Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides

Definitions

• the present invention relates to a resin modifier that can be suitably blended with various resins, a resin composition containing the resin modifier and a base resin, a cured product of the resin composition, a sheet made of the aforementioned resin composition, and a prepreg containing the aforementioned cured product.
• a resin composition has been proposed that contains a modified polyphenylene ether, the end of which has been modified with a specific radically polymerizable functional group, as a base resin, and that contains a specific styrene-based thermoplastic elastomer to improve the dielectric properties (see Patent Document 1).
• Wiring boards are usually copper-clad laminates (CCL).
• CCL copper-clad laminates
• the present invention has been made in consideration of the above problems, and aims to provide a resin modifier that, when blended with a substrate, can improve the adhesion of the substrate or the cured product of the substrate to copper foil without significantly deteriorating the dielectric properties of the substrate or the cured product of the substrate, a resin composition containing the resin modifier and a substrate resin, a cured product of the resin composition, a sheet made of the resin composition, and a prepreg containing the cured product.
• the present invention provides the following (1) to (15).
• a composition comprising a modified resin (A) and core-shell polymer particles (B),
• the modified resin (A) contains a modified styrene-based elastomer (A1) or a modified polyolefin-based resin (A2), the modified resin (A) and the core-shell polymer particles (B) are modified with a monomer having one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group, and an ethylenically unsaturated bond;
• a resin modifier in which the type of group present in the largest amount among one or more polar groups contained in the modified resin (A) is the same as the type of group present in the largest amount among one or more polar groups contained in the core-shell polymer particles (B).
• the resin modifier according to (1) wherein the most abundant group among the one or more polar groups contained in the modified resin (A) and the most abundant group among the one or more polar groups contained in the core-shell polymer particles (B) are epoxy groups.
• the content of the polar group in the core-shell polymer particle (B) is 0.5% by mass or more and 10% by mass or less, based on the mass of the core-shell polymer particle (B).
• the modified resin (A) contains a modified styrene-based elastomer (A1),
• the resin modifier according to any one of (1) to (4), comprising 25 parts by mass or more and 98 parts by mass or less of a modified resin (A) and 2 parts by mass or more and 75 parts by mass or less of a core-shell polymer particle (B) relative to 100 parts by mass of the resin modifier.
• the modified resin (A) contains the modified polyolefin resin (A2), the ratio of the mass of the modified resin (A) to the total mass of the modified resin (A) and the core-shell polymer particles (B) is 25% by mass or more and 90% by mass or less; The ratio of the mass of the core-shell polymer particles (B) to the total mass of the modified resin (A) and the mass of the core-shell polymer particles (B) is 10 mass% or more and 75 mass% or less.
• the resin modifier according to any one of (1) to (4).
• the modified resin (A) contains a modified polyolefin resin (A2), The resin modifier according to any one of (1) to (4) and (6), further comprising a styrene-based elastomer (C).
• the ratio of the mass of the styrene-based elastomer (C) to the total mass of the modified resin (A) and the core-shell polymer particles (B) is 20 mass% or more and 70 mass% or less.
• the styrene-based elastomer (C) comprises at least one selected from the group consisting of styrene/isoprene/styrene elastomer, styrene/isobutylene/styrene elastomer, styrene/ethylenebutylene/styrene elastomer, hydrogenated styrene/isoprene/styrene elastomer, and hydrogenated styrene/(butadiene/isoprene)/styrene elastomer.
• a resin modifier comprising one or more substrates selected from a resin and a curable compound, and the resin modifier according to any one of (1) to (9); when the modified resin (A) contains a modified styrene-based elastomer (A1), the total mass of the modified resin (A) and the mass of the core-shell polymer particles (B) is 0.1 parts by mass or more and 80 parts by mass or less relative to 100 parts by mass of the base material, A resin composition, wherein, when the modified resin (A) contains a modified polyolefin resin (A2), the sum of the mass of the modified resin (A) and the mass of the core-shell polymer particles (B) is 5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the base material.
• a resin composition wherein, when the modified resin (A) contains a modified polyolefin resin (A2), the sum of the mass of the modified resin (A) and the mass of the core-shell polymer particles (B) is 5 parts by mass or more and
• the present invention provides a resin modifier that, when blended with a substrate, can improve the adhesion of the substrate or the cured product of the substrate to copper foil without significantly deteriorating the dielectric properties of the substrate or the cured product of the substrate, a resin composition containing the resin modifier and the substrate, a cured product of the resin composition, a sheet made of the resin composition, and a prepreg containing the cured product.
• the resin modifier includes a modified resin (A) and core-shell polymer particles (B).
• the modified resin (A) includes a modified styrene-based elastomer (A1) or a modified polyolefin-based resin (A2).
• the modified resin (A) and the core-shell polymer particles (B) are modified with a monomer having one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group, and an ethylenically unsaturated bond.
• the type of the group that is present in the largest amount among the one or more polar groups contained in the modified resin (A) is the same as the type of the group that is present in the largest amount among the one or more polar groups contained in the core-shell polymer particles (B).
• the above-mentioned resin modifier is blended into the substrate.
• the adhesion of the substrate or the cured product of the substrate to the copper foil can be improved without significantly deteriorating the dielectric properties of the substrate or the cured product of the substrate.
• the resin modifier contains a modified styrene-based elastomer (A1) and a modified polyolefin-based resin (A2) as the modified resin (A).
• the resin modifier containing the modified styrene-based elastomer (A1) will also be referred to as the "first modifier.”
• the resin modifier containing the modified polyolefin-based resin (A2) will also be referred to as the "second modifier.”
• the first modifier preferably contains 25 parts by mass or more and 98 parts by mass or less of the modified resin (A) and 2 parts by mass or more and 75 parts by mass or less of the core-shell polymer particles (B) relative to 100 parts by mass of the first modifier.
• the lower limit of the content of the modified resin (A) in the first modifier may be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more, relative to 100 parts by mass of the first modifier.
• the upper limit of the content of the modified resin (A) in the first modifier may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, relative to 100 parts by mass of the first modifier.
• the lower limit of the content of the core-shell polymer particles (B) in the first modifier may be 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, relative to 100 parts by mass of the first modifier.
• the upper limit of the content of the core-shell polymer particles (B) in the first modifier may be 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less, relative to 100 parts by mass of the first modifier.
• the modified resin (A) is a resin modified with a monomer having an ethylenically unsaturated bond and one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group.
• the structural unit derived from the monomer having a polar group and an ethylenically unsaturated bond is typically bonded to the resin as a side chain by graft polymerization.
• the structural unit derived from the monomer having a polar group and an ethylenically unsaturated bond may be bonded to the main chain of the resin by copolymerizing the monomer having a polar group and an ethylenically unsaturated bond with the main monomer constituting the resin.
• the content of the polar group in the modified resin (A) is not particularly limited as long as the desired effect is not impaired.
• the content of the polar group in the modified resin (A) is preferably 0.1% by mass or more and 8% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less, based on the mass of the modified resin (A).
• the content of the polar group in the modified resin (A) can be measured by various methods according to the type of the polar group.
• the polar group is an epoxy group
• the content of the epoxy group in the modified resin (A) can be measured using a potentiometric titration device in accordance with JIS K7236.
• the type of the group that is present in the largest amount among the one or more polar groups contained in the modified resin (A) is the same as the type of the group that is present in the largest amount among the one or more polar groups contained in the core-shell polymer particles (B) described below.
• the ratio of the mass of the polar group having the largest amount to the total mass of the polar groups in the modified resin (A) is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass%.
• the ratio of the mass of the polar group having the largest amount to the total mass of the polar groups in the core-shell polymer particles (B) is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass%.
• the modified resin (A) contains a modified styrene-based elastomer (A1).
• the modified resin (A) may contain a modified resin other than the modified styrene-based elastomer (A1) as long as the desired effects are not impaired.
• modified resins other than the modified styrene-based elastomer (A1) include modified polyolefin-based resins (A2), modified (meth)acrylic resins, modified polystyrene resins, modified polyphenylene ether resins, modified silicone resins, modified polyester resins, and modified fluororesins, which will be described later. Of these, the modified polyolefin resin (A2) is preferred.
• modified resins other than the modified styrene-based elastomer (A1) can be obtained by using the above-mentioned specific monomer having a polar group and an ethylenically unsaturated bond when producing the modified resin, or by reacting the above-mentioned specific monomer having a polar group and an ethylenically unsaturated bond with the main chain of a resin to introduce a branch having a polar group and an ethylenically unsaturated bond into the main chain.
• the content of the modified styrene-based elastomer (A1) in the modified resin (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, based on the mass of the modified resin (A).
• the styrene-based elastomer is a block copolymer containing a polystyrene-based block derived from a styrene-based monomer consisting of styrene and a styrene derivative.
• the modified styrene-based elastomer (A1) is a modified resin obtained by modifying the above-mentioned styrene-based elastomer with a monomer having one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group, and an ethylenically unsaturated bond.
• the styrene monomer used as the raw material of the styrene elastomer is not particularly limited. Suitable examples of the styrene monomer include styrene, 4-methylstyrene, ⁇ -methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, ⁇ -methyl-4-methylstyrene, 2,4,6-trimethylstyrene, ⁇ -methyl-2,4-dimethylstyrene, 4-chlorostyrene, ⁇ -chloro-4-chlorostyrene, 2,4,6-trichlorostyrene, ⁇ -chloro-2,4-dichlorostyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-chloromethylstyrene, and styrene derivatives substituted with a silyl group.
• styrene monomers styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferred, and from the viewpoint of cost, styrene and ⁇ -methylstyrene are more preferred.
• the blocks other than the polystyrene-based block in the styrene-based elastomer may be any of various known blocks that have been conventionally applied to styrene-based elastomers.
• styrene-based elastomer styrene/isoprene/styrene elastomer, styrene/isobutylene/styrene elastomer, styrene/ethylenebutylene/styrene elastomer, hydrogenated styrene/isoprene/styrene elastomer, and hydrogenated styrene/(butadiene/isoprene)/styrene elastomer are preferred.
• the polystyrene block in the styrene elastomer may be a block made of polystyrene, a block made of a homopolymer of a styrene derivative, or a block made of a copolymer of two or more kinds of styrene monomers.
• the polystyrene block in the styrene elastomer is preferably a block made of polystyrene.
• an epoxy group is preferred in that it has an excellent effect of improving adhesion between the substrate containing the first modifier or the cured product of the substrate and the copper foil.
• the monomer having a polar group and an ethylenically unsaturated bond may have two or more polar groups.
• a compound having one or two polar groups is preferable, and a compound having one polar group is more preferable.
• Examples of monomers having a polar group and an ethylenically unsaturated bond include unsaturated group-containing epoxy compounds such as glycidyl (meth)acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, monoglycidyl allyl succinate, 4-carboxystyrene, styrene glycidyl ester, allyl glycidyl ether, methacryl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, and vinylcyclohexene monoxide; allyl a unsaturated amines such as maleic anhydride, vinyl succinic acid, and allyl succinic acid; hydroxyl group-containing unsaturated compounds such as 2-hydroxyethyl (meth)acrylate, allyl alcohol, methallyl alcohol, 1-butenyl alcohol, and 4-
• the modification with a monomer having a polar group and an ethylenically unsaturated bond may be a graft modification, or a modification in which a monomer having a polar group and an ethylenically unsaturated bond is incorporated into a block that constitutes a styrene-based elastomer by copolymerization.
• the graft-modified styrene-based elastomer (A1) is preferably graft-modified with a monomer having a polar group and an ethylenically unsaturated bond, and an aromatic vinyl monomer not having a polar group, and more preferably graft-modified with glycidyl (meth)acrylate and styrene.
• Radical polymerization initiators that can be used when graft-modifying styrene-based elastomers include, for example, methyl ethyl ketone peroxide, methyl acetoacetate peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(tert-butylperoxy)butane, permethane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, ⁇ , ⁇ '-bis(tert-butylperoxy-m-isopropyl)benzene, di-tert-butyl peroxide, benzoyl peroxide, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di-2-methoxybutylperoxydicarbonate, tert-butylperoxyoctate, tert-butylperoxyisobutyrate, and di-tert-butylperoxy
• the amount of radical polymerization initiator used is not particularly limited as long as the graft modification reaction proceeds well.
• the amount of radical polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of styrene-based elastomer.
• the amount of the monomer having a polar group and an ethylenically unsaturated bond used in the graft modification of the styrene-based elastomer is preferably 0.1 parts by mass or more and 12 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less, per 100 parts by mass of the styrene-based elastomer.
• modified styrene-based elastomer (A1) modified with a monomer having a polar group and an ethylenically unsaturated bond in amounts within this range provides an excellent effect in improving adhesion between the substrate containing the first modifier or the cured product of the substrate and the copper foil.
• the graft-modified modified styrene-based elastomer (A1) is preferably graft-modified with a monomer having a polar group and an ethylenically unsaturated bond, and an aromatic vinyl monomer not having a polar group.
• the grafting reaction is stabilized, making it easier to graft the desired amount of vinyl monomer that has a polar group.
• styrene styrene, ⁇ -methylstyrene, 4-methylstyrene, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, or a mixture of divinylbenzene isomers is preferred because of its low cost, with styrene being particularly preferred.
• Aromatic vinyl monomers can be used alone or in combination of two or more.
• the amount of aromatic vinyl monomer without a polar group used in the graft modification of the styrene-based elastomer is preferably 0.1 parts by mass or more and 12 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less, per 100 parts by mass of the styrene-based elastomer.
• the modified styrene-based elastomer (A1) contains a structural unit derived from a monomer having a polar group and an ethylenically unsaturated bond in the main chain
• the modified styrene-based elastomer (A1) can be obtained by copolymerizing a monomer that gives a block constituting the styrene-based elastomer with a monomer having a polar group and an ethylenically unsaturated bond according to a well-known method.
• the preferred styrene elastomer is the same as that in the case of producing the modified styrene elastomer (A1) by graft modification.
• the core-shell polymer particles (B) have a core-shell structure and are polymer particles modified with a monomer having one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group, and an ethylenically unsaturated bond.
• the monomer having a polar group and an ethylenically unsaturated bond is as described above for the modified resin (A).
• the core and the shell may each be composed of two or more layers.
• the outermost layer of the shell layer is usually modified with the above-mentioned monomer having a polar group and an ethylenically unsaturated bond.
• the content of the polar group in the core-shell polymer particles (B) is not particularly limited as long as the desired effect is not impaired.
• the content of the polar group in the core-shell polymer particles (B) is preferably 0.5% by mass or more and 10% by mass or less, more preferably 0.7% by mass or more and 8% by mass or less, and even more preferably 1% by mass or more and 6% by mass or less, based on the mass of the core-shell polymer particles (B).
• the content of the polar group in the core-shell polymer particles (B) can be measured by various methods according to the type of the polar group.
• the polar group is an epoxy group
• the content of the epoxy group in the core-shell polymer particles (B) can be measured using a potentiometric titration device according to JIS K7236.
• the core-shell polymer particles (B) preferably have a core made of a crosslinked polymer.
• the ratio of the mass of the core to the mass of the shell in the core-shell polymer particles, core/shell is preferably 50/50 to 99/1, more preferably 60/40 to 95/5, and even more preferably 70/30 to 90/10.
• the core is preferably made of a cross-linked polymer.
• the cross-linked polymer is substantially insoluble in the solvent.
• the gel content of the core is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
• the core is preferably a rubber elastomer which is a polymer of monomers consisting of 50% by mass or more and 100% by mass or less of one or more monomers selected from the group consisting of diene monomers and (meth)acrylic acid ester monomers, and 0% by mass or more and 50% by mass or less of other copolymerizable vinyl monomers.
• the other copolymerizable vinyl monomer is preferably at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid derivatives, (meth)acrylamide derivatives, and maleimide derivatives.
• the core is more preferably made of a rubber elastomer that is a polymer of monomers consisting of 60% to 100% by mass of one or more monomers selected from the group consisting of diene monomers and (meth)acrylic acid ester monomers and 0% to 40% by mass of other copolymerizable vinyl monomers, and even more preferably made of a rubber elastomer that is a polymer of monomers consisting of 70% to 100% by mass of one or more monomers selected from the group consisting of diene monomers and (meth)acrylic acid ester monomers and 0% to 30% by mass of other copolymerizable vinyl monomers.
• a monomer selected from the group consisting of diene monomers and (meth)acrylic acid ester monomers will be referred to as "monomer A.”
• Other copolymerizable vinyl monomers are vinyl monomers that are copolymerizable with monomer A.
• (meth)acrylic refers to both acrylic and methacrylic.
• diene monomer examples include butadiene, isoprene, and chloroprene, with butadiene being preferred.
• (meth)acrylic acid ester monomers include butyl acrylate, 2-ethylhexyl acrylate, and lauryl methacrylate, and butyl acrylate and 2-ethylhexyl acrylate are preferred. These monomers may be used alone or in combination of two or more.
• the amount of monomer A used is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the mass of the core.
• the core may be a homopolymer formed by polymerization of one type of monomer A, or a copolymer of two or more types of monomer A.
• the core may also be a copolymer of one or more monomers A and one or more vinyl monomers copolymerizable with the monomers A.
• Examples of the vinyl monomer copolymerizable with the monomer A include one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid derivatives, (meth)acrylamide derivatives, and maleimide derivatives.
• Examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, and vinylnaphthalene.
• Examples of the vinyl cyanide compound include (meth)acrylonitrile and substituted acrylonitrile.
• Examples of the unsaturated carboxylic acid derivative include (meth)acrylic acid, itaconic acid, crotonic acid, and maleic anhydride.
• Examples of the (meth)acrylamide derivatives include (meth)acrylamide and N-substituted (meth)acrylamides.
• Examples of the maleimide derivative include maleimide and N-substituted maleimide. These monomers may be used alone or in combination of two or more kinds.
• the amount of these copolymerizable vinyl monomers used is preferably 50% by weight or less, more preferably 40% by weight or less, based on the mass of the core.
• a crosslinkable monomer When preparing the polymer constituting the core, a crosslinkable monomer may be used for the purpose of suppressing swelling of the core due to a solvent.
• the crosslinkable monomer include divinylbenzene, butanediol di(meth)acrylate, triallyl (iso)cyanurate, allyl (meth)acrylate, diallyl itaconate, and diallyl phthalate.
• the amount of the crosslinkable monomer used is preferably 0.2% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, and even more preferably 1% by mass or more and 3% by mass or less, based on the mass of the core-shell polymer particles (B).
• coating the core with a crosslinkable monomer and forming an intermediate layer between the core and shell is effective in suppressing fusion between the core-shell polymer particles (B).
• a crosslinkable monomer used to form the intermediate layer, but trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC) are preferred.
• a chain transfer agent may be used in the polymerization of the core.
• chain transfer agents that can be used include alkyl mercaptans having 5 to 20 carbon atoms.
• the amount of chain transfer agent used is preferably 5% by mass or less, more preferably 3% by mass or less, based on the mass of the core.
• the core may contain a crosslinked aromatic vinyl compound, such as a copolymer of an aromatic vinyl compound and the above-mentioned crosslinkable monomer.
• aromatic vinyl compounds include styrene, 2-vinylnaphthalene, ⁇ -methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene, and 2-chlorostyrene.
• the core may contain a polysiloxane rubber elastomer.
• a polysiloxane rubber elastomer for example, a polysiloxane rubber composed of di-substituted silyloxy units such as dimethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, etc. is preferable.
• the polysiloxane rubber-based elastomer is preferably crosslinked, if necessary, by using a polyfunctional alkoxysilane having three or more functional groups or a silane compound having an unsaturated group.
• the shell is a layer formed by graft polymerizing a graft copolymerizable monomer (shell-forming monomer) onto the core.
• the "shell” is a layer, at least a portion of which exists on the outermost side of the core-shell polymer particle (B).
• the entire shell does not have to exist on the outermost side of the core-shell polymer particle (B).
• a part of the shell may extend into the core.
• the type of polymer constituting the shell is not particularly limited.
• the polymer constituting the shell is preferably a polymer of one or more monomers selected from (meth)acrylic acid ester monomers, aromatic vinyl monomers, vinyl cyanide monomers, unsaturated carboxylic acid derivatives, (meth)acrylamide derivatives, and maleimide derivatives.
• Examples of the (meth)acrylic acid ester monomer include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
• Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, 4-bromostyrene, 2-chlorostyrene, and 4-chlorostyrene.
• Examples of the vinyl cyanide monomer include (meth)acrylonitrile and substituted (meth)acrylonitrile.
• Examples of the unsaturated carboxylic acid derivative include (meth)acrylic acid, itaconic acid, crotonic acid, and maleic anhydride.
• Examples of the (meth)acrylamide derivatives include (meth)acrylamide and N-substituted (meth)acrylamides.
• Examples of the maleimide derivative include maleimide and N-substitute
• the mass of the core-shell polymer particles (B) is 30% by mass or more of styrene units, more preferably 40% by mass or more of styrene units, and even more preferably 50% by mass or more of styrene units.
• the core-shell polymer particles (B) are modified with a monomer having one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group, and an ethylenically unsaturated bond. Therefore, in the core-shell polymer particles (B), it is preferred that the resin constituting the shell contains a structural unit derived from a monomer having the above-mentioned polar group and an ethylenically unsaturated bond, or that the resin constituting the shell is graft-polymerized with a monomer having the above-mentioned polar group and an ethylenically unsaturated bond.
• a monomer having a polar group and an ethylenically unsaturated bond is used so that the ratio of the mass of the polar group to the mass of the core-shell polymer particles (B) is within the preferred range described above.
• the shell may be a single layer structure or a multilayer structure. If the shell is a multilayer structure, the polymer composition of each layer may be different.
• the volume average particle diameter of the core-shell polymer particles (B) is preferably 10 nm or more and 400 nm or less, more preferably 30 nm or more and 350 nm or less, even more preferably 50 nm or more and 300 nm or less, even more preferably 80 nm or more and 250 nm or less, and particularly preferably 100 nm or more and 200 nm or less.
• the volume average particle diameter of the core-shell polymer particles (B) can be measured, for example, by using a laser diffraction/scattering type particle size distribution measuring device such as Microtrac (Microtrac UPA, manufactured by Nikkiso Co., Ltd.).
• the volume average particle diameter of the core-shell polymer particles (B) is preferably 10 nm or more and 400 nm or less, more preferably 30 nm or more and 350 nm or less, even more preferably 50 nm or more and 300 nm or less, even more preferably 80 nm or more and 250 nm or less, and particularly preferably 100 nm or more and 200 nm or less.
• the volume average particle size of the core-shell polymer particles (B) can be measured, for example, by using a laser diffraction/scattering type particle size distribution measuring device such as Microtrac (Microtrac UPA, manufactured by Nikkiso Co., Ltd.).
• the core-shell polymer particles (B) are usually dispersed as primary particles in a measurement sample when the particle size is measured by a laser diffraction/scattering type particle size distribution measurement device. Therefore, the volume average particle size measured by the laser diffraction/scattering type particle size distribution measurement device can be used as the average primary particle size.
• the method for producing the core-shell polymer particles (B) is not particularly limited.
• the core-shell polymer particles (B) can be produced by a well-known method. Examples of the well-known method include emulsion polymerization, suspension polymerization, and microsuspension polymerization. Among these methods, the production method based on multi-stage emulsion polymerization is particularly preferable.
• the first modifier may contain other components in addition to the modified resin (A) and the core-shell polymer particles (B) depending on the application of the resin composition obtained by blending the first modifier with a resin.
• Other components include various additives such as compatibilizers, fillers, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, colorants, rust inhibitors, crosslinking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, and release improvers.
• compatibilizers such as compatibilizers, fillers, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, colorants, rust inhibitors, crosslinking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, and release improvers.
• the first modifier may contain an organic solvent as necessary.
• the organic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, octane, decane, and dodecane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran; and halogenated hydrocarbons such as methylene chloride, methyl chloroform, carbon tetrachloride, dichlorodifluoromethane, and perchloroethylene.
• ketones such as methyl ethyl ketone and methyl isobutyl ketone
• aliphatic hydrocarbons such as pentane, cyclopentane, hexane,
• the solids concentration of the first modifier is not particularly limited.
• the solids concentration of the first modifier is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.
• the first modifier can be obtained by uniformly mixing the modified resin (A) and the core-shell polymer particles (B) described above together with other additives as required.
• the first modifier is prepared by mixing an organic solvent solution of the modified resin (A) with a dispersion in which the core-shell polymer particles (B) are dispersed in an organic solvent.
• the second modifier preferably contains the modifying resin (A) in an amount of 25% by mass or more and 90% by mass or less based on the total mass of the modifying resin (A) and the mass of the core-shell polymer particles (B).
• the second modifier preferably contains 10% by mass or more and 75% by mass or less of the core-shell polymer particles (B) based on the total mass of the modified resin (A) and the core-shell polymer particles (B).
• the lower limit of the ratio of the mass of the modified resin (A) to the sum of the mass of the modified resin (A) and the mass of the core-shell polymer particles (B) may be 30 mass% or more, 40 mass% or more, or 50 mass% or more.
• the upper limit of the ratio of the mass of the modified resin (A) to the sum of the mass of the modified resin (A) and the mass of the core-shell polymer particles (B) may be 80 mass% or less, 70 mass% or less, or 60 mass% or less.
• the lower limit of the content of the core-shell polymer particles (B) in the second modifier may be 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, relative to 100 parts by mass of the second modifier.
• the upper limit of the content of the core-shell polymer particles (B) in the second modifier may be 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less, relative to 100 parts by mass of the second modifier.
• the modified resin (A) is the same as the modified resin (A) in the first modifier, except that the modified resin (A) essentially contains the modified polyolefin resin (A2).
• the modified resin (A) includes a modified polyolefin resin (A2).
• the modified resin (A) may contain a modified resin other than the modified polyolefin resin (A1) as long as the desired effects are not impaired.
• modified resins other than the modified polyolefin resin (A2) include the above-mentioned modified styrene elastomer (A1), modified (meth)acrylic resin, modified polystyrene resin, modified polyphenylene ether resin, modified silicone resin, modified polyester resin, and modified fluororesin. Of these, the modified styrene-based elastomer (A1) is preferred.
• modified resins other than the modified polyolefin resin (A2) can be obtained by using the above-mentioned specific monomer having a polar group and an ethylenically unsaturated bond when producing the modified resin, or by reacting the above-mentioned specific monomer having a polar group and an ethylenically unsaturated bond with the main chain of the resin to introduce a branch having a polar group into the main chain.
• modified polyolefin resin (A2) in modified resin (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, based on the mass of modified resin (A).
• the modified polyolefin resin (A2) is a polyolefin resin modified with a monomer having an ethylenically unsaturated bond and one or more polar groups selected from the group consisting of an epoxy group, an amino group, an acid anhydride group, a hydroxyl group, and a carboxyl group.
• an epoxy group is preferred in that it has an excellent effect of improving the adhesion between a resin composition containing the resin modifier and a copper foil.
• the monomer having a polar group and an ethylenically unsaturated bond may have two or more polar groups.
• a compound having one or two polar groups is preferable, and a compound having one polar group is more preferable.
• the monomers described above for the modified styrene-based elastomer (A1) can be used.
• the monomer having a polar group and an ethylenically unsaturated bond may be used in combination of two or more kinds.
• the modified polyolefin resin (A2) is graft-modified
• the modified polyolefin resin (A2) is obtained by graft-modifying the polyolefin resin with a monomer having a polar group and an ethylenically unsaturated bond in the presence of a radical polymerization initiator.
• the graft-modified modified polyolefin resin (A2) is preferably graft-modified with a monomer having a polar group and an ethylenically unsaturated bond, and an aromatic vinyl monomer having no polar group.
• a monomer having a polar group and an ethylenically unsaturated bond in combination with an aromatic vinyl monomer having no polar group, the graft reaction is stabilized, making it easier to graft the desired amount of the monomer having a polar group and an ethylenically unsaturated bond.
• polyolefin resins examples include linear polyolefins such as polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene copolymers, ethylene-propylene-diene copolymers, ethylene/butene-1 copolymers, and ethylene/octene copolymers; and cyclic polyolefins such as copolymers of cyclopentadiene with ethylene and/or propylene.
• linear polyolefins such as polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene copolymers, ethylene-propylene-diene copolymers, ethylene/butene-1 copolymers, and ethylene/octene copolymers
• cyclic polyolefins such as copolymers of cyclopentadiene with ethylene and/or propylene.
• polymethylpentene polyethylene, polypropylene, and propylene-ethylene copolymers are preferred because they undergo modification reactions easily.
• Polymethylpentene is preferred in terms of heat resistance and low dielectric properties.
• Radical polymerization initiators that can be used when graft-modifying polyolefin resins include:
• the radical polymerization initiators usable in producing the graft-modified styrene-based elastomer (A1) include the above-mentioned radical polymerization initiators.
• the amount of radical polymerization initiator used is not particularly limited as long as the graft modification reaction proceeds well.
• the amount of radical polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of polyolefin resin.
• the amount of the monomer having a polar group and an ethylenically unsaturated bond used in the graft modification of the polyolefin resin is preferably 0.1 parts by mass or more and 12 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less, per 100 parts by mass of the polyolefin resin.
• the resin composition containing the resin modifier has an excellent effect of improving adhesion to copper foil.
• the type and amount of aromatic vinyl monomers without polar groups used are the same as those described for the modified styrene-based elastomer (A1).
• the modified polyolefin resin (A2) contains a structural unit derived from a monomer having a polar group and an ethylenically unsaturated bond in the main chain
• the modified polyolefin resin can be obtained by copolymerizing an olefin that gives a polyolefin resin with a monomer having a polar group and an ethylenically unsaturated bond according to a well-known method.
• the preferred polyolefin resin is the same as that in the case of producing the modified polyolefin resin (A2) by graft modification.
• Core-shell polymer particles (B) The core-shell polymer particles (B) are similar to those described for the first modifier.
• the second modifier preferably contains a styrene-based elastomer (C) as a compatibilizer to improve compatibility with the radical polymerizable compound contained in the base material, etc.
• a styrene-based elastomer (C) any conventionally known styrene-based elastomer can be used without any particular limitation.
• the amount of the styrene-based elastomer (C) used is not particularly limited as long as the desired effect is not impaired.
• the amount of the styrene-based elastomer (C) used is preferably 20% by mass or more and 70% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, based on the total mass of the modified resin (A) and the mass of the core-shell polymer particles (B).
• Suitable examples of the styrene-based elastomer (C) include at least one selected from the group consisting of styrene/isoprene/styrene elastomer, styrene/isobutylene/styrene elastomer, styrene/ethylenebutylene/styrene elastomer, hydrogenated styrene/isoprene/styrene elastomer, and hydrogenated styrene/(butadiene/isoprene)/styrene elastomer.
• the second modifier may contain components other than the modified resin (A), the core-shell polymer particles (B), and the styrene-based elastomer (C) depending on the application of the resin composition obtained by blending the second modifier with the resin.
• the second modifier may contain an organic solvent as necessary.
• the organic solvent that the second modifier may contain is the same as the organic solvent that the first modifier may contain.
• the resin composition includes a base material and the resin modifier described above.
• the base material is at least one selected from the group consisting of a resin and a curable compound.
• the total mass of the modified resin (A) derived from the first modifier and the mass of the core-shell polymer particles (B) in the resin composition is 0.1 parts by mass or more and 80 parts by mass or less, preferably 1 part by mass or more and 77 parts by mass or less, more preferably 5 parts by mass or more and 75 parts by mass or less, and even more preferably 10 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the base material.
• the total mass of the modified resin (A) derived from the second modifier and the mass of the core-shell polymer particles (B) in the resin composition is 5 parts by mass or more and 80 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the base material.
• the resin used as the base material is not particularly limited as long as it is a resin capable of dispersing the core-shell polymer particles (B) in the form of particles.
• the form of the resin composition is not particularly limited.
• the resin composition is preferably a varnish-like composition that contains the base material and the modified resin (A) in a state where the base material and the modified resin (A) are dissolved in an organic solvent, and contains the core-shell polymer particles (B) in a state where the core-shell polymer particles (B) are dispersed in the organic solvent.
• the organic solvent that the resin composition may contain is the same as the organic solvent that the resin modifier may contain.
• the solids concentration of the resin composition is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less.
• the substrate is one or more selected from a resin and a curable compound.
• the resin composition may contain a curing agent depending on the type of the curable composition.
• Typical examples of the curable compound include a radical polymerizable compound and a cationic polymerizable compound.
• the radical polymerizable compound will be described later.
• Examples of the cationic polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether compound.
• a polymer having a number average molecular weight of 10,000 or more is a resin
• a compound having a number average molecular weight of less than 10,000 and having a polymerizable group is a polymerizable compound.
• the resin may have a radical polymerizable group or a cationic polymerizable group as a polymerizable group.
• the radical polymerizable group will be described later.
• the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyloxy group.
• a polymer having a polymerizable group and a number average molecular weight of 10,000 or more is conveniently referred to as a "resin”.
• the resin for the base material for example, polyphenylene ether resin, polyolefin resin, and styrene-based elastomer are preferable because they have good dielectric properties in the high frequency band.
• a resin composition containing a resin having a polymerizable group and/or a polymerizable compound as a base material together with a resin modifier is a curable composition.
• Such a curable composition preferably contains a curing agent such as a radical polymerization initiator or a cationic polymerization initiator in terms of being easily cured.
• the substrate is preferably polyphenylene ether because of its excellent dielectric properties in the high frequency band.
• the polyphenylene ether may be a polyphenylene ether resin having a number average molecular weight of 10,000 or more, or a modified polyphenylene ether oligomer having a number average molecular weight of less than 10,000.
• the polyphenylene ether is preferably a modified polyphenylene ether having a carbon-carbon unsaturated double bond-containing group.
• Such modified polyphenylene ether may be a modified polyphenylene ether resin having a number average molecular weight of 10,000 or more, or may be a modified polyphenylene ether oligomer having a number average molecular weight of less than 10,000.
• the modified polyphenylene ether oligomer having a number average molecular weight of less than 10,000 corresponds to a curable compound in that it has a carbon-carbon unsaturated double bond-containing group.
• the modified polyphenylene ether preferably has a carbon-carbon unsaturated double bond-containing group bonded to an oxygen atom at the molecular chain terminal.
• Polyphenylene ether usually has a hydroxyl group bonded to an aromatic ring at the molecular chain terminal.
• the modified polyphenylene ether is obtained by replacing the hydrogen atom in this terminal hydroxyl group with a carbon-carbon unsaturated double bond-containing group.
• the carbon-carbon unsaturated double bond-containing group is preferably at least one selected from a vinylbenzyl group, a vinyl group, an allyl group, and a (meth)acryloyl group.
• the carbon-carbon unsaturated double bond-containing group is a vinylbenzyl group, an allyl group, or a (meth)acryloyl group
• the terminal hydroxyl group of the polyphenylene ether can be converted to a vinylbenzyloxy group, an allyloxy group, or a (meth)acryloyloxy group using a corresponding halide according to a conventional method.
• the terminal hydroxyl group of the polyphenylene ether can be converted to a vinyloxy group by a method such as an ether exchange reaction between a vinyl ether compound, such as an alkyl vinyl ether (e.g., methyl vinyl ether), and a terminal hydroxyl group; a vinylation reaction using a vinyl ester compound, such as vinyl acetate; or addition of acetylene to the terminal hydroxyl group.
• a vinyl ether compound such as an alkyl vinyl ether (e.g., methyl vinyl ether)
• a vinylation reaction using a vinyl ester compound such as vinyl acetate
• addition of acetylene to the terminal hydroxyl group.
• Modified polyphenylene ethers having carbon-carbon unsaturated double bond-containing groups bonded to oxygen atoms at the ends of the molecular chain may also be commercially available products.
• Specific examples of commercially available products include vinylbenzyl-terminated polyphenylene ethers such as OPE-2St-2200 and OPE-2st-1200 (both manufactured by Mitsubishi Gas Chemical Company, Inc.); and methacryloyl-terminated polyphenylene ethers such as Noryl (registered trademark) SA9000 (manufactured by SABIC Corporation).
• the molecular weight of the modified polyphenylene ether is not particularly limited as long as the desired effect is not impaired.
• the molecular weight of the modified polyphenylene ether is preferably 1000 or more, and more preferably 2000 or more, in terms of number average molecular weight (Mn).
• the resin composition is also preferably a radical polymerizable composition. That is, the resin composition may contain a radical polymerizable compound as a base material and a radical polymerization initiator in addition to the resin modifier.
• the radical polymerizable composition may contain a combination of a resin and a radical polymerizable compound as a base material.
• the radically polymerizable compound may be a monofunctional compound having one radically polymerizable group, or a polyfunctional compound having two or more radically polymerizable groups, with a polyfunctional compound being preferred.
• the radical polymerizable group is not particularly limited, but is typically a carbon-carbon double bond-containing group.
• Suitable examples of the carbon-carbon double bond-containing group include alkenyl groups such as vinyl groups, allyl groups, and methallyl groups, unsaturated acyl groups such as acryloyl groups and methacryloyl groups, and maleimide groups.
• Suitable radically polymerizable compounds include triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, trimethylolpropane tri(meth)acrylate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, 1,3-phenylenediamine bismaleimide, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, dipropargyl terephthalate, diallyl phthalate, and N,N',N'',N'''-tetraallyl terephthalamide.
• (meth)acrylate refers to both acrylate and methacrylate.
• triallyl cyanurate triallyl isocyanurate
• trimethallyl isocyanurate trimethallyl isocyanurate
• trimethylolpropane tri(meth)acrylate are more preferred.
• the content of the radically polymerizable compound in the resin composition is preferably 20% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 100% by mass or less, relative to the mass of the base material.
• radical polymerization initiator any conventionally known radical polymerization initiator can be used without any particular limitation. Suitable specific examples of the radical polymerization initiator are the same as those of the radical polymerization initiator that can be used when graft-modifying a styrene-based elastomer or a polyolefin-based resin. The above radical polymerization initiators can be used alone or in combination of two or more kinds.
• the amount of radical polymerization initiator used is not particularly limited as long as the resin composition is capable of radical polymerization by heating or exposure to light.
• the amount of radical polymerization initiator used is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, and even more preferably 2 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the radically polymerizable compound.
• the resin composition is a radically polymerizable composition and contains a resin as a base material and a radically polymerizable compound
• the resin as the base material has been modified to introduce a radically polymerizable group into the main chain.
• the resin since the resin is crosslinked by the radically polymerizable compound, a cured product having excellent dielectric properties and mechanical strength can be formed using the resin composition.
• an inorganic filler can be blended into the resin composition.
• inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, montmorillonite, gypsum, glass flakes, glass fiber, milled glass fiber, carbon fiber, alumina fiber, silica alumina fiber, aluminum borate whisker, and potassium titanate fiber.
• the inorganic fillers may be used alone or in combination of two or more.
• the amount of these inorganic fillers used is not particularly limited as long as the desired effect is not impaired.
• the amount of base-free fillers used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the base material.
• the resin composition can further contain various additives such as organic fillers, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, colorants, rust inhibitors, crosslinking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, and release improvers.
• additives such as organic fillers, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, colorants, rust inhibitors, crosslinking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, and release improvers.
• additives may be used alone or in combination of two or more.
• the resin composition described above is a radically polymerizable composition
• the resin composition is cured by applying energy to the resin composition by heating or exposure to light, etc., to form a cured product.
• the resin composition or the cured product of the resin composition is preferably used as a material for a wiring board.
• a sheet made of the resin composition or a prepreg made of a fiber sheet and a cured product of the resin composition composited with the fiber sheet is preferable.
• a sheet made of the resin composition can be formed by a solution casting method.
• the prepreg can be formed by impregnating a fiber sheet such as a glass fiber sheet with a radically polymerizable resin composition, and then curing the resin composition impregnated in the fiber sheet by a method such as heating or exposure to light.
• pellets of modified styrene-based elastomer A1-1 were obtained by vacuum devolatilization from a vent port.
• the obtained resin pellets were dissolved in xylene at 130°C, and then cooled to room temperature again to precipitate a recrystallized resin.
• the epoxy group content was measured using an automatic potentiometric titrator (AT700 manufactured by Kyoto Electronics Manufacturing Co., Ltd.) in accordance with JIS K7236.
• the epoxy group content of the modified styrene-based elastomer A1-1 was 0.21% by mass.
• the reaction liquid in the pressure-resistant polymerization vessel was depressurized to remove volatile matters such as remaining monomers, thereby terminating the polymerization.
• a styrene-butadiene rubber latex was obtained.
• the volume average particle size of the styrene-butadiene rubber particles contained in the obtained styrene-butadiene rubber latex was 100 nm.
• TBP triallyl isocyanurate
• CHP cumene hydroperoxide
• an aqueous latex containing the core-shell polymer particles B1 was obtained.
• the core-shell polymer particles B1 contained in the aqueous latex had a volume average particle diameter of 110 nm.
• the ratio of the mass of the epoxy group to the mass of the core-shell polymer particles B1 was 1.2% by mass.
• a dispersion of core-shell polymer B1 was obtained in which core-shell polymer particles B1 were dispersed in methyl ethyl ketone (MEK) at a solid content concentration of 25% by mass according to the method described in Production Example 1 of International Publication No. 2020/027189.
• MEK methyl ethyl ketone
• Example 1-1 7.2 g of the modified styrene-based elastomer A1-1 obtained in Production Example A1-1 was dissolved in 28.8 g of toluene. Then, 11.2 g of a methyl ethyl ketone (MEK) dispersion of the core-shell polymer particles B1 (solid content concentration: 25% by mass) was added to the toluene solution of the modified styrene-based elastomer A1-1 to obtain 47.2 g of a modifier 1-1. The resulting 47.2 g of Modifier 1-1 contains 2.8 g of core-shell polymer particles B1.
• MEK methyl ethyl ketone
• Example 1-2 The amount of modified styrene-based elastomer A1-1 used was changed from 7.2 g to 4.0 g, the amount of toluene used was changed from 28.8 g to 18.0 g, and the amount of MEK dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 24.0 g, but the same procedure as in Example 1-1 was repeated to obtain 46.0 g of modifier 1-2.
• the resulting 46.0 g of Modifier 1-2 contains 6.0 g of core-shell polymer particles B1.
• Examples 1 to 3 The amount of modified styrene-based elastomer particles A1-1 used was changed from 7.2 g to 7.0 g, the amount of toluene used was changed from 28.8 g to 28.0 g, and the amount of the dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 21.6 g, but the same procedure as in Example 1-1 was repeated to obtain 56.6 g of modifier 1-3.
• the resulting 56.6 g of Modifier 1-3 contains 5.4 g of core-shell polymer particles B1.
• Examples 1 to 4 The procedure of Example 1-1 was repeated except that 7.2 g of the modified styrene-based elastomer A1-1 was changed to 7.2 g of the modified styrene-based elastomer A1-2, to obtain 47.2 g of a modifier 1-4.
• the resulting 47.2 g of Modifier 1-4 contains 2.8 g of core-shell polymer particles B1.
• Examples 1 to 5 The procedure of Example 1-3 was repeated except that 7.0 g of the modified styrene-based elastomer A1-1 was changed to 7.0 g of the modified styrene-based elastomer A1-2, to obtain 56.6 g of a modifier 1-5.
• the resulting 56.6 g of Modifier 1-5 contains 5.4 g of core-shell polymer particles B1.
• Example 1 to 6 The amount of modified styrene-based elastomer A1-1 used was changed from 7.2 g to 9.9 g, the amount of toluene used was changed from 28.8 g to 39.6 g, and the amount of MEK dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 5.6 g, but the same procedure as in Example 1-1 was repeated to obtain 55.1 g of modifier 1-6. The resulting 55.1 g of Modifier 1-6 contains 1.4 g of core-shell polymer particles B1.
• Examples 1 to 7 The amount of modified styrene-based elastomer A1-1 used was changed from 7.2 g to 13.8 g, the amount of toluene used was changed from 28.8 g to 55.2 g, and the amount of MEK dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 5.2 g, but the same procedure as in Example 1-1 was repeated to obtain 74.2 g of modifier 1-7. The resulting 74.2 g of Modifier 1-7 contains 1.3 g of core-shell polymer particles B1.
• Examples 1 to 8 The procedure of Example 1-6 was repeated except that 9.9 g of the modified styrene-based elastomer A1-1 was changed to 9.9 g of the modified styrene-based elastomer A1-2, to obtain 55.1 g of a modifier 1-8.
• the resulting 55.1 g of Modifier 1-8 contains 1.4 g of core-shell polymer particles B1.
• Examples 1 to 9 The procedure of Example 1-7 was repeated except that 13.8 g of the modified styrene-based elastomer A1-1 was changed to 13.8 g of the modified styrene-based elastomer A1-2, to obtain 74.2 g of a modifier 1-9.
• the resulting 74.2 g of Modifier 1-9 contains 1.3 g of core-shell polymer particles B1.
• Example 1 to 10 The amount of modified styrene-based elastomer A1-2 used was changed from 13.8 g to 13.7 g, the amount of toluene used was changed from 55.2 g to 54.8 g, and the amount of MEK dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 10.4 g, but the same procedure as in Example 1-9 was repeated to obtain 78.9 g of modifier 1-10. The resulting 78.9 g of Modifier 1-10 contains 2.6 g of core-shell polymer particles B1.
• Examples 1-11 The amount of modified styrene-based elastomer A1-1 used was changed from 7.2 g to 0.18 g, the amount of toluene used was changed from 28.8 g to 0.72 g, and the amount of MEK dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 0.32 g, but the same procedure as in Example 1-1 was repeated to obtain 1.22 g of modifier 1-11. The resulting 1.22 g of Modifier 1-11 contains 0.08 g of core-shell polymer particles B1.
• Example 12 The amount of modified styrene-based elastomer A1-1 used was changed from 7.2 g to 1.9 g, the amount of toluene used was changed from 28.8 g to 7.6 g, and the amount of MEK dispersion of core-shell polymer particles B1 used was changed from 11.2 g to 0.4 g, but the same procedure as in Example 1-1 was repeated to obtain 9.9 g of modifier 1-12.
• the resulting 9.9 g of Modifier 1-12 contained 0.1 g of core-shell polymer particles B1.
• the modifiers obtained in Examples 1-1 to 1-12 were mixed with polyphenylene ether modified at both ends with methacrylate to prepare resin compositions.
• polyphenylene ether (manufactured by SABIC, trade name: Noryl (registered trademark) SA9000 resin, number average molecular weight: 1700) in an amount shown in Table 1
• a radical polymerizable compound (manufactured by Mitsubishi Chemical Corporation, triallyl isocyanurate (TAIC)) in an amount shown in Table 1
• silica manufactured by Admatechs, trade name: SC2300-SVJ, average particle size 0.5 ⁇ m
• initiator manufactured by NOF Corporation, trade name: Perbutyl P (PBP)
• the modifier of each Example was added to the toluene dispersion and stir
• the obtained resin composition was used to obtain a prepreg according to the following method. Specifically, a glass cloth (manufactured by Nitto Boseki Co., Ltd., product name: NE-1078, size: 100 mm x 200 mm) was impregnated with the resin composition of each Example. The glass cloth impregnated with the resin composition was passed between two Teflon rods arranged in parallel with a gap of 0.4 mm between them to remove excess resin composition. The glass cloth impregnated with the resin composition was heated at 60° C. for 100 minutes, at 100° C. for 10 minutes, and at 120° C. for 50 minutes in this order to obtain a prepreg.
• a glass cloth manufactured by Nitto Boseki Co., Ltd., product name: NE-1078, size: 100 mm x 200 mm
• Comparative Example 1-1 To 100.0 g of toluene, each of the components shown in Table 1 was added in the amount shown in Table 1. Each of the components shown in Table 1 was dissolved and dispersed in toluene to obtain a resin composition. The obtained resin composition was used to obtain a prepreg in the same manner as in Example 1-1.
• Comparative Example 1-2 To 85.8 g of toluene, 12.0 g of the dispersion (solid content concentration 25% by mass) in which the core-shell polymer particles B1 obtained in Production Example B1 were dispersed in methyl ethyl ketone (MEK) and each component shown in Table 1 were added in the amount shown in Table 1. The core-shell polymer particles B1 and each component shown in Table 1 were dissolved and dispersed in toluene to obtain a resin composition. The obtained resin composition was used to obtain a prepreg in the same manner as in Example 1-1.
• MEK methyl ethyl ketone
• Comparative Examples 1-3 To 85.8 g of toluene, 7.4 g of the modified styrene-based elastomer A1-1 and each of the components shown in Table 1 were added in the amounts shown in Table 1. The modified styrene-based elastomer A1-1 and each of the components shown in Table 1 were dissolved and dispersed in toluene to obtain a resin composition. The obtained resin composition was used to obtain a prepreg in the same manner as in Example 1-1.
• cured sheets were produced according to the following method.
• the prepreg was sandwiched between two Teflon sheets (manufactured by Nitto Denko Corporation, product name: Nitoflon (registered trademark), thickness 50 ⁇ m).
• the prepreg sandwiched between the two Teflon sheets was set in a press at a press temperature of 100 ° C. and a press pressure of 0.5 MPa (G), and then the press temperature was increased at a rate of 3 ° C. / min. When the press temperature reached 140 ° C., the press pressure was increased to 3.0 MPa (G).
• the press temperature was increased to 200 ° C. at a rate of 3 ° C. / min. After the press temperature reached 200 ° C., pressing was continued for 75 minutes to obtain a cured sheet in which the cured product of the resin composition and the glass sheet were combined.
• the dielectric loss tangent was measured using a network analyzer (manufactured by KEYSIGHT) as a measuring device. A 30 mm x 40 mm test piece cut out from the cured sheet was used for measuring the dielectric loss tangent. The test piece was left to stand for 24 hours under conditions of 23°C and 50% RH before measuring the dielectric loss tangent. The measurement conditions were as follows. Measurement frequency: 40GHz Temperature: 23°C Humidity: 50%R. H.
• metal laminates were produced according to the following method.
• the prepreg was sandwiched between two sheets of electrolytic copper foil (manufactured by Fukuda Metal Foil and Powder Co., Ltd., product name: CF-T49A-DS-HD2-18, thickness 18 ⁇ m, surface roughness 0.5 ⁇ m).
• the prepreg sandwiched between the two sheets of electrolytic copper foil was set in a press at a press temperature of 100 ° C. and a press pressure of 0.5 MPa (G), and then the press temperature was increased at a rate of 3 ° C. / min.
• the press pressure was increased to 3.0 MPa (G).
• the press temperature was increased to 200 ° C. at a rate of 3 ° C. / min.
• the press temperature reached 200 ° C., the press was continued for 75 minutes to obtain a metal laminate.
• electrolytic copper foil is laminated on both main surfaces of a cured sheet in which a cured product of a resin composition and a glass sheet are combined.
• the resulting metal laminate was used to measure the peel strength of the electrolytic copper foil in accordance with JIS C6471 "6.5 Peel Strength.” Specifically, a 1 mm wide metal foil portion was peeled off at a peel angle of 90° and a peel speed of 100 mm/min. The load applied during peeling was measured, and the measured value of the load was taken as the peel strength. The measured values of the peel strength are shown in Table 1.
• the component (A1) is a modified styrene-based elastomer (A1).
• Comparative Example 1-1 shows that even if the resin is modified with a modifier that satisfies the above-mentioned specified conditions, the electrical characteristics (dielectric tangent) are not significantly impaired.
• pellets of modified polyolefin resin A2-1 were obtained by vacuum devolatilization from a vent port.
• the obtained resin pellets were dissolved in xylene at 130°C, and then cooled to room temperature again to precipitate a recrystallized resin.
• the epoxy group content was measured using an automatic potentiometric titrator (AT700 manufactured by Kyoto Electronics Manufacturing Co., Ltd.) in accordance with JIS K7236.
• the epoxy group content of modified polyolefin resin A2-1 was 0.23% by mass.
• Example 2-1 6.8 g of the modified polyolefin resin A2-1 obtained in Production Example A2-1 and 4.8 g of a compatibilizer (product name: 8903P, styrene/ethylene butylene/styrene elastomer (SEBS), manufactured by ENEOS Materials Co., Ltd.) were dissolved in 34.8 g of toluene.
• a compatibilizer product name: 8903P, styrene/ethylene butylene/styrene elastomer (SEBS), manufactured by ENEOS Materials Co., Ltd.
• MEK methyl ethyl ketone
• Example 2-2 The amount of modified polyolefin resin A2-1 used was changed from 6.8 g to 13.7 g, the amount of toluene used was changed from 34.8 g to 55.5 g, and the amount of MEK dispersion of core-shell polymer B1 used was changed from 10.4 g to 20.8 g. Except for this, 94.8 g of modifier 2-2 was obtained in the same manner as in Example 2-1. The resulting 94.8 g of Modifier 2-2 contains 5.2 g of core-shell polymer particles B1.
• Example 2-3 Except for changing 6.8 g of modified polyolefin resin A2-1 to 7.6 g of modified polyolefin resin A2-2, changing the amount of toluene used from 34.8 g to 37.2 g, and changing the amount of MEK dispersion of core-shell polymer B1 used from 10.4 g to 7.2 g, 56.8 g of modifier 2-3 was obtained in the same manner as in Example 2-1.
• the resulting 56.8 g of Modifier 2-3 contains 1.8 g of core-shell polymer particles B1.
• Example 2-4 The procedure of Example 2-1 was repeated except that the modified polyolefin resin A2-1 was changed to the modified polyolefin resin A2-3, to obtain 56.8 g of a modifier 2-4.
• the resulting 56.8 g of Modifier 2-4 contains 2.6 g of core-shell polymer particles B1.
• the modifiers obtained in Examples 2-1 to 2-4 were mixed with polyphenylene ether, both ends of which were modified with methacrylate, to prepare resin compositions.
• PPE polyphenylene ether
• SA9000 resin number average molecular weight: 1700
• TAIC triallyl isocyanurate
• silica silica
• SC2300-SVJ average particle size 0.5 ⁇ m
• the obtained resin composition was used to obtain a prepreg according to the following method. Specifically, a glass cloth (manufactured by Nitto Boseki Co., Ltd., product name: NE-1078, size: 100 mm x 200 mm) was impregnated with the resin composition of each Example. The glass cloth impregnated with the resin composition was passed between two Teflon rods arranged in parallel with a gap of 0.4 mm between them to remove excess resin composition. The glass cloth impregnated with the resin composition was heated at 60° C. for 100 minutes, at 100° C. for 10 minutes, and at 120° C. for 50 minutes in this order to obtain a prepreg.
• a glass cloth manufactured by Nitto Boseki Co., Ltd., product name: NE-1078, size: 100 mm x 200 mm
• Comparative Example 2-1 To 100.0 g of toluene, each of the components shown in Table 2 was added in the amount shown in Table 2. Each of the components shown in Table 2 was dissolved and dispersed in toluene to obtain a resin composition. The obtained resin composition was used to obtain a prepreg in the same manner as in Example 2-1.
• Comparative Example 2-2 To 85.8 g of toluene, 12.0 g of the dispersion (solid content concentration 25% by mass) in which the core-shell polymer particles B1 obtained in Production Example B1 were dispersed in methyl ethyl ketone (MEK) and each component shown in Table 2 were added in the amount shown in Table 2. The core-shell polymer particles B1 and each component shown in Table 2 were dissolved and dispersed in toluene to obtain a resin composition. The obtained resin composition was used to obtain a prepreg in the same manner as in Example 2-1.
• MEK methyl ethyl ketone
• Comparative Example 2-3 7.0 g of the modified polyolefin resin A2-1 obtained in Production Example A2-1 and 4.9 g of a compatibilizer (product name: 8903P, styrene/ethylene butylene/styrene elastomer (SEBS), manufactured by ENEOS Materials Co., Ltd.) were dissolved in 27.2 g of toluene to obtain a modifier 2-5. To 85.8 g of toluene, the obtained Modifier 2-5 and each component shown in Table 2 were added in the amounts shown in Table 2. The modified polyolefin resin A2-1, the compatibilizer, and each component shown in Table 2 were dissolved and dispersed in toluene to obtain a resin composition. The obtained resin composition was used to obtain a prepreg in the same manner as in Example 2-1.
• a compatibilizer product name: 8903P, styrene/ethylene butylene/styrene elastomer (SEBS), manufactured by ENEOS Materials Co., Ltd
• Comparative Example 2-4 6.8 g of the modified polyolefin resin A2-1 obtained in Production Example A2-1 and 4.8 g of a compatibilizer (product name: 8903P, styrene/ethylene butylene/styrene elastomer (SEBS), manufactured by ENEOS Materials Co., Ltd.) were dissolved in 42.6 g of toluene. Next, 2.6 g of core-shell polymer particles B2 (butadiene-based rubber type, manufactured by Kaneka Corporation, Kane Ace (registered trademark) M-732) having no polar group was added to the toluene solution of the modified polyolefin resin to obtain a modifier 2-6.
• a compatibilizer product name: 8903P, styrene/ethylene butylene/styrene elastomer (SEBS), manufactured by ENEOS Materials Co., Ltd.
• the obtained modifier 2-6 and each component shown in Table 2 were added in the amounts shown in Table 2.
• the modified polyolefin resin A2-1, the compatibilizer, and each component shown in Table 2 were dissolved and dispersed in toluene to obtain a resin composition.
• the obtained resin composition was used to obtain a prepreg in the same manner as in Example 2-1.
• Comparative Examples 2-1 to 2-4 when the resin was not modified using both the modified resin (A) containing the modified polyolefin resin (A2) and the core-shell polymer particles (B), or when the modified resin (A) or the core-shell polymer particles (B) did not have a polar group, the cured product formed using the resin composition had poor adhesion to the copper foil.
• a comparison between Comparative Example 2-1 and Examples 2-1 to 2-4 shows that even if the resin is modified with a modifier that satisfies the above-mentioned specified conditions, the electrical characteristics (dielectric tangent) are not significantly impaired.

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