Resin particles, methods for producing the same, and their applications

Abstract

This invention provides resin particles that are flexible and have excellent heat resistance. It also provides applications for such resin particles and methods for producing such resin particles. [Solution] The resin particles according to the embodiment of the present invention have a first glass transition temperature and a second glass transition temperature, the first glass transition temperature being -40°C to -20°C, the second glass transition temperature being 100°C to 140°C, and the 5% thermoweight loss temperature when heated at 10°C / min in an air atmosphere is 280°C or higher.

Description

Technical Field

[0001] The present invention relates to resin particles, a method for producing the same, and uses thereof.

Background Art

[0002] In semiconductor members, in order to suppress transmission loss in response to high-frequency signals for next-generation high-speed communication, reduction of dielectric constant, reduction of dielectric tangent, and thinning are required. Further, with thinning, suppression of warpage caused by heat history or the like is required. In order to reduce the dielectric constant, reduce the dielectric tangent, and suppress warpage, adding resin particles having softness to the semiconductor member has been considered.

[0003] For example, as conventional resin particles, organic fine particles having a core portion with a glass transition temperature of -100°C to -30°C and a shell portion with a glass transition temperature of 80°C to 120°C have been reported (Patent Document 1). However, since the shell portion is formed by polymerization of an acrylic monomer, the value of the dielectric tangent is high and the heat resistance is low. Further, the particle diameter is large, which forms irregularities in the base resin, leading to deterioration of the dielectric tangent and adhesion.

[0004] Further, as conventional resin particles having a small particle diameter, fine particles having a core containing an acrylic resin and a glass transition temperature of 45°C or higher have been reported (Patent Document 2). However, since the fine particles described in Patent Document 2 have a high acrylic composition ratio, the value of the dielectric tangent is high and the heat resistance is low. Further, since the glass transition temperature is high and it does not have softness, it is not suitable for the above uses.

[0005] Further, as conventional resin particles having a small particle diameter, there are particles produced by preparing polybutadiene latex by emulsion polymerization and then grafting it by seed emulsion polymerization of methyl methacrylate and styrene (Patent Document 3). However, since the particles described in Patent Document 3 have a high acrylic composition ratio, the value of the dielectric tangent is high and the heat resistance is low.

Prior Art Documents

Patent Documents

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-154756 [Patent Document 2] Japanese Patent Publication No. 2018-184550 [Patent Document 3] Japanese Patent Publication No. 2020-164578 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] This invention was made to solve the above-mentioned conventional problems, and its main objective is to provide resin particles having flexibility and excellent heat resistance. It also aims to provide a method for producing such resin particles. Furthermore, it aims to provide applications for such resin particles. [Means for solving the problem]

[0008] [1] The resin particles according to the embodiment of the present invention are It has a first glass transition temperature and a second glass transition temperature, The above first glass transition temperature is -40.0°C to -20.0°C. The above second glass transition temperature is 100.0°C to 140.0°C. The temperature at which the 5% thermogravimetric loss occurs when the temperature is raised at 10°C / min in an air atmosphere is 280°C or higher. [2] The resin particles described in [1] above may have an average particle diameter of 0.1 μm to 10.0 μm. [3] The resin particles described in [1] or [2] above may also include a polymer P obtained by the reaction of a composition C comprising a compound (A) having an ether structure and a radical reactive group represented by formula (1), and a monomer component (M) that reacts with the compound (A). [ka] [4] In the resin particles described in [3] above, composition C may contain a reactive soft component that is reactive with the monomer component (M). [5] In the resin particles described in [4] above, the monomer component (M) includes an aromatic crosslinkable monomer. When the total amount of the above compound (A), the above monomer component (M), and the above reactive soft component is 100 parts by weight, the aromatic crosslinkable monomer may be greater than 0 parts by weight and less than 30 parts by weight. [6] In the resin particles described in [4] or [5] above, the monomer component (M) includes an aromatic monofunctional monomer. When the total of the above compound (A), the above monomer component (M), and the above reactive soft component is 100 parts by weight, the aromatic monofunctional monomer may be 50 parts by weight or more. [7] In the resin particles described in any one of the above items [4] to [6], when the total of the above compound (A), the above monomer component (M), and the above reactive soft component is 100 parts by weight, the amount of the above compound (A) may be greater than 0 parts by weight and less than 30 parts by weight. [8] In the resin particles described in any one of the above items [4] to [7], when the total of the above compound (A), the above monomer component (M), and the above reactive soft component is 100 parts by weight, the amount of the above reactive soft component may be greater than 0 parts by weight and 30 parts by weight or less. [9] In the resin particles described in any one of the above items [4] to [8], the reactive soft component may contain polybutadiene.

[10] In the resin particles described in any one of the above items [4] to [9], when the total of the above compound (A), the above monomer component (M), and the above reactive soft component in composition C is 100 parts by weight, the block copolymer may be 0 to 30 parts by weight.

[11] The resin particles described in any one of the above items [1] to

[10] may have a dielectric loss tangent of 0.0030 or less at a measurement frequency of 10 GHz.

[12] The resin particles described in any one of the above items [1] to

[11] may be used in a resin composition for semiconductor components.

[13] A resin composition for semiconductor components according to an embodiment of the present invention contains resin particles as described in any one of the above [1] to

[12] .

[14] The dispersion according to the embodiment of the present invention contains the resin particles described in any one of the above [1] to

[11] .

[15] The method for producing resin particles according to embodiments of the present invention is The method involves a suspension polymerization reaction of a composition C containing a compound (A) having an ether structure and a radical-reactive group represented by formula (1), a monomer component (M) that reacts with compound (A), and a reactive soft component. [ka]

[16] In the method for producing resin particles described in

[15] above, the monomer component (M) may include an aromatic crosslinkable monomer and an aromatic monofunctional monomer.

[17] In the method for producing resin particles described in

[15] or

[16] above, the reactive soft component may contain polybutadiene. [Effects of the Invention]

[0009] According to embodiments of the present invention, it is possible to provide resin particles having flexibility and excellent heat resistance. Furthermore, a method for producing such resin particles can be provided. In addition, applications for such resin particles can be provided. [Modes for carrying out the invention]

[0010] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0011] In this specification, the term "(meth)acrylic" means "acrylic and / or methacrylic," the term "(meth)acrylate" means "acrylate and / or methacrylate," and the term "(meth)acrylonitrile" means "acrylonitrile and / or methacrylonitrile."

[0012] <<Resin Particles>> The resin particles according to the embodiment of the present invention have a first glass transition temperature and a second glass transition temperature. The first glass transition temperature is -40.0°C to -20.0°C, and the second glass transition temperature is 100.0°C to 140.0°C. The resin particles according to the embodiment of the present invention have softness due to the first glass transition temperature, and by adding them to a base resin such as a semiconductor member, flexibility is imparted to the member, and an excellent stress relaxation effect against external stress is exhibited. Therefore, the resin particles according to the embodiment of the present invention can be used as a stress relaxant.

[0013] The resin particles according to the embodiment of the present invention have a 5% thermogravimetric reduction temperature of 280°C or higher when heated at 10°C / min in an air atmosphere. Thus, since the resin particles according to the embodiment of the present invention have a high 5% thermogravimetric reduction temperature and excellent heat resistance, high heat resistance can be exhibited in the resin in which the resin particles are mixed. The 5% thermogravimetric reduction temperature of the resin particles according to the embodiment of the present invention is preferably 285°C or higher, more preferably 290°C or higher, and still more preferably 293°C or higher when heated at 10°C / min in an air atmosphere. The higher the 5% thermogravimetric reduction temperature, the better, but realistically, the upper limit can be 500°C or lower. The higher the 5% weight loss temperature within the above range, the higher heat resistance can be exhibited by the resin particles according to the embodiment of the present invention. If the 5% weight loss temperature is lower than 280°C in the above range, deformation will occur in the resin particles due to heating. For example, when the resin particles are kneaded with a thermosetting resin, deformation will occur in the resin particles due to heating for the curing reaction, and the effects obtained by adding the resin particles, such as the stress relaxation effect and the low dielectric tangent effect, may decrease.

[0014] Thus, the resin particles according to the embodiment of the present invention have softness and excellent heat resistance, and in addition to stress relaxation of the resin in which the resin particles are mixed, improvement in heat resistance is also possible, and they are suitable as a stress relaxant to be added to a resin composition for a semiconductor member, for example.

[0015] The glass transition temperature of resin particles can be measured using a differential scanning calorimeter (DSC) according to the method described in JIS K7121:1987, 2012 "Method for Measuring Transition Temperature of Plastics".

[0016] In order to better exhibit the effects of the present invention, the first glass transition temperature is preferably -40.0°C to -25.0°C, more preferably -40.0°C to -27.0°C, even more preferably -40.0°C to -30.0°C, and particularly preferably -39.0°C to -32.0°C.

[0017] In order to better exhibit the effects of the present invention, the second glass transition temperature is preferably 100.0°C to 135.0°C, more preferably 105.0°C to 135.0°C, and even more preferably 110.0°C to 130.0°C.

[0018] The resin particles according to the embodiment of the present invention may have one glass transition temperature (only a first glass transition temperature) as a glass transition temperature of -40.0°C to -20.0°C, or may have multiple glass transition temperatures. The resin particles according to the embodiment of the present invention may have one glass transition temperature (only a second glass transition temperature) as a glass transition temperature of 100°C to 140°C, or may have multiple glass transition temperatures.

[0019] The resin particles according to the embodiments of the present invention typically have a dielectric loss tangent of 0.0050 or less at a frequency of 10 GHz, preferably 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 0.0011 or less. If the dielectric loss tangent of the resin particles according to the embodiments of the present invention is within the above range, the resin particles will have even better low dielectric properties in addition to stress relaxation and improved heat resistance of the resin in which the resin particles are mixed, so that, for example, excellent low dielectric properties can be realized in semiconductor materials. Therefore, it is more suitable for addition to semiconductor materials. The lower limit of the above dielectric loss tangent may preferably be 0 or more.

[0020] The average particle size of the resin particles according to the embodiments of the present invention is preferably 0.1 μm to 10.0 μm, more preferably 0.1 μm to 5.0 μm or less, and even more preferably 0.1 μm to 1.0 μm. Resin particles having such an average particle size are suitable for, for example, thinning semiconductor components.

[0021] The average particle diameter of the resin particles according to the embodiments of the present invention is preferably 100 nm to 900 nm, more preferably 200 nm to 850 nm, and even more preferably 250 nm to 800 nm. If the average particle diameter of the resin particles according to the embodiments of the present invention is within the above range, it is more suitable for thinning semiconductor materials.

[0022] The resin particles according to the embodiments of the present invention are typically solid particles. If the resin particles according to the embodiments of the present invention are solid particles, they can exhibit better flexibility.

[0023] The resin particles according to embodiments of the present invention typically include a polymer containing an ether structure represented by formula (1). Such a polymer is, for example, polymer P obtained by the reaction of a composition C containing a compound (A) having an ether structure and a radical-reactive group represented by formula (1), and a monomer component (M) that reacts with compound (A). Therefore, a preferred embodiment of polymer P includes an ether structure represented by formula (1) and a monomer-derived structural unit contained in the monomer component (M). By including such a polymer P, the effects of the present invention can be more fully expressed. [ka]

[0024] Polymer P can thus be defined as being obtained by the reaction of composition C containing compound (A) and a monomer component (M) that reacts with compound (A). This is because, since polymer P is formed by the reaction of composition C containing compound (A) and a monomer component (M) that reacts with compound (A), it is impossible and impractical to directly identify polymer P by its structure. Therefore, the provision that "it is obtained by the reaction of composition C containing compound (A) and a monomer component (M) that reacts with compound (A)" appropriately identifies polymer P as a "substance." Polymer P may consist of only one type or two or more types.

[0025] The content of polymer P in the resin particles according to the embodiments of the present invention is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably 98% to 100% by weight, in order to better exhibit the effects of the present invention.

[0026] As compound (A), any suitable compound can be used as long as it has an ether structure represented by formula (1) above and a radical reactive group, provided that it does not impair the effects of the present invention. Preferably, such compound (A) is polyphenylene ether, as it can more effectively exhibit the effects of the present invention. Polyphenylene ether is a reactive polyphenylene ether that reacts with the above monomer component (M) by a polymerization initiator, and is typically a modified polyphenylene ether having a polymerizable double bond at at least one end. The modified polyphenylene ether preferably has polymerizable double bonds at both ends, and more preferably is a modified oligomer with a low molecular weight and a difunctional group based on polyphenylene ether. Here, "having a difunctional group" means that a functional group having a double bond, or a functional group having a substituent with a double bond, is located at both ends of the oligomer. The number-average molecular weight Mn of the above oligomer is preferably 500 to 3500, as this allows for the simpler creation of resin particles that are flexible and have excellent heat resistance.

[0027] A preferred example of such a modified polyphenylene ether is the compound represented by the following formula (2). [ka]

[0028] In equation (2), n1 and n2 represent integers from 0 to 300 independently of each other, provided that at least one of them is an integer greater than or equal to 1. 3 This represents a divalent linking group. 3The group is preferably selected from the group consisting of alkylene groups, alkenylene groups, -O-, -CO-, -CS-, -SO-, and -SO2-, more preferably an alkylene group, and even more preferably an isopropylidene group (-C(CH3)2-). Examples of commercially available compounds represented by formula (2) include the "Noryl®" series (Noryl® SA9000, etc.) (manufactured by SABIC). As described above, it is preferable that the modified polyphenylene ether has (meth)acryloyl groups at both ends. That is, compound (A) may be a polyphenylene ether having (meth)acryloyl groups at both ends.

[0029] Another preferred example of a modified polyphenylene ether is the compound represented by the following formula (3). [ka]

[0030] In equation (3), n1 and n2 represent integers from 0 to 300, independent of each other, provided that at least one of them is an integer of 1 or greater. A commercially available example of the compound represented by equation (3) is the "OPE-2St" series (manufactured by Mitsubishi Gas Chemical).

[0031] Other commercially available polyphenylene ethers include, for example, the "Yupiace®" series (manufactured by Mitsubishi Chemical Corporation) and the "Zylon®" series (manufactured by Asahi Kasei Corporation).

[0032] The content of compound (A) in composition C is preferably greater than 0% by weight and less than 30% by weight, more preferably 1% to 25% by weight, even more preferably 2% to 22% by weight, particularly preferably 2.5% to 20% by weight, and most preferably 3% to 15% by weight, in order to better exhibit the effects of the present invention. If the content of compound (A) in composition C is too low and outside the above range, the effects of the present invention may not be exhibited, for example, high heat resistance or excellent flexibility may not be exhibited. If the content of compound (A) in composition C is too high and outside the above range, the effects of the present invention may not be exhibited, for example, compound (A) may not dissolve easily in composition C, and resin particles may not be obtained.

[0033] The monomer component (M) is a radical polymerizable monomer, preferably a vinyl monomer, and more preferably a crosslinkable monomer (a) and a monofunctional monomer (b). Therefore, a preferred embodiment of polymer P includes an ether structure represented by formula (1), a structural unit derived from the crosslinkable monomer (a), and a structural unit derived from the monofunctional monomer (b). By including such a polymer P, the effects of the present invention can be more fully expressed.

[0034] The crosslinkable monomer (a) has two or more double bonds in its molecule. Examples of crosslinkable monomers (a) include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylenebis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinkable monomers such as divinylbenzene, divinylnaphthalene, diallyl phthalate, and divinylbiphenyl. In terms of being able to better express the effects of the present invention, aromatic crosslinkable monomers are preferred as crosslinkable monomer (a), and divinylbenzene is more preferred. There may be only one crosslinkable monomer (a) or there may be two or more.

[0035] Monofunctional monomer (b) has one double bond in its molecule. Examples of monofunctional monomer (b) include aromatic monofunctional monomers such as styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinylnaphthalene; alkyl (meth)acrylic acid esters with 1 to 16 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; carboxyl group-containing hydrophilic monomers such as (meth)acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalic acid. In order to better express the effects of the present invention, it is preferable that monofunctional monomer (b) includes an aromatic monofunctional monomer. The aromatic monofunctional monomer is preferably styrene or ethyl vinylbenzene. Monofunctional monomer (b) may be one type or two or more types.

[0036] The total content ratio of the crosslinkable monomer (a) and monofunctional monomer (b) in the monomer component (M) is preferably 50 to 100 parts by weight, more preferably 80 to 100 parts by weight, even more preferably 90 to 100 parts by weight, and particularly preferably 95 to 100 parts by weight, when the monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention. The total content ratio of the aromatic crosslinkable monomer and aromatic monofunctional monomer in the monomer component (M) is preferably 50 to 100 parts by weight, more preferably 80 to 100 parts by weight, even more preferably 90 to 100 parts by weight, and particularly preferably 95 to 100 parts by weight, when the monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention.

[0037] In order to better exhibit the effects of the present invention, the content ratio of the crosslinkable monomer (a) in the monomer component (M) is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and even more preferably 3 to 10 parts by weight, when the monomer component (M) is 100 parts by weight.

[0038] In order to better exhibit the effects of the present invention, the content of aromatic crosslinkable monomers in monomer component (M) is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and even more preferably 3 to 10 parts by weight, when monomer component (M) is 100 parts by weight.

[0039] In order to better express the effects of the present invention, the content ratio of monofunctional monomer (b) in monomer component (M) is preferably 20 to 99 parts by weight, more preferably 40 to 99 parts by weight, even more preferably 50 to 99 parts by weight, even more preferably 70 to 99 parts by weight, particularly preferably 80 to 98 parts by weight, and most preferably 90 to 97 parts by weight, when monomer component (M) is 100 parts by weight.

[0040] In order to better express the effects of the present invention, the content of aromatic monofunctional monomers in monomer component (M) is preferably 20 to 99 parts by weight, more preferably 40 to 99 parts by weight, even more preferably 50 to 99 parts by weight, particularly preferably 70 to 99 parts by weight, and most preferably 80 to 98 parts by weight, when monomer component (M) is 100 parts by weight.

[0041] In order to better exhibit the effects of the present invention, the content of (meth)acrylic monomer in monomer component (M) is preferably 0 to 20 parts by weight, more preferably 0 to 15 parts by weight, and even more preferably 0 to 10 parts by weight, when monomer component (M) is 100 parts by weight. This reduces the dielectric loss tangent of the resin particles according to the embodiments of the present invention and improves the dielectric properties. In this specification, (meth)acrylic monomer means monomer having a (meth)acryloyl group.

[0042] The monomer component (M) may include, in addition to the crosslinkable monomer (a) and monofunctional monomer (b) described above, any other monomer of appropriate reactivity. The other monomer may be one type or two or more types.

[0043] The content of monomer component (M) in composition C is preferably 70% by weight or more and less than 100% by weight, more preferably 70% by weight to 99% by weight, even more preferably 75% by weight to 95% by weight, and particularly preferably 75% by weight to 90% by weight. If the content of monomer component (M) in composition C is too low and outside the above range, the effects of the present invention may not be realized, for example, excellent dielectric properties may not be realized. Herein, in the present invention, monomer component (M) does not include polymerization initiators and surfactants used in the polymerization reaction.

[0044] In embodiments of the present invention, composition C typically includes a flexible component (S) in addition to compound (A) and monomer component (M). The flexible component (S) is preferably a reactive flexible component that reacts with monomer component (M). The reactive flexible component preferably has a radical reactive group, and for example, includes a double bond. The resin particles according to embodiments of the present invention can have excellent flexibility by containing a polymer P obtained by the reaction of composition C containing such a flexible component (S).

[0045] The reactive flexible component preferably includes a polymer of a conjugated diolefin monomer. Examples of polymers of conjugated diolefin monomers include polybutadiene and polyisoprene. The reactive flexible component preferably includes polybutadiene. Polybutadiene may also be partially hydrogenated polybutadiene. Such a configuration can further enhance the effects of the present invention.

[0046] The soft component (S) may include thermoplastic elastomers in addition to those described above. Examples of thermoplastic elastomers include styrene-butadiene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, styrene-ethylene-propylene-styrene block copolymers, styrene-ethylene-butene-styrene copolymers, styrene-isoprene-styrene block copolymers, styrene-isobutylene-styrene copolymers, and styrene-isobutylene copolymers. The thermoplastic elastomer is preferably a block copolymer.

[0047] The block copolymer is preferably reactive with the monomer component (M). That is, the reactive soft component may further contain a block copolymer in addition to those described above, and may further contain a block copolymer that is a thermoplastic elastomer. Examples of such block copolymers include polymers having a polymer block of a vinyl monomer and a polymer block of a conjugated diolefin monomer. The vinyl monomer is preferably an aromatic vinyl monomer. Examples of such block copolymers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, methylene methacrylate-butadiene-styrene copolymers, and hydrogenated versions thereof, preferably styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and hydrogenated versions thereof, and more preferably styrene-butadiene-styrene block copolymers and hydrogenated versions thereof.

[0048] Therefore, the reactive flexible component preferably includes polymers of conjugated diolefin monomers and polymers having polymer blocks of vinyl monomers and polymer blocks of conjugated diolefin monomers, and more preferably includes polybutadiene and styrene-butadiene-styrene block polymers. With this configuration, the effects of the present invention can be more fully expressed. Furthermore, the block copolymer (styrene-butadiene-styrene block polymer) can improve the dispersibility of the reactive flexible component (polybutadiene) in the monomer component (M), which is the matrix, during the polymerization reaction of composition C in the production of polymer P. In this respect as well, the effects of the present invention can be more fully expressed.

[0049] In order to better express the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, compound (A) is preferably greater than 0 parts by weight and less than 30 parts by weight, more preferably 1 to 25 parts by weight, even more preferably 2 to 22 parts by weight, particularly preferably 2.5 to 20 parts by weight, and most preferably 3 to 15 parts by weight.

[0050] In order to better express the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the amount of crosslinkable monomer (a) is preferably 0 to less than 30 parts by weight, more preferably greater than 0 parts by weight and less than 30 parts by weight, even more preferably 1 to 25 parts by weight, particularly preferably 2 to 20 parts by weight, and most preferably 3 to 10 parts by weight.

[0051] In order to better express the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the aromatic crosslinkable monomer is preferably 0 to less than 30 parts by weight, more preferably greater than 0 parts by weight and less than 30 parts by weight, even more preferably 1 to 25 parts by weight, particularly preferably 2 to 20 parts by weight, and most preferably 3 to 20 parts by weight.

[0052] In order to better exhibit the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the amount of monofunctional monomer (b) is preferably 50 parts by weight or more, more preferably 50 to 99 parts by weight, even more preferably 60 to 98 parts by weight, particularly preferably 65 to 95 parts by weight, and most preferably 70 to 90 parts by weight.

[0053] In order to better exhibit the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the aromatic monofunctional monomer is preferably 50 parts by weight or more, more preferably 50 to 99 parts by weight, even more preferably 60 to 98 parts by weight, particularly preferably 65 to 95 parts by weight, and most preferably 70 to 90 parts by weight.

[0054] In order to better exhibit the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the reactive soft component is preferably greater than 0 parts by weight and 30 parts by weight or less, more preferably 1 to 25 parts by weight, even more preferably 2 to 20 parts by weight, particularly preferably 3 to 15 parts by weight, and most preferably 5 to 15 parts by weight.

[0055] In order to better exhibit the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the amount of polybutadiene is preferably greater than 0 parts by weight and 30 parts by weight or less, more preferably 1 to 25 parts by weight, even more preferably 1 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, and most preferably 2 to 15 parts by weight.

[0056] In order to better express the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the block copolymer that reacts with monomer component (M) is preferably 0 to 30 parts by weight, more preferably 0 to 25 parts by weight, even more preferably 0 to 20 parts by weight, particularly preferably 0 to 15 parts by weight, and most preferably more than 0 to 15 parts by weight.

[0057] In order to better exhibit the effects of the present invention, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the (meth)acrylic compound is preferably 0 parts by weight or more and less than 20 parts by weight, more preferably 0 to 15 parts by weight, and even more preferably 0 to 10 parts by weight. This makes it possible to realize resin particles with excellent dielectric properties. In this specification, (meth)acrylic compound means a compound having a (meth)acryloyl group. (Meth)acrylic compound also includes (meth)acrylic monomers.

[0058] <<<Applications of resin particles>>> The resin particles according to the embodiments of the present invention can be used in various applications. For example, in addition to applications in resin compositions for semiconductor components, the resin particles according to the embodiments of the present invention can be applied to applications that can utilize the effects of the present invention, such as paint compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films. In terms of better utilization of the effects of the present invention, the resin particles according to the embodiments of the present invention are suitable for semiconductor components, and are particularly suitable for use in resin compositions for semiconductor components. Because the resin particles according to the embodiments of the present invention are flexible and have excellent heat resistance, they can relieve stress in semiconductor components while improving heat resistance. Furthermore, because the resin particles according to the embodiments of the present invention also have excellent low dielectric properties, they can also realize excellent low dielectric properties in semiconductor components.

[0059] Semiconductor components refer to the components that make up a semiconductor, such as semiconductor packages and semiconductor modules. In this specification, resin compositions for semiconductor components refer to resin compositions used in semiconductor components.

[0060] A semiconductor package is a component in which an IC chip is an essential component, and is constructed using at least one material selected from molding resin, underfill material, molded underfill material, die bonding material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.

[0061] A semiconductor module is a component in which a semiconductor package is an essential component, and which is composed of at least one component selected from prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic shielding films, and adhesive sheets for printed circuit boards.

[0062] ≪≪Method for manufacturing resin particles≫≫ Resin particles according to embodiments of the present invention can be produced, for example, by the polymerization reaction of composition C described above.

[0063] The polymerization reaction is preferably a suspension polymerization reaction.

[0064] A method for producing resin particles according to embodiments of the present invention typically involves a suspension polymerization reaction of a composition C comprising a compound (A) having an ether structure and radical reactive group represented by formula (1), a monomer component (M) that reacts with compound (A), and a soft component (S). Composition C preferably comprises a compound (A) having an ether structure and radical reactive group represented by formula (1), a monomer component (M) that reacts with compound (A), and a reactive soft component. This makes it possible to obtain resin particles with flexibility and excellent heat resistance.

[0065] Suspension polymerization is a polymerization method in which monomers and an aqueous medium are mechanically stirred to suspend the monomers in the aqueous medium and polymerize them. In embodiments of the present invention, it is preferable to carry out the suspension polymerization reaction by adding an oil phase containing composition C to the aqueous phase and dispersing it.

[0066] The dispersion of the oil phase into the aqueous phase can be carried out using any suitable dispersion method, 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 dispersion methods include those using homomixers or homogenizers, such as high-speed homomixers, polytron homogenizers, ultrasonic homogenizers, and high-pressure homogenizers.

[0067] For composition C, the explanation in the section on "Resin Particles" can be directly applied. That is, for compound (A), monomer component (M), and soft component (S), the explanation in the section on "Resin Particles" can be directly applied.

[0068] In addition to the components described above, the oil phase may contain any other suitable components as long as they do not impair the effects of the present invention.

[0069] The aqueous phase typically includes water-based solvents. Typical examples of water-based solvents include water and mixed solvents of water and lower alcohols (methanol, ethanol, etc.).

[0070] The amount of aqueous solvent used can be any appropriate amount, as long as it does not impair the effects of the present invention. The amount of aqueous solvent used is preferably 10 to 5000 parts by weight, more preferably 50 to 3000 parts by weight, and even more preferably 100 to 2000 parts by weight, per 100 parts by weight of composition C.

[0071] The aqueous phase may contain any other suitable components in addition to the components described above, as long as they do not impair the effects of the present invention.

[0072] When carrying out the reaction of composition C, any suitable additive that does not fall under compound (A), monomer component (M), or softening component (S) may be used, as long as it does not impair the effects of the present invention. There may be only one additive or two or more additives.

[0073] Examples of additives include polymerization initiators, surfactants, dispersion stabilizers, chain transfer agents, and antioxidants.

[0074] Any suitable polymerization initiator can be used as the polymerization initiator, as long as it does not impair the effects of the present invention. Examples of polymerization initiators include organic peroxides such as cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexyn-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentane hydroperoxide, tert-butylperoxybenzoate, etc.; 2,2'-azobibisisobutyronitrile, 2,2'-azobi 2,2'-Azobis(2-methylbutyronitrile), 2,2'-Azobis(2-isopropylbutyronitrile), 2,2'-Azobis(2,3-dimethylbutyronitrile), 2,2'-Azobis(2,4-dimethylbutyronitrile), 2,2'-Azobis(2-methylcapronitrile), 2,2'-Azobis(2,3,3-trimethylbutyronitrile), 2,2'-Azobis(2,4,4-trimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylbutyronitrile) Examples of azo compounds include valeronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-ethoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-n-butoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid). Polymerization initiators may be used individually or in combination of two or more.

[0075] Polymerization initiators may be added to the aqueous phase or the oil phase, but they are typically added to the oil phase.

[0076] The amount of polymerization initiator added is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight.

[0077] As the surfactant, any suitable surfactant can be used as long as it does not impair the effects of the present invention. There may be only one type of surfactant or two or more types. Examples of such surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0078] Examples of anionic surfactants include sodium oleate; fatty acid soaps such as potassium castor oil soap; polysulfonates; polycarboxylates; alkyl sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkylaryl sulfonates; alkylnaphthalene sulfonates; alkanesulfonates; dialkyl sulfonates; dialkyl sulfosuccinates; alkyl phosphates; alkyl phosphate esters; naphthalene sulfonic acid formalin condensates or their salts, such as sodium salts of β-naphthalene sulfonic acid formalin condensates; and polyoxyethylene nonylphenyl Examples include polyoxyethylene alkylphenyl ether sulfates such as ether sulfates (commercial products include, for example, Newcol 707-SF manufactured by Nippon Emulsifier Co., Ltd.); polyoxyethylene sulfonated phenyl ether phosphate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and ammonium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkyl sulfates; polyoxyethylene alkyl phosphate sulfonates; glycerol borate fatty acid esters; polyoxyethylene glycerol fatty acid esters; phosphate ester surfactants; and phosphite ester surfactants. The anionic surfactant may be one type or two or more types. Furthermore, the countercation of the anionic group is preferably an ammonium salt.

[0079] Examples of cationic surfactants include alkylamine salts such as laurylamine acetate and stearylamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride. The cationic surfactant may be present in a single form or in a combination of two or more forms.

[0080] Examples of nonionic surfactants include (meth)acrylate sulfate ester surfactants (commercial products such as RMA-564, RMA-568, and RMA-1114 from Nippon Emulsifier Co., Ltd.); polyoxyalkylene branched decyl ethers; polyoxyalkylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene isodecyl ether, polyoxyethylene lauryl ether, and polyoxyethylene oleyl cetyl ether; polyoxyalkylene aryl ethers such as polyoxyethylene naphthyl ether and polyoxyethylene phenyl ether; polyoxyalkylene alkylaryl ethers; polyether polyols; polyoxyethylene styrene phenyl ether; polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl isostearate; polyoxyethylene fatty acid esters; sorbitan fatty acid esters; polyoxysorbitan fatty acid esters; polyoxyethylene alkylamines; glycerin fatty acid esters; and oxyethylene-oxypropylene block polymers. The nonionic surfactant may be one type or two or more types.

[0081] Examples of amphoteric surfactants include lauryldimethylamine oxide, alkyldiaminoethylglycine hydrochloride, sodium laurylaminopropionate, and alkylbetaine. The amphoteric surfactant may be present in a single form or in two or more forms.

[0082] A reactive surfactant may be used as the surfactant. A reactive surfactant is a surfactant having a radical reactive group, such as a surfactant having a vinyl group. There may be only one type of reactive surfactant or two or more types. When a reactive surfactant is used, the surfactant can be incorporated into the polymer, so the surfactant can be effectively unevenly distributed on the particle surface during suspension polymerization, and the surfactant effect can be improved. As a result, an excellent surfactant effect can be obtained, particle aggregation and coalescence during manufacturing can be suppressed, the generation of substandard particles as by-products can be reduced, and more uniform dielectric properties can be exhibited.

[0083] Examples of reactive surfactants include anionic surfactants having a vinyl group and nonionic surfactants having a vinyl group.

[0084] Examples of anionic surfactants having a vinyl group include polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium, polyoxyethylene styrene-propenylphenyl ether sulfate ammonium, polyoxyalkylene alkenyl ether sulfate ammonium, α-sulfo-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium, polyoxypropylene allyl ether phosphate, and bis(polyoxyethylene phenyl ether) methacrylate sulfate. Furthermore, ammonium salts are preferred as the countercation of the anionic group. By using such surfactants, the average particle size of the resin particles can be reduced. In addition, the amount of metal residue can be reduced.

[0085] Examples of commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium products include the trade names "Aqualon KH-10" and "Aqualon KH-1025" (a 25% by weight aqueous solution of "Aqualon KH-10") manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0086] Examples of commercially available polyoxyethylene styrene-propenylphenyl ether sulfate ammonium products include the product names "Aqualon AR-10," "Aqualon AR-20," "Aqualon AR-3025" (a 25% by weight aqueous solution of "Aqualon AR-30"), and "Aqualon AR-1025" (a 25% by weight aqueous solution of "Aqualon AR-10"), all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0087] One example of a commercially available polyoxyalkylene alkenyl ether ammonium sulfate product is "Latemul PD-104" manufactured by Kao Corporation.

[0088] Examples of commercially available α-sulfo-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium products include "Adekaria Soap SR-10" and "Adekaria Soap SR-20" manufactured by ADEKA Corporation.

[0089] A commercially available product containing polyoxypropylene allyl ether phosphate is, for example, "ADEKA Soap PP-70" manufactured by ADEKA Corporation.

[0090] A commercially available product containing bis(polyoxyethylene phenyl ether) methacrylate sulfate is, for example, "Antox MS-60" manufactured by Nippon Emulsifier Co., Ltd.

[0091] Examples of nonionic surfactants having a vinyl group include polyoxyethylene styrene-propenylphenyl ether, polyoxyethylene-1-(allyloxymethyl) alkyl ether, and polyoxyalkylene alkenyl ether.

[0092] Examples of commercially available polyoxyethylene styrene-propenylphenyl ether include the product names "Aqualon AN-10," "Aqualon AN-20," "Aqualon AN-30," and "Aqualon AN-5065" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0093] Examples of commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ethers include the product names "Aqualon KN-10," "Aqualon KN-20," "Aqualon KN-30," and "Aqualon KN-5065" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the product names "Adekaria Soap ER-10," "Adekaria Soap ER-20," "Adekaria Soap ER-30," and "Adekaria Soap ER-40" manufactured by ADEKA Corporation.

[0094] Examples of commercially available polyoxyalkylene alkenyl ethers include the product names "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0095] Surfactants may be added to the aqueous phase or the oil phase, but they are typically added to the aqueous phase.

[0096] The amount of surfactant used is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, and even more preferably 0.01 to 0.1 parts by weight, per 100 parts by weight of the aqueous solvent contained in the aqueous phase.

[0097] As a dispersion stabilizer, any suitable dispersion stabilizer can be used as long as it does not impair the effects of the present invention. There may be only one dispersion stabilizer or two or more. Examples of dispersion stabilizers that can better express the effects of the present invention include: polyvinyl alcohol; polycarboxylic acid; celluloses such as hydroxyethylcellulose and carboxymethylcellulose; inorganic water-soluble polymers such as polyvinylpyrrolidone and 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; and 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 that it can better express the effects of the present invention.

[0098] Dispersion stabilizers may be added to the aqueous phase or the oil phase, but they are typically added to the aqueous phase.

[0099] The amount of dispersion stabilizer used is preferably 0 to 50 parts by weight, and more preferably 0 to 10 parts by weight, per 100 parts by weight of the aqueous solvent contained in the aqueous phase.

[0100] Furthermore, if composition C contains a block copolymer as one of the softening components (S), the block copolymer can improve the dispersibility of the softening component (S), such as polybutadiene, in the monomer component (M) which is the matrix. In other words, in addition to its function as a softening component (S) that imparts softness to resin particles, the block copolymer may also have a function similar to that of a so-called dispersion stabilizer, but the block copolymer is not included in the dispersion stabilizer as referred to herein.

[0101] Examples of chain transfer agents include thiol compounds and α-methylstyrene dimers. From the viewpoint of improving heat resistance, it is preferable to use thiol compounds as chain transfer agents.

[0102] As the thiol compound, any suitable thiol compound can be used as long as it does not impair the effects of the present invention. There may be only one thiol compound or two or more. Examples of such thiol compounds include polyfunctional thiol compounds and monofunctional thiol compounds having an alkyl group with 1 to 20 carbon atoms in the molecule.

[0103] As for the polyfunctional thiol compound, any suitable polyfunctional thiol compound can be used as long as it has two or more thiol groups in its molecule, as long as it does not impair the effects of the present invention. There may be only one polyfunctional thiol compound or two or more. 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 tristhiog Examples include trimethylolpropane tristhioglycolate (TMTG), trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthioglycolate (PETG), pentaerythritol tetrakisthioglycolate, dipentaerythritol hexathiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 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.

[0104] As monofunctional thiol compounds having an alkyl group with 1 to 20 carbon atoms in the molecule, any suitable monofunctional thiol compound having an alkyl group with 1 to 20 carbon atoms in the molecule can be used, as long as it has one thiol group and an alkyl group with 1 to 20 carbon atoms in the molecule, and does not impair the effects of the present invention. There may be only one monofunctional thiol compound having an alkyl group with 1 to 20 carbon atoms in the molecule, or there may be two or more. Examples of such monofunctional thiol compounds having an alkyl group with 1 to 20 carbon atoms in the molecule include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanthiol, dodecanethiol, and compounds having a branched chain structure thereof.

[0105] The amount of 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, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight. That is, the monomer composition contains preferably 5 parts by weight or less of thiol compound, more preferably 0.05 to 5 parts by weight of thiol compound, even more preferably 0.1 to 3 parts by weight of thiol compound, and particularly preferably 0.3 to 2 parts by weight of thiol compound per 100 parts by weight of the monomer composition.

[0106] Thiol compounds function as chain transfer agents and can become building blocks of polymer P. In radical polymerization systems (for example, radical polymerization systems using hydrolyzable silicon compounds having hydrolyzable silyl groups and groups that react with radically polymerizable unsaturated groups, monofunctional (meth)acrylic monomers, and polyfunctional (meth)acrylic monomers), thiol compounds can stop the elongation of polymer chains by receiving radicals from the growing polymer chain, and can also generate new radicals to initiate the growth reaction of another polymer chain. As a result, it becomes possible to standardize the molecular weight of the resulting polymer P, and consequently the resin particles according to the embodiments of the present invention, and to standardize the particle size distribution.

[0107] As an antioxidant, any suitable antioxidant can be used as long as it does not impair the effects of the present invention. There may be only one antioxidant or two or more antioxidants. Examples of such antioxidants include those with a melting point of 30°C to 105°C. If an antioxidant with a melting point below 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. If an antioxidant with a melting point above 105°C is used, there is a risk that it may affect the dispersion stability of the resin particle dispersion during heat treatment.

[0108] As an antioxidant, it can be used in powder form at room temperature (25°C). Alternatively, it may be used in a dispersed or dissolved state in water, alcohol, etc.

[0109] Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. From the viewpoint of being able to better express the effects of the present invention, antioxidants having radical scavenging ability are preferred, phenolic antioxidants and amine-based antioxidants are preferred, and phenolic antioxidants are more preferred.

[0110] As the phenolic antioxidant, any suitable phenolic antioxidant can be used, as long as it does not impair the effects of the present invention. Such phenolic antioxidants are preferably compounds having substituents such as alkyl groups at the ortho position relative to the phenolic hydroxyl group. Furthermore, from the viewpoint of better exhibiting 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, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4-[[4,6-bis(octylthio)-1,3,5-triazine-2-yl]amino]-2,6-di-tert-butylphenol, and 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0111] As a phosphorus-based antioxidant, any suitable phosphorus-based antioxidant can be used, as long as it does not impair the effects of the present invention. Examples of such phosphorus-based antioxidants include 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane.

[0112] As a sulfur-based antioxidant, any suitable sulfur-based antioxidant can be used, as long as it does not impair the effects of the present invention. Examples of such sulfur-based antioxidants include dioctadecyl 3,3'-thiodipropionate and tetrakis[3-(dodecylthio)propionate]pentaerythritol.

[0113] As the amine-based antioxidant, any suitable amine-based antioxidant can be used, as long as it does not impair the effects of the present invention. Examples of such amine-based antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) butane-1,2,3,4-tetracarboxylic acid, and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

[0114] The amount of antioxidant added is preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight.

[0115] The polymerization temperature can be any suitable temperature within a range that does not impair the effects of the present invention, as long as it is suitable for suspension polymerization. Preferably, such a polymerization temperature is 30°C to 90°C.

[0116] The polymerization time can be any appropriate time, as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. Such a polymerization time is preferably 1 to 48 hours.

[0117] Post-heating, which is preferably performed after polymerization, is a suitable treatment for obtaining high-quality resin particles.

[0118] The temperature of the post-heating, which is preferably performed after polymerization, can be any suitable temperature within a range that does not impair the effects of the present invention. The temperature of such post-heating is preferably 70°C to 120°C.

[0119] The duration of the post-heating, which is preferably performed after polymerization, can be any appropriate time within a range that does not impair the effects of the present invention. Such post-heating is preferably 1 to 24 hours.

[0120] The polymerization described above yields a slurry, which is a dispersion containing particles. After the polymerization step, the particles may be washed, classified, dried, or otherwise removed as needed.

[0121] ≪Dispersion body≫ The resin particles according to the embodiments of the present invention may be used as a dispersion if necessary. Such a dispersion includes the resin particles according to the embodiments of the present invention and a dispersion medium, wherein the resin particles according to the embodiments of the present invention are dispersed in the dispersion medium as a dispersed phase. The dispersion may be used as is, in the form of a slurry obtained after the polymerization step in the above manufacturing method, or it may be used as a solvent dispersion or resin dispersion substituted with another dispersion medium, for example. [Examples]

[0122] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0123] <Average particle size> The Z-mean particle diameter of the resin particles was measured using dynamic light scattering, and the measured Z-mean particle diameter was defined as the average particle diameter of the obtained resin particles. Specifically, the obtained slurry-like resin particles were first diluted with deionized water, and the resulting aqueous dispersion was adjusted to 0.1% by weight. Laser light was then irradiated onto the dispersion, and the scattered light intensity from the resin particles was measured over time in microseconds. The Z-mean particle diameter of the resin particles was then determined by fitting the detected scattering intensity distribution attributable to the resin particles to a normal distribution and calculating the average particle diameter using the cumulant analysis method. The measurement of the Z-mean particle diameter can be easily performed using a commercially available particle size analyzer. In the following examples and comparative examples, the Z-mean particle diameter was measured using a particle size analyzer (Malvern Zetasizer Nano ZS). Typically, commercially available particle size analyzers are equipped with data analysis software, which automatically analyzes the measurement data to calculate the Z-mean particle diameter.

[0124] <Measurement of the 5% thermogravimetric loss temperature when the temperature is raised at 10°C / min in an air atmosphere> The 5% thermogravimetric loss temperature was measured using a differential thermogravimetric simultaneous measurement device (Hitachi High-Tech Science Corporation, "NEXTA STA200RV"). The sampling method and temperature conditions were as follows. A platinum measuring container was filled with 10.5 ± 0.5 mg of the sample, ensuring there were no gaps at the bottom, to prepare the sample for measurement. The 5% thermogravimetric loss temperature was measured using alumina as the reference material under an air flow rate of 200 mL / min. The TG / DTA curve was obtained by heating the sample from 30°C to 800°C at a heating rate of 10°C / min. Using the analysis software provided with the instrument, the temperature at which a 5% weight loss occurred was calculated from this curve and defined as the 5% thermogravimetric loss temperature.

[0125] <Glass transition temperature of resin particles> The glass transition temperature (Tg) of the resin particles was measured using the method described in JIS K7121:1987, 2012 "Method for Measuring the Transition Temperature of Plastics". However, the temperature conditions were as follows: A differential scanning calorimeter DSC7000X, AS-3 (manufactured by Hitachi Science Co., Ltd.) was used. Approximately 6 mg of the sample was packed into the bottom of an aluminum measuring container without any gaps. Using alumina as the reference material under a nitrogen gas flow rate of 20 ml / min, the temperature was raised from -80°C to 200°C at a heating rate of 20°C / min and held for 10 minutes. After the heat treatment, the temperature was raised to 200°C at a heating rate of 20°C / min under a nitrogen gas flow rate of 20 ml / min and held for 10 minutes. The midpoint glass transition temperature was calculated from the DSC curve obtained when the temperature was raised to 200°C at a heating rate of 20°C / min. This intermediate glass transition temperature was determined according to the standard (9.3 "Method for determining the glass transition temperature"). If multiple glass transition temperatures were present in the range of -40.0°C to -20.0°C, the intermediate glass transition temperature determined from the largest endothermic shift in the DSC curve within the range of -40.0°C to -20.0°C was defined as the first glass transition temperature (Tg1). If multiple glass transition temperatures were present in the range of 100.0°C to 140.0°C, the intermediate glass transition temperature determined from the largest endothermic shift in the DSC curve within the range of 100.0°C to 140.0°C was defined as the second glass transition temperature (Tg2).

[0126] <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. The measurements were performed at a frequency of 10 GHz, in a measurement environment of 23°C, and with a relative humidity of 51 ± 1%. The dielectric loss tangent of the resin particles was calculated based on perturbation theory using a resonator.

[0127] <Raw materials used> The ingredients used are as follows:

[0128] [Compounds having an ether structure and radical-reactive groups (A)] • Reactive low molecular weight polyphenylene ether (product name "Noryl(registered trademark) SA9000-111 resin", manufactured by SABIC Corporation)

[0129] [Aromatic monofunctional monomers] ·styrene

[0130] [Aromatic crosslinkable monomers] • Divinylbenzene (DVB) 810 (Nippon Steel Chemical & Material Co., Ltd., containing 81% by weight of divinylbenzene, 19% by weight of ethyl vinylbenzene)

[0131] [Reactive softening component] • Partially hydrogenated polybutadiene (hydrogenation rate 85%) (manufactured by Nippon Soda Co., Ltd., product name "BI-3015") • Styrene-butadiene-styrene block polymer (manufactured by Nippon Soda Co., Ltd., number average molecular weight 35,000)

[0132] [Polymerization initiator] • Lauroyl peroxide (manufactured by NOF Corporation, product name "Perloyl L")

[0133] [Chain transport agent] Dodecanethiol

[0134] [Antioxidant] • Irganox 1010 (manufactured by BASF Japan Ltd.)

[0135] [Aqueous medium] • Ion-exchanged water

[0136] [Surfactants] • Polyoxyethylene styrene-propenylphenyl ether sulfate ammonium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "Aqualon AR-10") • Bis(polyoxyethylene phenyl ether) methacrylate sulfate ammonium salt (manufactured by Nippon Emulsifier Co., Ltd., product name "Antox MS-60") • Polyoxyethylene styrene-propenylphenyl ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "Aqualon AN-5065")

[0137] [Example 1] The oil phase and aqueous phase were prepared with the compositions shown in Table 1. The oil phase and aqueous phase were mixed and dispersed for 5 minutes at a rotation speed of 7,000 rpm using a Polytron homogenizer "PT10-35" (manufactured by Central Science Trading Co., Ltd.). Then, the mixture was emulsified at a processing pressure of 20 MPa using a high-pressure emulsifier NVL-AS200 (manufactured by Yoshida Machinery Industry Co., Ltd.) to prepare a suspension. The obtained suspension was heated at 70°C for 5 hours, and then the temperature was raised to 90°C for 2 hours to carry out polymerization. After the polymerization reaction was complete, the resulting dispersion was cooled and then classified by passing it through a 500-mesh (24 μm mesh opening) screen to obtain a dispersion containing the resin particles of Example 1. The obtained dispersion was heated and dried to obtain resin particles (1) as a dried powder. The results of various measurements are shown in Table 1.

[0138] [Examples 2-5] Resin particles (2) to (5) of Examples 2 to 5 were obtained in the same manner as in Example 1, except that the composition of the oil phase and the water phase were changed as shown in Table 1. The results of various measurements are shown in Table 1.

[0139] [Comparative Example 1] As shown in Table 1, the resin particles (C1) of Comparative Example 1 were obtained in the same manner as in Example 1, except that the composition of the oil phase and the water phase were changed. The results of various measurements are shown in Table 1.

[0140] [Table 1]

[0141] Table 1 shows that the resin particles of Examples 1 to 5 have a first glass transition temperature of -40.0°C to -20.0°C and a second glass transition temperature of 100.0°C to 140.0°C, and have a sufficiently low dielectric loss tangent, thus possessing flexibility and excellent dielectric properties.

[0142] <Performance evaluation: Breaking point strain of particle-doped film> A mixture for evaluation was prepared by defoaming and stirring 0.425 g of particles obtained in the examples and comparative examples, 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) using a planetary stirring defoamer ("Mazelstar KK-250" manufactured by KURABO Co., Ltd.). The evaluation mixture was coated onto a 5 mm thick glass plate using an applicator set to a wet thickness of 250 μm. The ethyl acetate was removed by heating at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes, and then cooled to room temperature to obtain a film containing particles. Furthermore, a film without particles was manufactured in the same manner, except that no particles were added. The obtained film was cut into pieces measuring 10 mm in width and 80 mm in length, which were used as test specimens. Tensile tests were performed on each test specimen using a Shimadzu Corporation "Autograph AG-X plus 100kN" universal testing machine and a Shimadzu Corporation "TRAPEZIUM-X" universal testing machine data processing machine, and the fracture strain was measured. The test specimens were conditioned for 16 hours under a standard atmosphere of JIS K 7100:1999 symbol "23 / 50" and class 2 before being used for measurement. Measurements were performed under the same environment, specifically according to the following conditions. • Chuck spacing: 60mm • Test speed: 5 mm / min Based on the above test, the length L of the specimen at the point of fracture (fracture point) was measured, and the fracture strain (%) was calculated using L and the initial specimen length L0 with the following formula. Fracture point strain (%) = 100 × (L - L0) / L0 The measurement results are shown in Table 2.

[0143] [Table 2]

[0144] Table 2 shows that the film containing the particles of Example 3 is less prone to breakage. Therefore, the resin particles of the present invention can alleviate the stress on the film. [Industrial applicability]

[0145] Resin particles according to embodiments of the present invention can be used in semiconductor components and the like.

Claims

1. It has a first glass transition temperature and a second glass transition temperature, The first glass transition temperature is -40.0°C to -20.0°C. The second glass transition temperature is 100.0°C to 140.0°C. The temperature at which the 5% thermogravimetric loss occurs when the temperature is raised at 10°C / min in an air atmosphere is 280°C or higher. Resin particles.

2. The resin particles according to claim 1, wherein the average particle diameter is 0.1 μm to 10.0 μm.

3. The resin particles according to claim 1, comprising a polymer P obtained by the reaction of a composition C containing a compound (A) having an ether structure and a radical reactive group represented by formula (1), and a monomer component (M) that reacts with the compound (A). 【Chemistry 1】

4. The resin particles according to claim 3, wherein the composition C comprises a reactive soft component that has reactivity with the monomer component (M).

5. The monomer component (M) includes an aromatic crosslinkable monomer. The resin particles according to claim 4, wherein when the total of the compound (A), the monomer component (M), and the reactive soft component is 100 parts by weight, the aromatic crosslinkable monomer is greater than 0 parts by weight and less than 30 parts by weight.

6. The monomer component (M) includes an aromatic monofunctional monomer. The resin particles according to claim 4, wherein when the total of the compound (A), the monomer component (M), and the reactive soft component is 100 parts by weight, the aromatic monofunctional monomer is 50 parts by weight or more.

7. The resin particles according to claim 4, wherein when the total of the compound (A), the monomer component (M), and the reactive soft component is 100 parts by weight, the compound (A) is greater than 0 parts by weight and less than 30 parts by weight.

8. The resin particles according to claim 4, wherein when the total of the compound (A), the monomer component (M), and the reactive soft component is 100 parts by weight, the reactive soft component is greater than 0 parts by weight and 30 parts by weight or less.

9. The resin particles according to claim 4, wherein the reactive soft component comprises polybutadiene.

10. The resin particles according to claim 4, wherein in composition C, when the total amount of compound (A), monomer component (M), and reactive soft component is 100 parts by weight, the block copolymer is 0 to 30 parts by weight.

11. The resin particles according to claim 1, wherein the dielectric loss tangent at a measurement frequency of 10 GHz is 0.0030 or less.

12. Resin particles according to claim 1, for use in a resin composition for semiconductor components.

13. A resin composition for semiconductor components containing the resin particles described in claim 12.

14. A dispersion containing resin particles as described in claim 1.

15. The method involves a suspension polymerization reaction of a composition C comprising a compound (A) having an ether structure and a radical-reactive group represented by formula (1), a monomer component (M) that reacts with compound (A), and a reactive soft component. A method for manufacturing resin particles. 【Chemistry 2】

16. The method for producing resin particles according to claim 15, wherein the monomer component (M) comprises an aromatic crosslinkable monomer and an aromatic monofunctional monomer.

17. The method for producing resin particles according to claim 15, wherein the reactive soft component contains polybutadiene.

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