Resin composition, prepreg, laminated plate, metal-clad laminated plate, printed wiring board, and semiconductor package

Abstract

Provided is a resin composition containing an acrylic polymer that is an easily combustible component, the resin composition having exceptional flame retardancy while maintaining excellent adhesive strength with copper foil and desmear resistance. Also provided are a prepreg, a laminated plate, a metal-clad laminated plate, a printed wiring board, and a semiconductor package that are produced using the resin composition. Specifically, the resin composition contains (A) an acrylic polymer, (B) a thermosetting resin, and (C) an inorganic filler that is surface-treated with a silane coupling agent, the resin composition furthermore containing (D) a silane coupling agent.

Description

Resin compositions, prepregs, laminates, metal-clad laminates, printed wiring boards, and semiconductor packages

[0001] The present disclosure relates to a resin composition, a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a semiconductor package.

[0002] Traditionally, halogen-based flame retardants containing halogens such as bromine have been used as flame retardants in resin compositions used in electronic components such as printed wiring boards and semiconductor encapsulants. However, in recent years, due to environmental considerations, the introduction of halogen-free products that do not use conventional bromine-based flame retardants containing halogens has been promoted. "Halogen-free" refers to the complete absence of halogen atoms or the presence of only trace amounts of halogen atoms. For example, the Japan Electronics Packaging and Circuits Association (JPC) specifies that halogen-free copper-clad laminates for printed wiring boards must contain chlorine (Cl) and bromine (Br) atoms at a concentration of 900 ppm or less each, with a total content of 1,500 ppm or less. Therefore, halogen-free flame retardants, such as phosphorus-based flame retardants such as phosphazene compounds, phosphate ester compounds, and phosphate ester amide compounds, have been proposed as alternative flame retardants to halogen-containing compounds (see, for example, Patent Document 1).

[0003] Excerpt from paragraph

[0077] of JP 2023-040078 A

[0004] However, although the inclusion of a phosphorus-based flame retardant in a resin composition increases flame retardancy, properties such as adhesive strength with copper foil and desmear resistance, which are necessary for printed wiring board and semiconductor package applications, tend to decrease. In recent years, relatively flammable components such as acrylic polymers have been used in view of dielectric properties (dielectric constant and dielectric loss tangent) or flexibility, and in such cases, improved flame retardancy is required. However, due to the above-mentioned tendency, it is not possible to incorporate a large amount of phosphorus-based flame retardants. Therefore, there is a strong demand for the development of a resin composition containing an acrylic polymer, which is a flammable component, that contains a component that can improve flame retardancy while maintaining adhesive strength with copper foil and desmear resistance.

[0005] In view of the above circumstances, the present disclosure aims to provide a resin composition containing an acrylic polymer, which is a combustible component, that exhibits excellent flame retardancy while maintaining good adhesive strength to copper foil and desmear resistance. It also aims to provide a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a semiconductor package produced using the resin composition.

[0006] The present inventors have conducted extensive research to achieve the above-mentioned object, and have found that the above-mentioned object can be achieved by the present disclosure. The present disclosure includes the following embodiments [1] to

[12] . [1] A resin composition containing (A) an acrylic polymer, (B) a thermosetting resin, and (C) an inorganic filler surface-treated with a silane coupling agent, further containing (D) a silane coupling agent. [2] The resin composition according to [1] above, wherein the weight-average molecular weight (Mw) of the component (A) is 50,000 to 1,500,000. [3] The resin composition according to [1] or [2] above, wherein the content of the component (A) is 1 to 50 parts by mass per 100 parts by mass of the total amount of the components (A) and (B). [4] The resin composition according to any one of [1] to [3] above, wherein the component (B) comprises at least one selected from the group consisting of epoxy resins, polyimide resins, maleimide compounds, phenolic resins, modified polyphenylene ether resins, bismaleimide triazine resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. [5] The resin composition according to any one of [1] to [4] above, wherein the component (B) comprises at least one selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof. [6] The resin composition according to any one of [1] to [5] above, wherein the component (B) comprises a siloxane-modified maleimide compound. [7] The resin composition according to any one of [1] to [6] above, wherein the component (D) has a functional group capable of reacting with the component (A) or the component (B). [8] A prepreg comprising a substrate and the resin composition described in any one of [1] to [7] above or a semi-cured product of the resin composition. [9] A laminate comprising one or more selected from the group consisting of a cured product of the resin composition described in any one of [1] to [7] above and a cured product of the prepreg described in [8] above.

[10] A metal-clad laminate comprising a metal foil and one or more selected from the group consisting of a cured product of the resin composition described in any one of [1] to [7] above and a cured product of the prepreg described in [8] above.

[11] A printed wiring board comprising one or more selected from the group consisting of a cured product of the resin composition according to any one of [1] to [7] above, a cured product of the prepreg according to [8] above, the laminate according to [9] above, and the metal-clad laminate according to

[10] above.

[12] A semiconductor package comprising the printed wiring board according to

[11] above and a semiconductor element.

[0007] The present disclosure provides a resin composition containing an acrylic polymer, which is a combustible component, that exhibits excellent flame retardancy while maintaining good adhesive strength to copper foil and desmear resistance. Furthermore, the present disclosure also provides a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a semiconductor package manufactured using the resin composition.

[0008] In the numerical ranges described in this disclosure, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. Furthermore, the lower and upper limits of a numerical range can be arbitrarily combined with the lower or upper limit of another numerical range. In the expression "AA to BB," the numerical values ​​AA and BB at both ends are included as the lower and upper limits, respectively, within the numerical range. In this disclosure, for example, the expression "10 or more" means 10 and a numerical value greater than 10, and this also applies when the numerical values ​​are different. Furthermore, for example, the expression "10 or less" means a numerical value less than 10 and this also applies when the numerical values ​​are different.

[0009] In addition, unless otherwise specified, each component and material exemplified in this disclosure may be used alone or in combination of two or more. In this disclosure, when a resin composition contains multiple substances corresponding to each component, the content of each component in the resin composition means the total amount of the multiple substances present in the resin composition, unless otherwise specified.

[0010] In the present disclosure, "solid content" refers to components in a resin composition other than the organic solvent described below, and components that are liquid at room temperature around 25°C are also considered to be solid content. The expression "containing XX" described in the present disclosure may mean that XX is contained in a reacted state if XX is reactive, or may simply mean that XX is contained as is, or may include both of these aspects. In addition, aspects in which the descriptions in the present disclosure are combined in any way are also included in the present embodiment.

[0011] [Resin composition] One aspect of this embodiment is a resin composition containing (A) an acrylic polymer (hereinafter sometimes referred to as "component (A)"), (B) a thermosetting resin (hereinafter sometimes referred to as "component (B)"), and (C) an inorganic filler surface-treated with a silane coupling agent (hereinafter sometimes referred to as "component (C)"), and further containing (D) a silane coupling agent (hereinafter sometimes referred to as "component (D)"). Each component contained in the resin composition of this embodiment will be described in detail below.

[0012] ((A) Acrylic Polymer) The resin composition of this embodiment contains an acrylic polymer as component (A), which improves low elasticity and flexibility. The acrylic polymer is a polymer having a (meth)acrylic acid ester as a monomer, but is not limited to polymers having an acrylic acid ester as a monomer. In this embodiment, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid," and either can be selected.

[0013] The acrylic polymer can also be said to be an acrylic polymer containing structural units derived from a (meth)acrylic acid ester, and is preferably an acrylic polymer containing structural units derived from a (meth)acrylic acid ester represented by the following general formula (A1).

[0014] (In the formula, R Ａ１ represents a hydrogen atom or a methyl group, and R Ａ２ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

[0015] R Ａ１ may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom. Ａ２ The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 to 20, more preferably 1 to 15, and even more preferably 2 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-ethylhexyl group. The alkyl group may have a substituent. Examples of the substituent on the alkyl group include a cycloalkyl group, a hydroxyl group, a halogen atom, an oxygen-containing hydrocarbon group, and a nitrogen-containing cyclic group. The total number of carbon atoms in the cycloalkyl-substituted alkyl group is preferably 6 to 13, and more preferably 7 to 10. Examples of the cycloalkyl-substituted alkyl group include a norbornylmethyl group and a tricyclodecylethyl group. R Ａ２ The number of carbon atoms in the cycloalkyl group represented by the formula (I) is preferably 6 to 13, and more preferably 7 to 10. Examples of the cycloalkyl group include a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, an isobornyl group, and an adamantyl group. Among these, the norbornyl group, a tricyclodecanyl group, and an isobornyl group are preferred as the cycloalkyl group. R Ａ２ The number of carbon atoms in the aryl group represented by the formula (I) is preferably 6 to 13, and more preferably 6 to 10. Examples of the aryl group include a phenyl group and a nonylphenyl group. Ａ２ The number of carbon atoms in the aralkyl group represented by the formula (I) is preferably 7 to 15, more preferably 7 to 11. Examples of the aralkyl group include a benzyl group and a 4-methylbenzyl group.

[0016] Specific examples of the component (A) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0(2,6)]dec-8-yl (meth)acrylate, isodecyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, allyl (meth)acrylate, norbornylmethyl (meth)acrylate, tricyclodecylethyl (meth)acrylate, phenyl (meth)acrylate, nonylphenyl (meth)acrylate, benzyl (meth)acrylate, and 4-methylbenzyl (meth)acrylate.

[0017] Component (A) is not particularly limited, but is preferably an acrylic polymer having a crosslinkable functional group. Examples of acrylic polymers having a crosslinkable functional group include copolymers of (meth)acrylic acid esters and copolymerizable monomers having a crosslinkable functional group (hereinafter, sometimes simply referred to as "crosslinkable copolymerizable monomers"). The crosslinkable copolymerizable monomer preferably has one or more crosslinkable functional groups selected from the group consisting of carboxyl groups, hydroxyl groups, amino groups, vinyl groups, and epoxy groups. Among these, the crosslinkable functional group is preferably one or more selected from the group consisting of carboxyl groups, hydroxyl groups, amino groups, and epoxy groups. From the viewpoints of low moisture absorption and solder heat resistance, epoxy groups are more preferred. The crosslinkable copolymerizable monomer is preferably a compound having a double bond.

[0018] Examples of the crosslinkable copolymerizable monomer include monomers having a carboxy group such as acrylic acid and methacrylic acid; monomers having an epoxy group such as glycidyl acrylate and glycidyl methacrylate; monomers having a hydroxyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; monomers having an amino group such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; monomers having an amide group such as acrylamide, methacrylamide, dimethylacrylamide, and dimethylmethacrylamide; and monomers having a nitrile group such as acrylonitrile. These may be used alone or in combination of two or more. Among these, from the viewpoint of electrical insulation reliability, monomers having a carboxy group, monomers having an epoxy group, monomers having a hydroxyl group, and monomers having an amino group are preferred, and from the viewpoint of low moisture absorption and solder heat resistance, monomers having an epoxy group are more preferred, and glycidyl acrylate and glycidyl methacrylate are even more preferred.

[0019] Furthermore, the component (A) may be a copolymer of a (meth)acrylic acid ester and a polymerizable monomer selected from the group consisting of N-vinylpyrrolidone acrylate, N-vinylpyrrolidone methacrylate, N-acryloylmorpholine, N-methacryloylmorpholine, aromatic vinyl compounds, N-substituted maleimide compounds, and (meth)acrylic acid esters other than those represented by the general formula (A1) above.

[0020] When component (A) is a copolymer of a (meth)acrylic acid ester and a crosslinkable copolymerizable monomer, the amount of the (meth)acrylic acid ester used is preferably 70 to 99.5 parts by mass, more preferably 80 to 98 parts by mass, and even more preferably 90 to 97 parts by mass, per 100 parts by mass of the total amount of the (meth)acrylic acid ester and the crosslinkable copolymerizable monomer. The amount of the crosslinkable copolymerizable monomer used is preferably 0.5 to 30 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 20 parts by mass, per 100 parts by mass of the total amount of the (meth)acrylic acid ester and the crosslinkable copolymerizable monomer. By using an amount within this range, solder heat resistance, adhesive strength with metal foil, insulation reliability, and the like tend to be further improved. The total content of the (meth)acrylic acid ester and the crosslinkable copolymerizable monomer among all raw material monomers of component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and may even be 100% by mass.

[0021] When component (A) has an epoxy group, its epoxy equivalent is preferably 1,000 to 18,000 g / eq, more preferably 2,000 to 15,000 g / eq, even more preferably 3,000 to 10,000 g / eq, and particularly preferably 3,500 to 7,000. When the epoxy equivalent is equal to or greater than the lower limit, the dimensional stability of the substrate tends to be maintained. When the epoxy equivalent is equal to or less than the upper limit, the decrease in the glass transition temperature of the cured product tends to be suppressed, and the solder heat resistance of the substrate tends to be improved. The epoxy equivalent of component (A) can be adjusted by appropriately adjusting the copolymerization ratio when copolymerizing glycidyl (meth)acrylate with another monomer copolymerizable therewith. Commercially available acrylic polymers having epoxy groups include, for example, "HTR-860" (trade name, manufactured by Nagase ChemteX Corporation, epoxy equivalent: 2,900 g / eq), "Teisan Resin SG-P3" (trade name, manufactured by Nagase ChemteX Corporation, epoxy equivalent: 4,761 to 14,285 g / eq, weight-average molecular weight: 350,000 to 850,000), and "KH-CT-865" (trade name, manufactured by Resonac Corporation, epoxy equivalent: 3,300 g / eq).

[0022] The weight-average molecular weight (Mw) of component (A) is preferably 50,000 to 1,500,000, and from the viewpoint of improving low modulus and elongation, more preferably 100,000 to 1,300,000. It may be 100,000 to 1,100,000, 100,000 to 950,000, 300,000 to 1,100,000, 500,000 to 1,000,000, or 700,000 to 1,000,000. If the weight-average molecular weight of component (A) is equal to or greater than the lower limit, components (A) and (B) tend to be incompatible with each other and form a phase-separated structure. If the weight-average molecular weight is equal to or less than the upper limit, the component (A) tends to be easily dissolved in a solvent, resulting in excellent handleability and dispersibility. Two or more components with different weight-average molecular weights may be combined. Here, in this specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) analysis and means a value converted into standard polystyrene. GPC analysis can be performed using tetrahydrofuran (THF) as a solvent. The detailed method for measuring the weight average molecular weight is as described in the Examples.

[0023] The component (A) may be in a powder form or a liquid form at 25° C., but from the viewpoint of solubility in organic solvents and dispersibility of the acrylic polymer in the resin composition, it is preferably in a liquid form at 25° C. The component (A) may be used alone or in combination of two or more types.

[0024] (Content of Component (A)) The content of component (A) in the resin composition of this embodiment is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 3 to 45 parts by mass, even more preferably 5 to 40 parts by mass, particularly preferably 10 to 35 parts by mass, and most preferably 10 to 30 parts by mass, relative to 100 parts by mass of the total amount of components (A) and (B). If the content of component (A) is equal to or greater than the lower limit, the properties of component (A) tend to be more readily exhibited, and if the content is equal to or less than the upper limit, the adhesive strength to the metal foil and heat resistance tend to be excellent.

[0025] <(B) Thermosetting Resin> Examples of the (B) component include epoxy resins, polyimide resins, maleimide compounds, phenolic resins, modified polyphenylene ether resins, bismaleimide triazine resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. Among these, epoxy resins and maleimide compounds are preferred as the (B) component. One type of the (B) component may be used alone, or two or more types may be used in combination.

[0026] (Epoxy Resin) The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred. Epoxy resins are classified into various epoxy resins based on differences in their main skeletons, and each of the above types of epoxy resins can be further classified into bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; alicyclic epoxy resins such as dicyclopentadiene-type epoxy resins; aliphatic chain epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, bisphenol F novolac-type epoxy resins, phenol aralkyl novolac-type epoxy resins, and biphenyl aralkyl novolac-type epoxy resins; stilbene-type epoxy resins; naphthalene-skeleton-containing epoxy resins such as naphthol novolac-type epoxy resins and naphthol aralkyl-type epoxy resins; biphenyl-type epoxy resins; xylylene-type epoxy resins; dihydroanthracene-type epoxy resins, etc. Among these, from the viewpoints of solder heat resistance and low thermal expansion, naphthalene-skeleton-containing epoxy resins are preferred, and naphthol aralkyl-type epoxy resins are more preferred.

[0027] The weight-average molecular weight of the epoxy resin may be 200 to 1,000, or 300 to 900. When the weight-average molecular weight of the epoxy resin is equal to or greater than the lower limit, the epoxy resin tends to have excellent solder heat resistance, and when it is equal to or less than the upper limit, the epoxy resin tends to exhibit low elasticity and flexibility. From the viewpoint of compatibility, the epoxy equivalent of the epoxy resin may be 150 to 500 g / eq, 150 to 450 g / eq, or 150 to 300 g / eq.

[0028] (Maleimide Compound) The maleimide compound preferably includes at least one selected from the group consisting of a maleimide compound (b1) having two or more N-substituted maleimide groups [hereinafter, sometimes simply referred to as "maleimide compound (b1)" or "component (b1)"] and derivatives thereof. In other words, a preferred embodiment is that the component (B) includes at least one selected from the group consisting of a maleimide compound having two or more N-substituted maleimide groups and derivatives thereof. Examples of the "derivative thereof" include an addition reaction product of a maleimide compound (b1) having two or more N-substituted maleimide groups with an amine compound such as a diamine compound described below.

[0029] The maleimide compound (b1) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups. Specific examples of the maleimide compound (b1) include aromatic maleimide compounds such as bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane; and aliphatic maleimide compounds such as 1,6-bismaleimido-(2,2,4-trimethyl)hexane and pyrophosphate binder-type long-chain alkyl bismaleimide. Among these, from the viewpoints of adhesion to metal foil and mechanical properties, aromatic maleimide compounds are preferred as the maleimide compound (b1), aromatic bismaleimide compounds are more preferred, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide are even more preferred.

[0030] The maleimide compound (b1) is preferably a compound represented by the following general formula (B1-1).

[0031] (In the formula, X ｂ１ represents a divalent organic group.

[0032] X in the above general formula (B1-1) ｂ１ Examples of the divalent organic group represented by the formula (B1-2), (B1-3), (B1-4) or (B1-5) below are groups represented by the formula (B1-2), (B1-3), (B1-4) or (B1-5).

[0033] (In the formula, R ｂ１ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ｂ１ represents an integer of 0 to 4. * represents a bonding position.)

[0034] R ｂ１Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by n include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. ｂ１ represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferred, and 0 is more preferred. ｂ１ is an integer of 2 or more, a plurality of R ｂ１ They may be the same or different.

[0035] (In the formula, R ｂ２ and R ｂ３ Each of X independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ｂ２ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (B1-3-1): ｂ２ and n ｂ３ each independently represents an integer of 0 to 4. * indicates the bonding position.

[0036] R ｂ２ and R ｂ３ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (B1-2) is explained below. ｂ１ The same applies to the aliphatic hydrocarbon group having 1 to 5 carbon atoms as shown by X. ｂ２ Examples of the alkylene group having 1 to 5 carbon atoms represented by X include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group. ｂ２ Examples of the alkylidene group having 2 to 5 carbon atoms represented by the formula (I) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. As the alkylidene group, an isopropylidene group is preferred. ｂ２ and nｂ３ represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferred, and 0 or 2 is more preferred. ｂ２ is an integer of 2 or more, a plurality of R ｂ２ may be the same or different. ｂ３ is an integer of 2 or more, a plurality of R ｂ３ X may be the same or different. ｂ２ The divalent group represented by formula (B1-3-1) is as follows:

[0037] (In the formula, R ｂ４ and R ｂ５ Each of X independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ｂ３ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. ｂ４ and n ｂ５ each independently represents an integer of 0 to 4. * indicates the bonding position.

[0038] R ｂ４ and R ｂ５ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (B1-2) is explained below. ｂ１ The same applies to the aliphatic hydrocarbon group having 1 to 5 carbon atoms as shown by X. ｂ３ The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (B1-3) are ｂ２ Among these, an isopropylidene group is preferred from the viewpoints of adhesion to metal foil, soldering heat resistance, glass transition temperature, and thermal expansion coefficient. ｂ３ Among the groups represented by the formula (I), alkylidene groups having 2 to 5 carbon atoms are preferred, and isopropylidene groups are more preferred. ｂ４ and n ｂ５ represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferred, and 0 is more preferred. ｂ４is an integer of 2 or more, a plurality of R ｂ４ may be the same or different. ｂ５ is an integer of 2 or more, a plurality of R ｂ５ They may be the same or different from each other.

[0039] (In the formula, n ｂ６ represents an integer from 1 to 10. * represents a bonding position.)

[0040] n ｂ６ From the viewpoint of availability, is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

[0041] (In the formula, R ｂ６ and R ｂ７ Each of n independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. ｂ７ represents an integer of 1 to 8. * represents a bonding position.)

[0042] R ｂ６ and R ｂ７ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (B1-2) is explained below. ｂ１ The same applies to the aliphatic hydrocarbon group having 1 to 5 carbon atoms as shown by n ｂ７ represents an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1. ｂ７ is an integer of 2 or more, a plurality of R ｂ６ may be the same or different, and multiple R ｂ７ They may be the same or different from each other.

[0043] X in the above general formula (B1-1) ｂ１ From the viewpoint of the relative permittivity and the dielectric loss tangent (hereinafter, these are referred to as "dielectric properties"), the following formula (X ｂ１ -1) to (X ｂ１ Preferably, the divalent group is a divalent group represented by any one of the following formulas (X ｂ１ It is more preferable that the divalent group is represented by the formula:

[0044] (In the formula, * indicates the bonding position with the nitrogen atom in the maleimide group.)

[0045] From the viewpoints of solubility in organic solvents, compatibility, adhesion to metal foils, and dielectric properties, the maleimide compound is preferably a derivative of maleimide compound (b1). The derivative of maleimide compound (b1) is preferably a modified maleimide compound (Z) [hereinafter, sometimes abbreviated as "modified maleimide compound (Z)" or "component (Z)"] having a structural unit derived from maleimide compound (b1) and a structural unit derived from amine compound (b2) having a primary amino group [hereinafter, sometimes abbreviated as "amine compound (b2)" or "component (b2)"]. That is, the resin composition of this embodiment preferably contains the maleimide compound as component (B), and the maleimide compound is a modified maleimide compound having a structural unit derived from maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from amine compound (b2) having a primary amino group. The structural units derived from the component (b1) and the structural units derived from the component (b2) contained in the modified maleimide compound (Z) may each consist of one type or a combination of two or more types.

[0046] The modified maleimide compound (Z) is preferably a compound having a structure represented by the following formula (B-1), which is formed by an addition reaction between a maleimide group in the component (b1) and a primary amino group in the component (b2): (* indicates the bond position to other structures.)

[0047] Examples of the structural unit derived from the component (b1) include one or more types selected from the group consisting of groups represented by the following general formula (B1-6) and groups represented by the following general formula (B1-7).

[0048] (In the formula, X ｂ１ represents X in the above general formula (B1-1). ｂ１ and * indicates the position of attachment to other structures.)

[0049] The content of the structural unit derived from component (b1) in the modified maleimide compound (Z) is not particularly limited, but is preferably 50 to 95 mass %, more preferably 70 to 92 mass %, and even more preferably 75 to 90 mass %. When the content of the structural unit derived from component (b1) is within the above range, the dielectric properties tend to be good.

[0050] The amine compound (b2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups. Examples of the amine compound (b2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, and 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline aromatic diamine compounds such as 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, and 9,9-bis(4-aminophenyl)fluorene; and amine-modified siloxane compounds having a primary amino group.

[0051] Among these, from the viewpoint of low thermal expansion, the component (b2) is preferably an amine-modified siloxane compound having a primary amino group. In other words, the modified maleimide compound (Z) is preferably a siloxane-modified maleimide compound (Z). In other words, the component (B) preferably contains a siloxane-modified maleimide compound.

[0052] The amine compound (b2) is preferably a compound represented by the following general formula (B2-1).

[0053] (In the formula, X ｂ４ represents a divalent organic group.

[0054] The component (b2) is X in the above general formula (B2-1). ｂ４ It is preferable that the composition contains an aromatic diamine compound which is a divalent group represented by the following general formula (B2-2) [hereinafter, sometimes abbreviated as "aromatic diamine compound (B2-2)"].

[0055] (In the formula, R ｂ１１ and R ｂ１２ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ｂ５ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formula (B2-2-1) or (B2-2-2): ｂ８ and n ｂ９ each independently represents an integer of 0 to 4. * indicates the bonding position.

[0056] R in the above general formula (B2-2) ｂ１１ and R ｂ１２ Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by X include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. ｂ５Examples of the alkylene group having 1 to 5 carbon atoms represented by X include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. ｂ５ Examples of the alkylidene group having 2 to 5 carbon atoms represented by the formula (1) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. ｂ８ and n ｂ９ represents an integer of 0 to 4, and is preferably 0 or 1 from the viewpoint of availability. ｂ８ or n ｂ９ is an integer of 2 or more, a plurality of R ｂ１１ R ｂ１２ In the general formula (B2-2), X may be the same or different. ｂ５ The divalent group represented by formula (B2-2-1) is as follows:

[0057] (In the formula, R ｂ１３ and R ｂ１４ Each of X independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ｂ６ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. ｂ１０ and n ｂ１１ each independently represents an integer of 0 to 4. * indicates the bonding position.

[0058] R in the above general formula (B2-2-1) ｂ１３ and R ｂ１４ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (B2-2) is explained below. ｂ１１ and R ｂ１２ The same applies to the aliphatic hydrocarbon group having 1 to 5 carbon atoms as shown by X. ｂ６ The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X in the above general formula (B2-2) are explained below. ｂ５The same applies to the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms. ｂ１０ and n ｂ１１ represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferred, and 0 is more preferred. ｂ１０ is an integer of 2 or more, a plurality of R ｂ１３ may be the same or different. ｂ１１ is an integer of 2 or more, a plurality of R ｂ１４ In the general formula (B2-2), X may be the same or different. ｂ５ The divalent group represented by formula (B2-2-2) is as follows:

[0059] (In the formula, R ｂ１５ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ｂ７ and X ｂ８ each independently represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. ｂ１２ represents an integer of 0 to 4. * represents a bonding position.)

[0060] R in the above general formula (B2-2-2) ｂ１５ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (B2-2) is explained below. ｂ１１ and R ｂ１２ The same applies to the aliphatic hydrocarbon group having 1 to 5 carbon atoms as shown by X. ｂ７ and X ｂ８ The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (B2-2) above include X ｂ５ Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are the same as those shown in the above. ｂ７ and X ｂ８ is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group. ｂ１２represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferred, and 0 is more preferred. ｂ１２ is an integer of 2 or more, a plurality of R ｂ１５ They may be the same or different.

[0061] From the viewpoint of low thermal expansion, the component (b2) is preferably X in the general formula (B2-1). ｂ４ Preferably, the component (b2) contains an "amine-modified siloxane compound" containing a structural unit represented by the following general formula (B2-3): ｂ４ It is more preferable that the compound contains a "terminal amine-modified siloxane compound" containing a structural unit represented by the following general formula (B2-4):

[0062] (In the formula, R ｂ１６ and R ｂ１７ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. * indicates the bonding position.

[0063] (In the formula, R ｂ１６ and R ｂ１７ is the same as in the general formula (B2-3), and R ｂ１８ and R ｂ１９ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. ｂ９ and X ｂ１０ each independently represents a divalent organic group; n ｂ１３ represents an integer of 2 to 100. * represents a bonding position.)

[0064] R in the above general formulas (B2-3) and (B2-4) ｂ１６ ~R ｂ１９ Examples of the alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. ｂ１６ ~R ｂ１９Examples of the substituent that the phenyl group has in the substituted phenyl group represented by the formula (I) include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group. X ｂ９ and X ｂ１０ Examples of the divalent organic group represented by include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group formed by combining these. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, or a propylene group. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms, such as a phenylene group or a naphthylene group. Among these, X ｂ９ and X ｂ１０ is preferably an alkylene group or an arylene group, more preferably an alkylene group. ｂ１３ represents an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and even more preferably an integer of 5 to 30. ｂ１３ is an integer of 2 or more, a plurality of R ｂ１６ R ｂ１７ They may be the same or different from each other.

[0065] Examples of the structural unit derived from the component (b2) include one or more types selected from the group consisting of groups represented by the following general formula (B2-5) and groups represented by the following general formula (B2-6). (In the formula, X ｂ４ represents X in the above general formula (B2-1). ｂ４ where * indicates the bond position.)

[0066] The content of the structural unit derived from component (b2) in the modified maleimide compound (Z) is not particularly limited, but is preferably 5 to 50 mass %, more preferably 8 to 30 mass %, and even more preferably 10 to 25 mass %. When the content of the structural unit derived from component (b2) is within the above range, the compound tends to have excellent low thermal expansion properties and dielectric properties, as well as good solder heat resistance, flame retardancy, and glass transition temperature.

[0067] The total content of the structural units derived from the component (b1) and the structural units derived from the component (b2) in the modified maleimide compound (Z) is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass (i.e., consisting only of structural units derived from the component (b1) and structural units derived from the component (b2)).

[0068] The content ratio of the structural unit derived from the component (b1) and the structural unit derived from the component (b2) in the modified maleimide compound (Z) is not particularly limited. ２ Group derived from the group (-NH ２ The content ratio is such that the equivalent ratio (Ta1 / Ta2) of the total equivalent (Ta1) of groups (including maleimide groups) derived from component (b1) to the total equivalent (Ta2) of groups (including maleimide groups) derived from maleimide groups is preferably 0.05 to 10, more preferably 2 to 8. When the equivalent ratio (Ta1 / Ta2) is within the above range, the composition tends to have excellent low thermal expansion properties and dielectric properties, as well as good solder heat resistance, flame retardancy, and glass transition temperature.

[0069] From the viewpoints of dielectric properties, insulation reliability, solubility in organic solvents, adhesion to metal foil, moldability, etc., the maleimide compound preferably contains a compound represented by the following general formula (B-2):

[0070] (In the formula, X ｂ１ and X ｂ４ is as explained in the above general formulas (b1-1) and (b2-1).

[0071] (Method for Producing Modified Maleimide Compound (Z)) The component (Z) can be produced, for example, by reacting the component (b1) with the component (b2) in an organic solvent. Specifically, the component (b1), the component (b2), and, if necessary, other components are charged in predetermined amounts into a reactor, and the component (b1) and the component (b2) are subjected to a Michael addition reaction (hereinafter, sometimes referred to as a "pre-reaction") to obtain the modified maleimide compound (Z). The reaction conditions are not particularly limited, but from the viewpoint of suppressing gelation while obtaining good reactivity and workability, the reaction temperature is preferably 50 to 160°C, more preferably 90 to 140°C, and the reaction time is preferably 1 to 10 hours, more preferably 1 to 5 hours.

[0072] In the pre-reaction, a reaction catalyst may be used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. There are no particular restrictions on the amount of the reaction catalyst used, but it is, for example, 0.01 to 5 parts by mass per 100 parts by mass of the total amount of component (b1) and component (b2).

[0073] In the pre-reaction, the solids concentration of the reaction raw materials and the viscosity of the reaction solution may be adjusted by adding or concentrating an organic solvent as needed. The solids concentration of the reaction raw materials is not particularly limited, but is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. If the solids concentration of the reaction raw materials is equal to or greater than the lower limit, a sufficient reaction rate can be obtained, which tends to be advantageous in terms of production costs. If the solids concentration is equal to or less than the upper limit, good solubility can be obtained, stirring efficiency is improved, and gelation tends to be less likely.

[0074] The weight average molecular weight (Mw) of the modified maleimide compound (Z) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.

[0075] (Content of Component (B)) The content of component (B) in the resin composition of this embodiment is preferably 50 to 99 parts by mass, more preferably 55 to 97 parts by mass, even more preferably 60 to 95 parts by mass, particularly preferably 65 to 90 parts by mass, and most preferably 70 to 90 parts by mass, relative to 100 parts by mass of the total amount of components (A) and (B). If the content of component (B) is at least the lower limit, the adhesive strength to the metal foil and solder heat resistance tend to be excellent, and if the content is at most the upper limit, the properties of component (A) tend to be more easily exhibited.

[0076] <(C) Inorganic filler surface-treated with a silane coupling agent> The resin composition of this embodiment further contains, as component (C), an inorganic filler surface-treated with a silane coupling agent. Component (C) can prevent the reduction of the effect of adding silane coupling agent (D) to the resin composition of this embodiment by surface-treating the inorganic filler with a silane coupling agent. In other words, by surface-treating component (C) with a silane coupling agent, it is possible to prevent the silane coupling agent (D) from being used for surface treatment of the inorganic filler, and the effect of component (D) can be fully exerted. From this viewpoint, the (C) component preferably contains 80% by mass or more (preferably 90% by mass or more, including 100% by mass; the same applies below) of an inorganic filler in which 70% or more of the surface of the inorganic filler has been treated with a silane coupling agent, more preferably 80% by mass or more of an inorganic filler in which 80% or more of the surface of the inorganic filler has been treated with a silane coupling agent, even more preferably 80% by mass or more of an inorganic filler in which 90% or more of the surface of the inorganic filler has been treated with a silane coupling agent, particularly preferably 80% by mass or more of an inorganic filler in which 98% or more of the surface of the inorganic filler has been treated with a silane coupling agent, and most preferably 80% by mass or more of an inorganic filler in which 100% or more of the surface of the inorganic filler has been treated with a silane coupling agent.

[0077] Examples of materials for component (C) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (e.g., calcined clay), molybdic acid compounds (e.g., zinc molybdate), talc, aluminum borate, and silicon carbide. One or more of the components (C) may be used alone or in combination. Among these, from the viewpoints of low thermal expansion, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred. Examples of silica include precipitated silica and dry-process silica. The precipitated silica is produced by a wet process and has a high water content. The dry-process silica is produced by a dry process and contains almost no bound water. Dry process silica further includes crushed silica, fumed silica, fused silica, and the like.

[0078] In component (C), the silane coupling agent used for the surface treatment of inorganic filler can be exemplified by aminosilane coupling agent, epoxysilane coupling agent, phenylsilane coupling agent, alkylsilane coupling agent, alkenylsilane coupling agent, alkynylsilane coupling agent, silicone oligomer coupling agent, etc. Among these, aminosilane coupling agent, epoxysilane coupling agent, phenylsilane coupling agent are preferred, aminosilane coupling agent, phenylsilane coupling agent are more preferred, and phenylsilane coupling agent is even more preferred.Silane coupling agent can be used alone or in combination of two or more.

[0079] The average particle size of component (C) is preferably 0.1 to 2.5 μm, more preferably 0.2 to 1.5 μm, and even more preferably 0.3 to 0.8 μm. If the average particle size of component (C) is at least the lower limit, the filler is easily dispersed in the resin varnish, and aggregation tends to be less likely to occur. If the average particle size is at or below the upper limit, sedimentation of component (C) in the resin varnish tends to be less likely to occur. Here, the average particle size refers to the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated, assuming the total volume of the particles to be 100%, and can be measured using a particle size distribution analyzer using a laser diffraction scattering method, for example.

[0080] (Content of Component (C)) The content of component (C) in the resin composition of this embodiment is not particularly limited, but is preferably 30 to 300 parts by mass, more preferably 50 to 250 parts by mass, even more preferably 70 to 200 parts by mass, particularly preferably 100 to 200 parts by mass, and most preferably 130 to 170 parts by mass, relative to 100 parts by mass of the total amount of component (A) and component (B). When the content of component (C) is equal to or greater than the lower limit, excellent low thermal expansion properties and high heat resistance tend to be obtained. When the content of component (C) is equal to or less than the upper limit, the properties of component (A) tend to be more easily exhibited.

[0081] <(D) Silane Coupling Agent> The resin composition of this embodiment further contains a silane coupling agent as component (D). The silane coupling agent is a compound having a substituted silyl group. Examples of the substituent of the substituted silyl group include a hydroxyl group; an alkyl group such as a methyl group; an alkoxy group such as a methoxy group or an ethoxy group; and a carboxyl group. The substituent of the substituted silyl group is bonded to the silicon atom, and the number of the substituents is 1 to 3, and may be three. When the compound having a substituted silyl group has three substituents, the compound can be referred to as a compound having a tri-substituted silyl group.

[0082] The (D) component preferably has a functional group capable of reacting with the (A) component or the (B) component.The (D) component can be classified according to the type of functional group, and examples thereof include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, silicone oligomer coupling agents, (meth)acrylicsilane coupling agents, isocyanatesilane coupling agents, isocyanuratesilane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, carboxysilane coupling agents, alkylene glycol silane coupling agents, etc.Among these, from the viewpoints of adhesive strength with copper foil, desmear resistance, flame retardancy, etc., aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, and alkenylsilane coupling agents are preferred, and aminosilane coupling agents, epoxysilane coupling agents, and alkenylsilane coupling agents are more preferred. Examples of the alkenylsilane coupling agent include vinylsilane coupling agents, etc. The component (D) may be used alone or in combination of two or more types.

[0083] Component (D) can be a commercially available product, such as the KBM series and KBE series manufactured by Shin-Etsu Chemical Co., Ltd., or a silane coupling agent manufactured by Dow-Toray Industries, Inc.

[0084] (Content of Component (D)) The content of component (D) in the resin composition of this embodiment is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, even more preferably 0.1 to 1.5 parts by mass, particularly preferably 0.1 to 1.0 part by mass, and most preferably 0.1 to 0.7 parts by mass, relative to 100 parts by mass of the total amount of component (A) and component (B). When the content of component (D) is equal to or greater than the lower limit, there is a tendency for the flame retardancy to be easily improved while maintaining good adhesive strength to copper foil and desmear resistance, even in a resin composition containing component (A), which is an easily combustible component. When the content of component (D) is equal to or less than the upper limit, there is a tendency for the adhesive strength to copper foil to be easily maintained.

[0085] <(E) Curing Accelerator> The resin composition of this embodiment may contain a (E) curing accelerator (hereinafter, sometimes referred to as "component (E)"). The (E) component may be used alone or in combination of two or more types. For example, when the (B) thermosetting resin contains an epoxy resin or a maleimide compound, the (E) curing accelerator is not particularly limited, but preferably contains one or more selected from the group consisting of amine compounds and imidazole-based compounds, and more preferably contains an imidazole-based compound. Examples of the amine compound include dicyandiamide, diaminodiphenylethane, and guanylurea. Examples of the imidazole compound include 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, benzimidazole, and isocyanate-masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole).

[0086] (Content of Component (E)) When the resin composition of the present embodiment contains the component (E), the content thereof is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the total amount of the component (A) and the component (B).

[0087] <Other Components> The resin composition of the present embodiment may contain, as necessary, a resin other than the component (B), an elastomer other than the component (A), a curing agent, a crosslinking agent, a flame retardant, a flame retardant aid, conductive particles, a coupling agent, a flow adjuster, an antioxidant, a heat stabilizer, an antistatic agent, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, etc. Known components can be used as these other components.

[0088] The resin composition of this embodiment may be dissolved or dispersed in an organic solvent, or in the form of a so-called "resin varnish." Hereinafter, a resin composition containing an organic solvent may be referred to as a "resin varnish." Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon-based solvents such as toluene and xylene; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; amide-based solvents such as N-methylpyrrolidone, formamide, N-methylformamide, and N,N-dimethylacetamide; and alcohol-based solvents such as methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, and dipropylene glycol monopropyl ether. One type of organic solvent may be used alone, or two or more types may be used in combination. The solid content concentration in the varnish is preferably from 10 to 70% by mass, more preferably from 20 to 60% by mass, and even more preferably from 35 to 60% by mass.

[0089] [Prepreg] The prepreg of this embodiment includes a substrate and the resin composition of this embodiment or a semi-cured product of the resin composition. Here, the expression "including a substrate and a semi-cured product of the resin composition of this embodiment" means that the resin composition is impregnated into the substrate and semi-cured (B-staged). In this specification, B-staging refers to achieving the B-stage state defined in JIS K6900 (1994). The prepreg can be produced, for example, by impregnating or coating the substrate with the varnish-like resin composition of this embodiment, and then heating and drying the resin composition to semi-cure (B-stage).

[0090] The following hot melt method or solvent method can be used to impregnate or coat a substrate with a resin composition. The hot melt method is a method in which the resin composition does not contain an organic solvent, and (1) the resin composition is first coated on coated paper that has good peelability from the resin composition and then laminated onto the substrate, or (2) the resin composition is directly coated onto the substrate using a die coater. On the other hand, the solvent method is a method in which the resin composition contains an organic solvent, and the substrate is immersed in the resulting resin composition to impregnate the substrate with the resin composition, followed by drying.

[0091] As the substrate, a fibrous substrate such as a woven fabric or a nonwoven fabric is usually used, with a woven fabric being preferred. Furthermore, the substrate is preferably a sheet-like fibrous substrate. Examples of materials for the fibrous substrate include inorganic fibers such as glass, alumina, asbestos, boron, silica alumina glass, silica glass, Tyranno, silicon carbide, silicon nitride, and zirconia; organic fibers such as aramid, polyether ether ketone, polyetherimide, polyethersulfone, carbon, and cellulose; and mixtures thereof. Among these, inorganic fibers are preferred, and glass fibers are more preferred. In other words, the substrate is preferably a woven fabric of glass fibers, i.e., glass cloth. The thickness of the substrate is preferably 5 to 200 μm, but may be 10 to 100 μm, or may be 20 to 50 μm. By setting the thickness of the substrate to the above upper limit or less, dimensional changes due to temperature changes, moisture absorption, and the like during the manufacturing process can be reduced.

[0092] The conditions for producing the prepreg are not particularly limited, but in the case of a solvent method, it is preferable that 80% by mass or more of the organic solvent used in the resin varnish has evaporated in the resulting prepreg. The drying temperature after impregnating or coating the substrate with the resin composition is preferably 80 to 180°C, more preferably 100 to 140°C, and the drying time is appropriately set taking into account the gelation time of the resin composition.

[0093] The solid content of the resin composition in the prepreg of this embodiment is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, even more preferably 40 to 70% by mass, and particularly preferably 45 to 60% by mass. If the solid content of the resin composition in the prepreg is within the above range, good moldability tends to be obtained when the prepreg is formed into a laminate.

[0094] The thickness of the prepreg of this embodiment is not particularly limited, and may be 10 to 200 μm, 10 to 150 μm, or 10 to 100 μm.

[0095] [Laminate, Metal-Clad Laminate] The laminate of this embodiment is a laminate including a cured product of the resin composition of this embodiment. Alternatively, the laminate of this embodiment may be a laminate including a cured product of the prepreg of this embodiment. The metal-clad laminate of this embodiment is a metal-clad laminate including a metal foil and a cured product of the resin composition of this embodiment. Alternatively, the metal-clad laminate of this embodiment may be a metal-clad laminate including a cured product of the prepreg of this embodiment. The metal-clad laminate can be produced, for example, by stacking both adhesive surfaces of a single prepreg of this embodiment or a laminate of two or more prepregs (preferably 2 to 20 prepregs) on top of a metal foil, and then heating and pressurizing the laminate in a vacuum press at preferably 130 to 260°C, more preferably 180 to 250°C, and even more preferably 210 to 250°C, at a pressure of 0.5 to 10 MPa, preferably 1 to 5 MPa.

[0096] Examples of metal foils used in metal-clad laminates include copper foil, aluminum foil, tin foil, tin-lead alloy (solder) foil, and nickel foil. Other examples include a three-layer composite foil in which an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy is provided on both sides with a 0.5-15 μm copper layer and a 10-300 μm copper layer, and a two-layer composite foil in which aluminum and copper foil are combined. Copper foil and aluminum foil are preferred as metal foils, with copper foil being more preferred. The thickness of the metal foil can be a thickness typically used in laminates, for example, 1-200 μm.

[0097] In the laminate and metal-clad laminate of this embodiment, the prepreg (more specifically, the resin composition in the prepreg) is C-staged and cured. In other words, the laminate of this embodiment contains a C-staged prepreg, and the metal-clad laminate of this embodiment can also be said to contain a C-staged prepreg and a metal foil. Here, C-staging in this specification refers to bringing the material into a C-stage state as defined in JIS K6900 (1994).

[0098] [Printed Wiring Board] The printed wiring board of this embodiment is a printed wiring board containing a cured product of the resin composition of this embodiment. The printed wiring board of this embodiment may also contain one or more selected from the group consisting of the cured product of the prepreg of this embodiment, the laminate of this embodiment, and a metal-clad laminate. The printed wiring board of this embodiment does not necessarily contain a laminate or a metal-clad laminate as is. For example, it may also contain a laminate or a metal-clad laminate that has been subjected to circuit formation processing such as drilling, metal plating, or etching of metal foil. The printed wiring board of this embodiment can be manufactured by using the laminate or metal-clad laminate of this embodiment to perform circuit formation processing such as drilling, metal plating, or etching of metal foil using a known method, and then further performing multi-layer processing as needed.

[0099] [Semiconductor Package] The semiconductor package of this embodiment includes the printed wiring board of this embodiment and a semiconductor element. In other words, the semiconductor package of this embodiment is formed by mounting a semiconductor element on the printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor element such as a semiconductor chip or memory at a predetermined position on the printed wiring board of this embodiment by a known method and sealing the semiconductor element with a sealing resin or the like.

[0100] The present embodiment will be specifically described below with reference to examples, but the present embodiment is not limited to the following examples.

[0101] In each example, the weight average molecular weight (Mw) was measured by the following method. It was calculated by gel permeation chromatography (GPC) from a calibration curve using standard polystyrene. The calibration curve was approximated by a cubic equation using standard polystyrene: TSKstandard POLYSTYRENE (Types: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The GPC measurement conditions are shown below. Apparatus: Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation] Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation] Column: Guard column; "TSK Guard column HHR-L" + column; "TSKgel G4000HHR" + "TSKgel G2000HHR" (all product names manufactured by Tosoh Corporation) Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column) Eluent: tetrahydrofuran Sample concentration: 30 mg / 5 mL Injection volume: 20 μL Flow rate: 1.00 mL / min Measurement temperature: 40°C

[0102] [Production Example 1: Production of Siloxane-Modified Maleimide Compound] 100 g of a siloxane modified at both ends with diamine (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-22-161A, amino functional group equivalent: 800 g / mol), 450 g of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 550 g of propylene glycol monomethyl ether were placed in a 2 L reactor equipped with a thermometer, a stirrer, and a reflux condenser and water content meter, and the mixture was allowed to react at 120° C. for 3 hours to produce a siloxane-modified maleimide compound-containing liquid. The weight-average molecular weight (Mw) of the resulting siloxane-modified maleimide compound was 2,500.

[0103] Examples 1 to 4, Comparative Examples 1 and 2 (Preparation of resin composition and resin varnish) The components shown in Table 1 were blended in the amounts shown in Table 1 (the blending amounts shown in Table 1 are parts by mass of solid content. In the case of a solution or dispersion, they are parts by mass converted to solid content), and mixed in methyl isobutyl ketone to obtain a resin composition (resin varnish) with a non-volatile content (solid content concentration) of 50 mass%. (Preparation of prepreg) The resin varnish prepared in each example was impregnated into glass cloth T2118 (trade name, manufactured by Nitto Boseki Co., Ltd.), and then heated and dried at 120°C for 5 minutes to obtain a prepreg. (Preparation of double-sided copper-clad laminate) A 12 μm thick electrolytic copper foil "3EC-M3-VLP-12" (trade name, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides of the four prepregs so that the M side (matte side) faced the prepreg, and heated and pressed at 240° C. for 80 minutes under vacuum pressing conditions of 3 MPa, to prepare a double-sided copper-clad laminate.

[0104] [Evaluation Method] (1) Flame Retardancy: In accordance with UL-94, five test specimens were used to measure the flaming combustion time (seconds), and the average value of the five was calculated. The test specimens were prepared by immersing a double-sided copper-clad laminate in a copper etching solution to remove the copper foil, and then cutting the laminate into a size of 125 mm x 13 mm.

[0105] (2) Adhesion Strength with Copper Foil The copper foil of each double-sided copper-clad laminate was partially etched to form a 3 mm wide copper foil line, which was used as a test piece. The adhesion strength with copper foil was evaluated by measuring the load when the copper foil line was peeled off at a speed of 50 mm / min in a direction 90° to the adhesive surface. If the peeling load was 0.3 kN / m or more, it was determined that the adhesion to the copper foil was sufficient.

[0106] (3) Desmear Resistance The double-sided copper-clad laminate obtained in each example was immersed in a copper etching solution to prepare a 40 mm x 40 mm test piece from which the copper foil had been removed. The test piece was treated with a swelling treatment solution "Swelling Dip Securigant P" (manufactured by Atotech Japan Co., Ltd.) at 70°C for 5 minutes. It was then rinsed with water at room temperature for 2 minutes, and then treated with a roughening solution "Concentrate Compact CP" (manufactured by Atotech Japan Co., Ltd.) at 80°C for 10 or 15 minutes to roughen the surface. It was then rinsed with water at 50°C for 2 minutes, neutralized with a neutralizing solution "Reduction Solution Securigant P500" (manufactured by Atotech Japan Co., Ltd.) at 40°C for 5 minutes, rinsed with water at room temperature for 5 minutes, and then dried. The desmear weight loss was calculated from the difference between the dry weight before desmearing and the dry weight after desmearing (dry weight before desmearing - dry weight after desmearing). In Examples 1 and 2, a percentage [100 × (desmear weight reduction in Example 1 or Example 2) / (desmear weight reduction in Comparative Example 1)] was calculated based on the desmear weight reduction in Comparative Example 1, and in Examples 3 and 4, a percentage [100 × (desmear weight reduction in Example 3 or Example 4) / (desmear weight reduction in Comparative Example 2)] was calculated based on the desmear weight reduction in Comparative Example 2.

[0107] (4) Thermal Expansion Coefficient The copper foil on both sides of the double-sided copper-clad laminate obtained in each example was removed by etching to prepare a 5 mm square test piece. Next, the thermal expansion coefficient of the test piece was measured using a thermomechanical analyzer (TMA) (manufactured by TA Instruments Japan, product name: Q400) in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard. More specifically, measurements were performed twice in the temperature range of 25 to 260 ° C, under conditions of a load of 0.1 N and a heating rate of 10 ° C / min, and the average thermal expansion coefficient of the second measurement was determined. The thermal expansion coefficient is the linear thermal expansion coefficient in the plane direction of the test piece.

[0108]

[0109] The details of the components in each table are as follows: [Component (A)] Acrylic polymer 1: "Teisan Resin SG-P3", an acrylic polymer having an epoxy group, weight average molecular weight = 850,000, epoxy equivalent: 4,800 g / eq (trade name, manufactured by Nagase ChemteX Corporation)

[0110] [Component (B)] Epoxy resin: "EPICLON HP-9500", a naphthalene skeleton-containing epoxy resin (manufactured by DIC Corporation, trade name) Maleimide compound: the siloxane-modified maleimide compound prepared in Production Example 1

[0111] [Component (C)] Inorganic filler 1: Fused spherical silica surface-treated with a phenylsilane coupling agent, average particle size 0.5 μm

[0112] [Component (D)] Vinylsilane coupling agent 1: "KBM-1083" (Shin-Etsu Chemical Co., Ltd.) Epoxysilane coupling agent 1: "KBM-4803" (Shin-Etsu Chemical Co., Ltd.) Aminosilane coupling agent 1: "KBM-6803" (Shin-Etsu Chemical Co., Ltd.) Aminosilane coupling agent 2: "KBM-603" (Shin-Etsu Chemical Co., Ltd.)

[0113] [Component (E)] Curing accelerator 1: Isocyanate masked imidazole "G-8009L" (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0114] As is clear from Table 1, the double-sided copper-clad laminates of the examples using the resin compositions of this embodiment contain the relatively flammable component (A), but they exhibit excellent flame retardancy while maintaining good adhesive strength to the copper foil and desmear resistance. The double-sided copper-clad laminates of the examples also exhibited good low thermal expansion properties. On the other hand, the double-sided copper-clad laminates of the comparative examples using resin compositions that did not contain the component (D) exhibited lower flame retardancy than the examples.

Claims

1. A resin composition comprising (A) an acrylic polymer, (B) a thermosetting resin, and (C) an inorganic filler that has been surface-treated with a silane coupling agent, and further comprising (D) a silane coupling agent.

2. The resin composition according to claim 1, wherein the weight average molecular weight (Mw) of component (A) is 50,000 to 1,500,000.

3. The resin composition according to claim 1, wherein the content of the component (A) is 1 to 50 parts by mass per 100 parts by mass of the total amount of the components (A) and (B).

4. The resin composition according to claim 1, wherein the (B) component comprises at least one selected from the group consisting of epoxy resins, polyimide resins, maleimide compounds, phenolic resins, modified polyphenylene ether resins, bismaleimide triazine resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins and melamine resins.

5. The resin composition according to claim 1, wherein the component (B) comprises at least one member selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof.

6. The resin composition according to claim 1, wherein the component (B) comprises a siloxane-modified maleimide compound.

7. The resin composition according to claim 1, wherein the component (D) has a functional group capable of reacting with the component (A) or the component (B).

8. A prepreg comprising a substrate and the resin composition according to any one of claims 1 to 7 or a semi-cured product of said resin composition.

9. A laminate comprising a cured product of the resin composition according to any one of claims 1 to 7.

10. A metal-clad laminate comprising a metal foil and a cured product of the resin composition according to any one of claims 1 to 7.

11. A printed wiring board comprising a cured product of the resin composition according to any one of claims 1 to 7.

12. A semiconductor package comprising the printed wiring board according to claim 11 and a semiconductor element.

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