 81% DVB, with 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. An aqueous phase was prepared by dissolving 0.4 g of sodium lauryl sulfate in 1,075 g of a 2.2 wt % aqueous dispersion of magnesium pyrophosphate. The oil phase was added to the aqueous phase, and the mixture was dispersed at 8,300 rpm for 5 minutes 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 increased to 105°C (secondary temperature increase). The polymerization reaction was completed by stirring at 105°C for 2 hours. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate, and the solids were separated by dehydration through filtration. The solids were purified by repeated washing with water and then dried at 80°C for 24 hours to obtain resin particles (C1). Furthermore, 0.425 g of the resulting resin particles (C1), 8.3 g of ethyl acetate, and 1.7 g of 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. The obtained mixture for evaluation was applied to a 5 mm thick glass plate using an applicator set to a wet thickness of 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. Thereafter, the mixture was cooled to room temperature to obtain a film containing resin particles (C1). The results are shown in Table 1.

[0136] Comparative Example 2 Resin particles (C2) were obtained in the same manner as in Example 1, except that the amount of SA9000 was changed to 40 g, the amount of St was changed to 360 g, and DVB-810 was not used. The results are shown in Table 1.

[0137]

[0138] The resin particles according to the embodiment of the present invention can be suitably used for semiconductor materials and the like.

Claims

1. Resin particles comprising a polymer P having an ether structure represented by formula (1), and having 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 load rate of 0.732 mN / sec, a maximum load of 9.81 mN, and a minimum load of 1.96 mN.

2. The resin particles according to claim 1, which have a 3% weight loss temperature of 270° C. or higher when heated at a rate of 10° C. / min in an air atmosphere.

3. The resin particles according to claim 1, which have a dielectric loss tangent of 0.0040 or less at a frequency of 10 GHz.

4. The resin particles according to claim 1, having 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, having an average circularity of 0.95 to 1.

00.

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

8. The resin particle according to claim 1, wherein the polymer P is 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 formula (1) and a monomer M that reacts with the compound A.

9. The resin particle according to claim 8, wherein the monomer M comprises an aromatic monofunctional monomer m1 and an aromatic crosslinking monomer m2.

10. The resin particles according to claim 8, wherein the content of said compound A in said 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 content of said aromatic monofunctional monomer m1 in said monomer M is 50% by weight to 99% by weight.

12. The resin particles according to claim 9, wherein the content of said aromatic crosslinkable monomer m2 in said monomer M is 1% by weight to 50% by weight.

13. Resin particles described in claim 9, wherein the content ratio of the aromatic crosslinkable monomer m2 relative to the compound A in the monomer composition is 1 part by weight to 1,000 parts by weight when the compound A is 100 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 per 100 parts by weight of the monomer composition.

15. The resin particles according to claim 1, which are for use in semiconductor parts.

16. A resin composition for semiconductor members, comprising the resin particles according to claim 15.

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