Resin composition, prepreg, resin film, laminate, printed wiring board, and semiconductor package

Abstract

Provided are a resin composition and the like which can exhibit low transmission loss and excellent flame retardancy, and which can make the appearance of a laminate good. Specifically, the resin composition is represented by the following. Provided is a resin composition containing (A) a thermosetting resin, (B) a polymer having a hydrocarbon chain or a polyether chain, (X) a phosphorus compound-based flame retardant, and (Y) a flame retardant other than the phosphorus compound-based flame retardant, the (X) component does not contain a filling flame retardant (X1), and the (Y) component does not contain a filling flame retardant (Y1). Or when the component (X) contains a filling flame retardant (X1) or the component (Y) contains a filling flame retardant (Y1), the total content of the filling flame retardant (X1) and the filling flame retardant (Y1) is 25 parts by mass or less per 100 parts by mass of the solid content in the resin composition.

Description

Technical Field

[0001] The present disclosure relates to a resin composition, a prepreg, a resin film, a laminate, a printed wiring board, and a semiconductor package. Background Art

[0002] The signals used in mobile communication devices, such as mobile phones, their base stations, network infrastructure equipment like servers and routers, and electronic devices like mainframe computers, are becoming increasingly faster and larger year by year. This is accompanied by a growing demand for substrate materials used in printed circuit boards (PCBs) used in these electronic devices to minimize transmission losses in high-frequency signals.

[0003] In recent years, in addition to the aforementioned electronic devices, new systems that process high-frequency wireless signals have been put into practical use or planned for use in the ITS (Intelligent Transport Systems) field, such as in the automotive and transportation systems sector, and in the field of indoor short-range communications. Consequently, the demand for substrate materials with excellent high-frequency characteristics for printed wiring boards used in these fields is expected to increase.

[0004] Printed wiring boards (PCBs) require high flame retardancy from a safety perspective. In PCBs, where extremely low transmission loss is required, hydrocarbon resins such as polybutadiene and styrene-ethylene-butylene-styrene block copolymer (SEBS) are used to reduce transmission loss (see, for example, Patent Document 1). However, while these hydrocarbon resins are effective in reducing transmission loss, increasing their added amount tends to deteriorate flame retardancy. Therefore, resin compositions containing these hydrocarbon resins struggle to achieve both low transmission loss and excellent flame retardancy.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-182851 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] Therefore, the present inventors investigated achieving both low transmission loss and excellent flame retardancy in a hydrocarbon-based resin composition by using a specific combination of flame retardants. However, it was discovered that low transmission loss and excellent flame retardancy are not always achieved simultaneously, and that scratches (kasre) tend to form on the surface of the laminate, resulting in poor appearance.

[0010] In view of the above-mentioned circumstances, the present disclosure aims to provide a resin composition that exhibits low transmission loss and excellent flame retardancy, and that can provide a laminate with a good appearance. Furthermore, the present disclosure aims to provide a prepreg, resin film, laminate, printed wiring board, and semiconductor package manufactured using the resin composition.

[0011] Means for solving problems

[0012] The present inventors have conducted studies to achieve the above-mentioned object, and as a result, have found that the above-mentioned object can be achieved by the present disclosure.

[0013] The present disclosure includes the following embodiments [1] to

[15] .

[0014] [1] A resin composition comprising (A) a thermosetting resin, (B) a polymer having a hydrocarbon chain or a polyether chain, (X) a phosphorus compound flame retardant, and (Y) a flame retardant other than the phosphorus compound flame retardant.

[0015] The component (X) does not contain the filler flame retardant (X1), and the component (Y) does not contain the filler flame retardant (Y1), or

[0016] When the component (X) contains the (X1) filling flame retardant or the component (Y) contains the (Y1) filling flame retardant, the total content of the (X1) filling flame retardant and the (Y1) filling flame retardant is 25 parts by mass or less per 100 parts by mass of the solid content in the resin composition.

[0017] [2] The resin composition according to [1], wherein the component (X) contains (X2) a compatible flame retardant.

[0018] [3] The resin composition according to [1] or [2], wherein the component (Y) contains (Y2) a compatible flame retardant.

[0019] [4] The resin composition according to any one of [1] to [3], wherein the component (A) comprises at least one selected from the group consisting of epoxy resins, maleimide compounds, phenolic resins, polyimide 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.

[0020] [5] The resin composition according to any one of [1] to [4], wherein the component (B) is at least one selected from a conjugated diene polymer, a styrene-based elastomer, and modified products thereof.

[0021] [6] The resin composition according to any one of [1] to [5], wherein the component (X) comprises at least one selected from the group consisting of (Xi) a phosphate ester compound, (X-ii) a phosphine oxide compound, (X-iii) a phosphaphenanthrene compound, (X-iv) a metal salt of phosphinic acid, and (Xv) an organic nitrogen-phosphorus compound.

[0022] [7] The resin composition according to any one of [1] to [6], wherein the component (X) has two or more phosphorus atoms in one molecule.

[0023] [8] The resin composition according to any one of [1] to [7], wherein the component (Y) is a halogen-based flame retardant.

[0024] [9] The resin composition according to any one of [1] to [8], further comprising (C) an inorganic filler.

[0025]

[10] The resin composition according to any one of [1] to [9], further comprising (D) a curing accelerator.

[0026]

[11] A prepreg comprising the resin composition described in any one of [1] to

[10] above or a semi-cured product of the resin composition.

[0027]

[12] A resin film comprising the resin composition described in any one of [1] to

[10] above or a semi-cured product of the resin composition.

[0028]

[13] A laminate comprising at least one of a cured product of a resin composition described in any one of [1] to

[10] , a cured product of a prepreg described in

[11] , and a cured product of a resin film described in

[12] , and a metal foil.

[0029]

[14] A printed wiring board comprising one or more of a cured product of a resin composition described in any one of [1] to

[10] , a cured product of a prepreg described in

[11] , a cured product of a resin film described in

[12] , and a laminate described in

[13] .

[0030]

[15] A semiconductor package comprising the printed wiring board described in

[14] above and a semiconductor element.

[0031] Effects of the Invention

[0032] According to the present disclosure, a resin composition can be provided that exhibits low transmission loss and excellent flame retardancy, and can also provide a laminate with a good appearance. Furthermore, a prepreg, a resin film, a laminate, a printed wiring board, and a semiconductor package using the resin composition can be provided. DETAILED DESCRIPTION

[0033] In the numerical ranges described in this disclosure, the lower limit or upper limit of the numerical range may be replaced with the values ​​shown in the Examples. Furthermore, the lower limit and upper limit of a numerical range may be arbitrarily combined with the lower limit or upper limit of another numerical range, respectively. In the numerical range "AA to BB," the values ​​AA and BB at both ends are included in the numerical range as the lower limit and upper limit, respectively.

[0034] In this disclosure, for example, a description such as "10 or more" means a value of 10 or more, and even if the value differs, this description shall prevail. In addition, for example, a description such as "10 or less" means a value of 10 or less, and even if the value differs, this description shall prevail.

[0035] 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 the resin composition contains multiple substances corresponding to a certain component (e.g., component (A)), the content of each component in the resin composition refers to the total amount of the multiple substances present in the resin composition unless otherwise specified.

[0036] In the present disclosure, the “resin component” is defined as all components excluding inorganic compounds such as (C) inorganic fillers described later, among the solid components constituting the resin composition.

[0037] In the present disclosure, the term "solid content" refers to components in the resin composition other than the organic solvent described below, and components that are liquid at room temperature around 25°C are also considered solid content.

[0038] The expression "containing XX" described in the present disclosure includes both the meaning of containing XX in a state after the reaction of XX and the meaning of simply containing XX when XX is capable of reacting.

[0039] Any combination of the matters described in the present disclosure is also included in the present disclosure and the embodiments.

[0040] [Resin composition]

[0041] This embodiment is the following resin composition.

[0042] A resin composition comprising (A) a thermosetting resin, (B) a polymer having a hydrocarbon chain or a polyether chain, (X) a phosphorus compound flame retardant, and (Y) a flame retardant other than the phosphorus compound flame retardant.

[0043] The component (X) does not contain the filler flame retardant (X1), and the component (Y) does not contain the filler flame retardant (Y1), or

[0044] When the component (X) contains the (X1) filling flame retardant or the component (Y) contains the (Y1) filling flame retardant, the total content of the (X1) filling flame retardant and the (Y1) filling flame retardant is 25 parts by mass or less per 100 parts by mass of the solid content in the resin composition.

[0045] Hereinafter, each component contained in the resin composition of this embodiment will be described in detail one by one.

[0046] ((A) Thermosetting resin)

[0047] Examples of the component (A) include epoxy resins, maleimide compounds, phenolic resins, polyimide 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, the component (A) preferably contains at least one selected from epoxy resins, maleimide compounds, phenolic resins, polyimide resins, cyanate resins, and isocyanate resins, more preferably contains at least one selected from epoxy resins and maleimide compounds, and even more preferably contains a maleimide compound from the viewpoint of low thermal expansion properties.

[0048] As the component (A), one type may be used alone, or two or more types may be used in combination.

[0049] As the above-mentioned epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferably used. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among them, glycidyl ether type epoxy resins are preferred.

[0050] Epoxy resins are also classified into various epoxy resins according to the differences in their main skeletons. Among the various types of epoxy resins mentioned above, they are further classified into: bisphenol-type epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; alicyclic epoxy resins such as dicyclopentadiene epoxy resin; aliphatic chain epoxy resins; 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, biphenyl aralkyl novolac-type epoxy resins, etc. novolac-type epoxy resins; stilbene-type epoxy resins; naphthol novolac-type epoxy resins, naphthol aralkyl epoxy resins, etc. naphthalene skeleton-containing epoxy resins; biphenyl-type epoxy resins; xylene-type epoxy resins; dihydroanthracene-type epoxy resins, etc.

[0051] The maleimide compound preferably comprises at least one selected from maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof. The maleimide compound having one or more N-substituted maleimide groups is preferably a maleimide compound having two or more N-substituted maleimide groups, more preferably a maleimide compound having 2 to 10 N-substituted maleimide groups, further preferably a maleimide compound having 2 to 5 N-substituted maleimide groups, and particularly preferably a maleimide compound having two N-substituted maleimide groups.

[0052] Furthermore, the maleimide compound having two or more N-substituted maleimide groups is preferably a compound in which nitrogen atoms of the maleimide groups are bonded to each other via an organic group.

[0053] The maleimide compound having one or more N-substituted maleimide groups is not particularly limited, but examples thereof include aromatic maleimide compounds preferably having one N-substituted maleimide group bonded to an aromatic ring, such as N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, and N-benzylmaleimide; 4,4'-diphenylmethanebismaleimide, bis(4-maleimidephenyl)ether, bis(4-maleimidephenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide; Examples of the present invention include aromatic bismaleimide compounds preferably having two N-substituted maleimide groups bonded to the aromatic ring, such as amine, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and aromatic bismaleimide containing an indane ring; aromatic polymaleimide compounds preferably having three or more N-substituted maleimide groups bonded to the aromatic ring, such as polyphenylmethanemaleimide and biphenylaralkyl maleimide; and aliphatic maleimide compounds such as N-dodecylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and pyrophosphate-bound long-chain alkyl bismaleimide. Among these, aromatic bismaleimide compounds having two N-substituted maleimide groups bonded to an aromatic ring are preferred from the perspectives of compatibility with other resins, adhesion to conductors, heat resistance, low thermal expansion, mechanical properties, and reduced transmission loss. Aromatic polymaleimide compounds having three or more N-substituted maleimide groups bonded to an aromatic ring are more preferred. Biphenylaralkyl maleimides and aromatic bismaleimides containing an indane ring are even more preferred. In this disclosure, the term "indane ring" refers to a fused bicyclic structure consisting of an aromatic six-membered ring and a saturated aliphatic five-membered ring. The aromatic bismaleimide containing an indane ring preferably has a divalent group represented by the following general formula (a1-1).

[0054] [Chemistry 1]

[0055]

[0056] (Where R a1 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, and n1 is an integer from 0 to 3. a2~R a4 Each independently represents an alkyl group having 1 to 10 carbon atoms. Indicates the bonding area.)

[0057] As the indane ring-containing aromatic bismaleimide containing a divalent group represented by the general formula (a1-1), preferably represented by the following general formula (a1-2) from the viewpoints of reducing transmission loss, adhesion to a conductor, heat resistance, and ease of production.

[0058] [Chemistry 2]

[0059]

[0060] (Where R a1 ~R a4 and n1 are the same as those in the above general formula (a1-1). a5 Each of them is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, n2 is independently an integer of 0 to 4, and n3 is a number of 0.95 to 10.0.

[0061] From the viewpoints of reducing transmission loss, adhesion to conductors, solvent solubility, and ease of production, the aromatic bismaleimide containing an indane ring represented by the above-mentioned general formula (a1-2) is more preferably a substance represented by the following general formula (a1-3) or a substance represented by the following general formula (a1-4).

[0062] [Chemistry 3]

[0063]

[0064] (Where R a1 ~R a5 and n1 and n3 have the same symbols as those in the above general formula (a1-2).

[0065] [Chemistry 4]

[0066]

[0067] (Where R a1 ~R a4 and n1 and n3 have the same symbols as those in the above general formula (a1-2).

[0068] The method for producing the indane ring-containing aromatic bismaleimide is not particularly limited, and it may be produced by a known method.

[0069] Examples of the “derivatives” of the maleimide compounds include addition reaction products of the maleimide compounds having one or more (preferably two or more) N-substituted maleimide groups and one or more amine compounds selected from monoamine compounds and diamine compounds.

[0070] Examples of the monoamine compound include monoamine compounds having an acidic substituent such as o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline.

[0071] Examples of the diamine compound include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 2,2'-bis(4,4'-diaminodiphenyl)propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, Diamine compounds having an aromatic hydrocarbon group, such as 4,4'-diaminodiphenyl sulfide, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetrachloro-4,4'-diaminodiphenylmethane, and 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane; and siloxane diamines.

[0072] (Content of ingredient (A))

[0073] The content of the thermosetting resin (A) in the resin composition of the present embodiment is not particularly limited. However, from the viewpoints of heat resistance and moldability, the content is preferably 3 to 95 parts by mass, more preferably 5 to 80 parts by mass, further preferably 5 to 60 parts by mass, particularly preferably 5 to 45 parts by mass, and most preferably 7 to 30 parts by mass, relative to 100 parts by mass of the solid content in the resin composition.

[0074] ((B) Polymer having a hydrocarbon chain or a polyether chain)

[0075] From the perspective of reducing transmission loss, the resin composition of this embodiment contains a polymer having a hydrocarbon chain or a polyether chain as component (B). The polymer having a hydrocarbon chain or a polyether chain is preferably a polymer having a hydrocarbon chain or a polyether chain in the main chain. In this disclosure, the term "main chain" refers to the relatively longest bond chain in the polymer molecule, and the term "side chain" refers to an atomic group branching from the main chain. In addition, the term "hydrocarbon chain" refers to a structure in which carbon atoms bonded to hydrogen atoms are connected in a chain. In addition, the term "polyether chain" refers to a structure in which units containing polyether bonds are connected in a chain.

[0076] The component (B) may be used alone or in combination of two or more.

[0077] The polymer having a hydrocarbon chain is preferably at least one selected from a conjugated diene polymer, a styrene-based elastomer, and modified products thereof. Modified products of conjugated diene polymers are sometimes hereinafter referred to as modified conjugated diene polymers. Modified conjugated diene polymers are preferably conjugated diene polymers modified with the maleimide compound described above, and more preferably conjugated diene polymers modified with the maleimide compound having two or more N-substituted maleimide groups.

[0078] Examples of the polymer having a polyether chain include polyphenylene ether and modified products of polyphenylene ether.

[0079] Among these, from the perspectives of compatibility with other resins, reduced transmission loss, and heat resistance, component (B) is preferably a polymer having a hydrocarbon chain, and more preferably a conjugated diene polymer or a styrene-based elastomer. Furthermore, from the perspectives of compatibility with other resins, reduced transmission loss, and heat resistance, a conjugated diene polymer having a vinyl group in its side chain is preferred.

[0080] Hereinafter, the conjugated diene polymer having a vinyl group in a side chain may be referred to as "(B1) conjugated diene polymer" or "(B1) component," and the styrene-based elastomer may be referred to as "(B2) styrene-based elastomer" or "(B2) component." Components (B1) and (B2) will be described in order.

[0081] ((B1) Conjugated diene polymer)

[0082] As mentioned above, component (B1) is a conjugated diene polymer having a vinyl group in its side chain. Using component (B1) as component (B) tends to improve the dielectric loss tangent (Df) of the resulting cured product of the resin composition, thereby reducing transmission loss.

[0083] The component (B1) may be used alone or in combination of two or more.

[0084] Component (B1) is preferably a conjugated diene polymer having multiple vinyl groups in its side chain. The number of vinyl groups in one molecule of component (B1) is not particularly limited; however, from the perspectives of reducing transmission loss and heat resistance, the number is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.

[0085] In the present disclosure, the conjugated diene polymer refers to a polymer of a conjugated diene compound.

[0086] Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.

[0087] The conjugated diene polymer may be a polymer of one conjugated diene compound or a polymer of two or more conjugated diene compounds.

[0088] The conjugated diene polymer may be a polymer obtained by copolymerizing one or more conjugated diene compounds with one or more monomers other than the conjugated diene compound. The polymerization method in this case is not particularly limited and may be any of random polymerization, block polymerization, and graft polymerization.

[0089] Specific examples of component (B1) include polybutadiene containing a 1,2-vinyl group, butadiene-styrene copolymer containing a 1,2-vinyl group, and polyisoprene containing a 1,2-vinyl group. Among these, polybutadiene containing a 1,2-vinyl group and butadiene-styrene copolymer containing a 1,2-vinyl group are preferred from the perspectives of reducing transmission loss and heat resistance, and polybutadiene containing a 1,2-vinyl group is more preferred. Furthermore, as the polybutadiene containing a 1,2-vinyl group, a butadiene homopolymer containing a 1,2-vinyl group is preferred.

[0090] The 1,2-vinyl group derived from butadiene contained in the component (B1) is a vinyl group contained in a structural unit derived from butadiene represented by the following formula (b1-1).

[0091] [Chemistry 5]

[0092]

[0093] When component (B1) is a polybutadiene containing a 1,2-vinyl group, the content of structural units containing a 1,2-vinyl group relative to the total structural units derived from butadiene constituting the polybutadiene (hereinafter sometimes referred to as the "vinyl content") is not particularly limited. However, from the perspectives of compatibility with other resins, reduced transmission loss, low thermal expansion, and heat resistance, it is preferably 50 mol% or greater, more preferably 60 mol% or greater, even more preferably 70 mol% or greater, particularly preferably 80 mol% or greater, and most preferably 85 mol% or greater. The upper limit of the vinyl content is not particularly limited and may be 100 mol% or less, 97 mol% or less, or 95 mol% or less. Structural units containing a 1,2-vinyl group are preferably butadiene-derived structural units represented by the above-mentioned formula (b1-1).

[0094] From the same viewpoint, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.

[0095] The number average molecular weight of component (B1) is not particularly limited, but is preferably 400 to 4000, more preferably 500 to 3000, further preferably 600 to 2000, and particularly preferably 700 to 1500, from the viewpoints of compatibility with other resins, reduced transmission loss, low thermal expansion, and heat resistance.

[0096] ((B2) Styrene-based elastomer)

[0097] Component (B2) is not particularly limited as long as it is an elastomer having structural units derived from a styrene-based compound. Including component (B2) in component (B) tends to improve the dielectric loss tangent (Df) of the resulting cured product of the resin composition, thereby reducing transmission loss.

[0098] The component (B2) may be used alone or in combination of two or more.

[0099] As the component (B2), those having a structural unit derived from styrene represented by the following general formula (b2-1) are preferred.

[0100] [Chemistry 6]

[0101]

[0102] (Where R b5 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R b6 is an alkyl group having 1 to 5 carbon atoms. k is an integer from 0 to 5.

[0103] As R b5 and R b6Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, and n-propyl. Among these, alkyl groups having 1 to 3 carbon atoms are preferred, alkyl groups having 1 or 2 carbon atoms are more preferred, and methyl groups are still more preferred.

[0104] k is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0105] Examples of the structural units other than the structural units derived from styrene compounds contained in the component (B2) include structural units derived from butadiene, structural units derived from isoprene, structural units derived from maleic acid, and structural units derived from maleic anhydride.

[0106] The structural units derived from butadiene and the structural units derived from isoprene may be hydrogenated. In the case of hydrogenation, the structural units derived from butadiene become structural units composed of a mixture of ethylene units and butene units, and the structural units derived from isoprene become structural units composed of a mixture of ethylene units and propylene units.

[0107] From the perspectives of reducing transmission loss, improving adhesion to conductors, heat resistance, and reducing thermal expansion, component (B2) is preferably one or more selected from hydrogenated styrene-butadiene-styrene block copolymers (SEBS and SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA). More preferably, one or more selected from SEBS and SEPS are used, and SEBS is even more preferred. SEBS is obtained by hydrogenating the butadiene units of a styrene-butadiene-styrene block copolymer (SBS) and is named after the initials of styrene-ethylene-butylene-styrene. SBBS is obtained by selectively hydrogenating the 1,2-linked units within the butadiene units of a styrene-butadiene-styrene block copolymer (SBS) and is named after the initials of styrene-(1,4-butadiene)-butylene-styrene. SEPS is obtained by hydrogenating the isoprene units of a styrene-isoprene-styrene block copolymer (SIS), and is named using the initials of styrene-ethylene-propylene-styrene.

[0108] The content of styrene-derived structural units in the SEBS (hereinafter sometimes referred to as "styrene content") is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, further preferably 15 to 70% by mass, further preferably 20 to 50% by mass, and particularly preferably 25 to 45% by mass from the viewpoints of low thermal expansion, low transmission loss, adhesion to conductors, and heat resistance.

[0109] Examples of commercially available SEBS include TUFTEC H series and M series manufactured by Asahi Kasei Corporation, SEPTON series manufactured by Kuraray Corporation, and KRATON G polymer series manufactured by KRATON POLYMERS JAPAN CO., LTD.

[0110] The weight-average molecular weight (Mw) of component (B2) is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, even more preferably 50,000 to 200,000, particularly preferably 70,000 to 150,000, and most preferably 90,000 to 130,000. The weight-average molecular weight (Mw) is measured by gel permeation chromatography (GPC) in terms of polystyrene, and more specifically, is a value obtained by the measurement method described in the Examples.

[0111] [Content ratio of (B1) conjugated diene polymer and (B2) styrene-based elastomer]

[0112] In the resin composition of the present embodiment, when the component (B1) and the component (B2) are used in combination, the content ratio of the component (B1) to the component (B2) [(B1) / (B2)] is not particularly limited. However, from the viewpoints of moldability, compatibility with other resins, and reduction of transmission loss, the ratio is preferably 2 / 98 to 70 / 30, more preferably 5 / 95 to 60 / 40, further preferably 10 / 90 to 50 / 50, and particularly preferably 20 / 80 to 40 / 60, based on mass.

[0113] (Content of component (B))

[0114] The content of component (B) in the resin composition of this embodiment is not particularly limited, but is preferably 3 to 35 parts by mass, more preferably 5 to 30 parts by mass, even more preferably 10 to 30 parts by mass, particularly preferably 15 to 30 parts by mass, and most preferably 15 to 25 parts by mass, relative to 100 parts by mass of the solid content of the resin composition. A content of component (B) of 3 parts by mass or greater relative to 100 parts by mass of the solid content of the resin composition tends to reduce transmission loss, while a content of 35 parts by mass or less tends to maintain good heat resistance and flame retardancy.

[0115] ((X) Phosphorus compound flame retardant)

[0116] The resin composition of this embodiment contains a phosphorus compound-based flame retardant as component (X). Phosphorus compound-based flame retardants have a flame retardant mechanism in which a phosphoric acid layer formed by decomposition blocks oxygen. Furthermore, dehydration carbonizes organic matter, forming a film called a carbonized layer on the surface of the burning material, blocking oxygen.

[0117] Phosphorus compound-based flame retardants include phosphorus oxide compounds. Here, the "phosphorus oxide compound" is a compound having the following phosphorus oxide structure.

[0118] [Chemistry 7]

[0119] Phosphorus oxide structure

[0120] ( Indicates the bonding position. )

[0121] The aromatic ring contained in component (X) is preferably an aromatic ring having 6 to 18 ring carbon atoms, examples of which include a benzene ring, a naphthalene ring, and an anthracene ring. A benzene ring is preferred. The aromatic ring may or may not have a substituent. Substituents that may be present in the aromatic ring include alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; and alkoxy groups such as methoxy, ethoxy, and isopropoxy. The substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0122] The component (X) preferably has two or more aromatic rings per molecule, more preferably 2 to 10 aromatic rings, even more preferably 2 to 6 aromatic rings, particularly preferably 4 to 6 aromatic rings, and most preferably 5 aromatic rings. When the component (X) has two or more aromatic rings per molecule, the multiple aromatic rings may be the same or different, but are preferably the same.

[0123] In the component (X), the aromatic ring may be directly bonded to the phosphorus atom, may be bonded to the phosphorus atom through an oxygen atom, or may be bonded to the phosphorus atom through an alkylene group such as a methylene group.

[0124] From the viewpoint of low thermal expansion, high elasticity, and low transmission loss, component (X) preferably has two or more phosphorus atoms per molecule, more preferably 2 to 4 phosphorus atoms per molecule, and even more preferably 2 phosphorus atoms per molecule.

[0125] The component (X) is not particularly limited. However, from the viewpoint of low thermal expansion, high elasticity, and low transmission loss, it preferably contains at least one selected from (Xi) a phosphate ester compound, (X-ii) a phosphine oxide compound, (X-iii) a phosphaphenanthrene compound, (X-iv) a metal salt of phosphinic acid, and (Xv) an organic nitrogen-containing phosphorus compound. It more preferably contains at least one selected from (Xi) a phosphate ester compound, (X-ii) a phosphine oxide compound, and (X-iv) a metal salt of phosphinic acid. It is even more preferably contains at least one selected from (X-ii) a phosphine oxide compound and (X-iv) a metal salt of phosphinic acid.

[0126] Hereinafter, components (Xi) to (Xv) will be described in detail one by one.

[0127] ((Xi) Phosphate ester compound)

[0128] The phosphate ester compound may be used alone or in combination of two or more. A commercially available phosphate ester compound may be used.

[0129] The component (Xi) preferably has two or more phosphate groups in the molecule, and more preferably has two phosphate groups in the molecule. Here, the phosphate group is a group represented by the following formula.

[0130] [Chemistry 8]

[0131] Phosphate group

[0132] ( Indicates the bonding position. )

[0133] A phosphate compound having two or more phosphate groups in its molecule preferably has a linking group connecting the two or more phosphate groups. The linking group is not particularly limited, and examples thereof include phenylene, xylylene, biphenylene, naphthylene, methylene, and ethylene. From the perspective of component (Xi) having a high melting point, the linking group preferably comprises at least one selected from phenylene, xylylene, biphenylene, and naphthylene, and more preferably comprises phenylene.

[0134] From the viewpoint of low thermal expansion, high elasticity, and low transmission loss, the oxygen atom of the phosphate group may be substituted on the aromatic ring.

[0135] The component (Xi) is preferably a compound represented by the following general formula (X-1) from the viewpoint of improving the bonding strength with the metal foil and the solder heat resistance while maintaining a good low thermal expansion property.

[0136] [Chemistry 9]

[0137]

[0138] (Where R x1 ~R x4 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. x1 represents a divalent group represented by the following general formula (X-2) or a divalent condensed polycyclic aromatic hydrocarbon group. x1 ~n x4 Each independently represents an integer from 0 to 5, n x5 Indicates an integer from 0 to 5.)

[0139] [Chemistry 10]

[0140]

[0141] (Where R x5 and R x6 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. x2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, -S-, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. x6 and n x7 Each independently represents an integer from 0 to 4. x8 Indicates an integer from 0 to 3.)

[0142] As R in the above general formula (X-1) x1 ~R x4 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

[0143] n x1 ~n x4 represents an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 2, and further preferably 2. x1 ~n x4 When the integer is 2 or more, multiple R x1 Between, R x2 Between, R x3 Between or R x4 They can be the same or different.

[0144] n x5 represents an integer of 0 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1. x5 When the number of Z is an integer greater than 2, x1 Between and multiple n x4 They can be the same or different.

[0145] The definitions of the groups in the above general formula (X-2) are as described above.

[0146] As R x5 and R x6 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by includes the group consisting of R x1 ~R x4 The aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by are the same groups.

[0147] As R x5 and R x6 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0148] As Z x2 Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, and 1,5-pentamethylene.

[0149] As Z x2 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene.

[0150] n x6 and n x7 Each independently represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0151] n x8 It is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.

[0152] The above-mentioned general formula (X-2) is preferably the following general formula (X-2-1).

[0153] [Chemistry 11]

[0154]

[0155] (In the formula, the definitions of the groups are the same as those of the groups in the general formula (X-2).)

[0156] As Z in the above general formula (X-1) x1 Examples of the divalent fused polycyclic aromatic hydrocarbon group include divalent groups formed by removing two hydrogen atoms from fused polycyclic aromatic hydrocarbons such as naphthalene, anthracene, and pyrene. These fused polycyclic aromatic hydrocarbon groups may or may not be substituted. Examples of substituents for the fused polycyclic aromatic hydrocarbon group include aliphatic hydrocarbon groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and halogen atoms, such as fluorine, chlorine, bromine, and iodine.

[0157] Specific examples of the phosphate compound (Xi) include 1,3-phenylene-bis(di-2,6-dimethylphenyl phosphate), 1,3-phenylene-bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,4-phenylene-bis(di-2,6-dimethylphenyl phosphate), 4,4'-biphenylene-bis(di-2,6-dimethylphenyl phosphate), bisphenol A-polyphenyl phosphate, 4,4'-biphenol-polycresyl phosphate, bisphenol A polycresyl phosphate, 4,4'-biphenol-poly(2,6-xylyl phosphate), and bisphenol A poly(2,6-xylyl phosphate).

[0158] It should be noted that the term "poly" in the specific examples of the phosphate ester compound mentioned above refers to a compound having two or more structural units formed from a structure derived from a divalent phenol compound and a structure derived from phosphoric acid, which constitute the phosphate ester compound. It may also refer to a compound in which the average number of the structural units is greater than one due to the inclusion of such a compound. The term "structural unit" herein refers to the structural unit enclosed in square brackets, for example, when described in the general formula (X-1).

[0159] ((X-ii) Phosphine oxide compound)

[0160] The phosphine oxide compound may be used alone or in combination of two or more. A commercially available phosphine oxide compound may be used.

[0161] The component (X-ii) preferably has two or more diphenylphosphine oxide groups in the molecule, and more preferably has two diphenylphosphine oxide groups in the molecule. Here, the diphenylphosphine oxide group is a group represented by the following formula.

[0162] [Chemistry 12]

[0163] diphenylphosphine oxide

[0164] ( Indicates the bonding position. )

[0165] The melting point of component (X-ii) is preferably 280°C or higher, more preferably 310°C or higher, from the perspective of reducing transmission loss. The melting point of the phosphine oxide compound is limited to approximately 450°C, from the perspective of the decomposition temperature of organic matter. For this reason, the melting point of component (X-ii) is preferably 280-450°C, more preferably 310-450°C. The melting point can be measured using a thermogravimetric / differential thermal analysis (TG / DTA) apparatus.

[0166] A phosphine oxide compound having two or more diphenylphosphine oxide groups in its molecule preferably has a linking group connecting the two or more diphenylphosphine oxide groups. The linking group is not particularly limited, and examples thereof include phenylene, xylylene, biphenylene, naphthylene, methylene, and ethylene. From the perspective of component (X-ii) having a high melting point, the linking group preferably comprises at least one selected from phenylene, xylylene, biphenylene, and naphthylene, and more preferably comprises phenylene.

[0167] Specific examples of the component (X-ii) include the following compounds.

[0168] [Chemistry 13]

[0169]

[0170] ((X-iii) Phosphaphenanthrene compounds)

[0171] The phosphaphenanthrene compound may be used alone or in combination of two or more. A commercially available phosphaphenanthrene compound may be used.

[0172] Examples of the component (X-iii) include compounds represented by the following formula (X-3).

[0173] [Chemistry 14]

[0174]

[0175] (Where R x10 and R x11 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. b and c are each independently an integer of 0 to 4. A is a hydrogen atom or a group represented by any of the following formulae (X-4) to (X-6).

[0176] [Chemistry 15]

[0177]

[0178] ( Indicates the bonding position. )

[0179] [Chemistry 16]

[0180]

[0181] ( Indicates the bonding position. )

[0182] [Chemistry 17]

[0183]

[0184] ( Indicates the bonding position. )

[0185] Examples of the component (X-iii) include 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide and 9,10-dihydro-10-(2,5-dihydroxyphenyl)-9-oxa-10-phosphaphenanthrene 10-oxide.

[0186] ((X-iv) Metal salt of phosphinic acid)

[0187] Component (X-iv) is preferably a metal salt of a dialkylphosphinic acid. Examples of the "metal salt" include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts. Among these metal salts, aluminum salts are preferred.

[0188] Examples of the alkyl group contained in the dialkylphosphinic acid include alkyl groups having 1 to 10 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably an ethyl group.

[0189] ((Xv) Organic nitrogen-phosphorus compounds)

[0190] Component (Xv) includes a phosphazene compound. The phosphazene compound preferably has a structural unit represented by the following general formula (X-7).

[0191] [Chemistry 18]

[0192]

[0193] (Where R x12 and R x13 Each independently represents an organic group having 1 to 20 carbon atoms.

[0194] As R in the above general formula (X-7) x12 and R x13 Examples of the organic group having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0195] About R x12 and R x13 Examples of the organic group having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, and alkynyl groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups may be linear, branched, or cyclic.

[0196] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-ethylhexyl, and cyclohexyl. Examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl, propenyl, and butenyl. Examples of the alkynyl group having 2 to 20 carbon atoms include 2-propynyl and 3-butynyl.

[0197] An aliphatic hydrocarbon group having 1 to 20 carbon atoms may or may not have a substituent. Examples of such substituents include a hydroxyl group, a carboxyl group, a halogen atom, an aromatic hydrocarbon group, an acyl group, an alkoxy group, and groups formed by linking these substituents. When an aliphatic hydrocarbon group has a substituent, the carbon number listed above also includes the carbon number of the substituent.

[0198] As R x12 and R x13 The number of carbon atoms in the aromatic hydrocarbon group having 6 to 20 exemplified by the organic group having 1 to 20 carbon atoms represented by the formula (C) is preferably 6 to 15, more preferably 6 to 10.

[0199] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, naphthyl, biphenyl, and anthracenyl.

[0200] The aromatic hydrocarbon group having 6 to 20 carbon atoms may or may not have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom, an aliphatic hydrocarbon group, an acyl group, an alkoxy group, a cyano group, and groups formed by linking these substituents. A cyano group is preferred as the substituent. It should be noted that when the aromatic hydrocarbon group has a substituent, the carbon number mentioned above also includes the carbon number of the substituent.

[0201] Among them, from the viewpoint of flame retardancy, R x12 and R x13 The organic group having 1 to 20 carbon atoms represented by the group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an unsubstituted phenyl group or a phenyl group having a substituent, and still more preferably an unsubstituted phenyl group or a cyanophenyl group.

[0202] The phosphazene compound may be a chain phosphazene compound or a cyclic phosphazene compound, but is preferably a cyclic phosphazene compound.

[0203] As the cyclic phosphazene compound, a phosphazene compound represented by the following general formula (X-8) is preferred, and a phosphazene compound represented by the following general formula (X-9) is more preferred.

[0204] [Chemistry 19]

[0205]

[0206] (Where Ar x1 and Ar x2Each independently represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. x9 Indicates an integer from 3 to 20.)

[0207] [Chemistry 20]

[0208]

[0209] (Where Ar x3 ~Ar x8 Each independently represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0210] Regarding Ar in the above general formula (X-8) x1 and Ar x2 The aromatic hydrocarbon group having 6 to 20 carbon atoms represented by and Ar in the above general formula (X-9) x3 ~Ar x8 The description of the aromatic hydrocarbon group having 6 to 20 carbon atoms is the same as that of R in the above general formula (X-7). x12 and R x13 The same applies to the description of the aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0211] n in the above general formula (X-8) x9 It represents an integer of 3 to 20, preferably an integer of 3 to 10, more preferably an integer of 3 to 5, and even more preferably 3.

[0212] ((Y) Flame retardants other than the above-mentioned phosphorus compound flame retardants)

[0213] The resin composition of this embodiment contains a flame retardant other than the aforementioned phosphorus compound-based flame retardant as component (Y). The flame retardant other than the aforementioned phosphorus compound-based flame retardant preferably has a flame retardant mechanism different from that of the aforementioned phosphorus compound-based flame retardant. Here, "having a flame retardant mechanism different from that of the aforementioned phosphorus compound-based flame retardant" means that the flame retardant mechanism is not the same as that of the aforementioned phosphorus compound-based flame retardant. The flame retardant mechanism different from that of the aforementioned phosphorus compound-based flame retardant is not particularly limited; for example, a flame retardant mechanism that suppresses combustion by stabilizing active OH radicals using a radical scavenger can be used.

[0214] Halogen-based flame retardants are preferred as flame retardants with a different flame retardant mechanism than the aforementioned phosphorus compound-based flame retardants. It is believed that by incorporating both the aforementioned component (X) and a halogen-based flame retardant into the resin composition of this embodiment, phosphorus halides and oxyhalides are generated, which exhibit excellent free radical scavenging effects, thereby facilitating a synergistic flame retardant effect. It should be noted that, from the perspective of the flame retardant mechanism, in this embodiment, the compound containing both phosphorus and halogen is not considered component (X) but is instead classified as component (Y).

[0215] Halogen-based flame retardants may be low-molecular-weight compounds or high-molecular-weight compounds. The molecular weight of the low-molecular-weight compound is not particularly limited, but is preferably 1,500 or less, more preferably 200 to 1,500, even more preferably 500 to 1,300, even more preferably 700 to 1,200, particularly preferably 800 to 1,100, and most preferably 900 to 1,100. The molecular weight of the high-molecular-weight compound is not particularly limited, but is preferably greater than 1,500, more preferably greater than 1,500 to 30,000, even more preferably 2,000 to 20,000, and particularly preferably 2,000 to 15,000.

[0216] Examples of the halogen-based flame retardant include chlorine compounds and bromine compounds. Among these, bromine compounds are preferred as the halogen-based flame retardant.

[0217] Examples of the chlorine compound include chain aliphatic chlorine compounds, cyclic aliphatic chlorine compounds, etc. Here, the chain aliphatic chlorine compound is a compound having a site where a chlorine atom is directly bonded to a chain aliphatic hydrocarbon group, and the cyclic aliphatic chlorine compound is a compound having a site where a chlorine atom is directly bonded to a cyclic aliphatic hydrocarbon group.

[0218] As bromine compounds, chain aliphatic bromine compounds, cyclic aliphatic bromine compounds, aromatic bromine compounds, etc. can be mentioned. Here, chain aliphatic chlorine compounds are compounds having a site where a bromine atom is directly bonded to a chain aliphatic hydrocarbon group, and cyclic aliphatic chlorine compounds are compounds having a site where a bromine atom is directly bonded to a cyclic aliphatic hydrocarbon group. In addition, so-called aromatic bromine compounds are compounds having a site where a bromine atom is bonded to an aromatic ring, but do not include compounds having a site where a bromine atom is bonded to an aliphatic hydrocarbon group. Among them, as bromine compounds, aromatic bromine compounds are preferred from the viewpoint of low thermal expansion, high elasticity and low transmission loss. As bromine compounds, specifically, the following compounds can be mentioned.

[0219] [Chemistry 21]

[0220] (Examples of chain aliphatic bromine compounds)

[0221]

[0222] [Chemistry 22]

[0223] (Examples of aromatic bromine compounds)

[0224]

[0225] (Contents of component (X) and component (Y))

[0226] The content of component (X) and component (Y) in the resin composition of this embodiment is not particularly limited. For example, with respect to 100 parts by mass of the solid content in the resin composition, preferably, component (X) is 0.5 to 10 parts by mass and component (Y) is 0.5 to 20 parts by mass, more preferably, component (X) is 1.0 to 7 parts by mass and component (Y) is 3 to 18 parts by mass, further preferably, component (X) is 1.0 to 8 parts by mass and component (Y) is 5 to 17 parts by mass, and particularly preferably, component (X) is 1.5 to 6.5 parts by mass and component (Y) is 8 to 16 parts by mass. If the content of component (X) and component (Y) is within the above numerical range, there is a tendency that the dielectric loss tangent (Df) is reduced, thereby achieving low transmission loss, a synergistic effect of flame retardancy can be obtained, and the appearance of the laminated board also tends to be improved.

[0227] (Regarding (X1) Filling Flame Retardants and (Y1) Filling Flame Retardants)

[0228] In this embodiment, the component (X) does not contain the (X1) filling flame retardant, and the component (Y) does not contain the (Y1) filling flame retardant, or when the component (X) contains the (X1) filling flame retardant or the component (Y) contains the (Y1) filling flame retardant, the content of the (X1) filling flame retardant and the total content of the (Y1) filling flame retardant are limited to a predetermined amount.

[0229] In the present disclosure, the so-called "filling property" refers to a flame retardant that does not dissolve in the resin varnish when an organic solvent is added to the resin composition to prepare a resin varnish. Whether it is dissolved in the resin varnish is determined by visually confirming the appearance of the flame retardant when 17 parts by mass of the flame retardant is added to 83 parts by mass of the resin varnish and stirred at 25°C for 30 minutes. When the flame retardant can be confirmed in the resin varnish, it is judged to be a filling flame retardant. It should be noted that the above-mentioned organic solvent is the same as the organic solvent that the resin varnish described later may contain. The above-mentioned organic solvent may be, for example, an aromatic hydrocarbon solvent or toluene.

[0230] Here, the (Y1) filling flame retardant is different from the (X1) filling flame retardant because it is assumed to be a flame retardant as the (Y) component.

[0231] The filling flame retardant (X1) is not particularly limited, and examples thereof include the metal salts of phosphinic acid (X-iv) described above, and more specifically, aluminum tris(diethylphosphinate). For example, 1,3-phenylenebis(di-2,6-ditolyl phosphate), which is a powder at 25°C, is soluble in organic solvents (e.g., aromatic hydrocarbon solvents such as toluene) and therefore is compatible with the resin varnish rather than a filler. Furthermore, 1,3-phenylenebis(diphenyl phosphate), which is a liquid at 25°C, and bisphenol A bis(diphenyl phosphate), which is a liquid at 25°C, are also compatible with the resin varnish rather than a filler.

[0232] The filler flame retardant (Y') is not particularly limited, but examples include ethylene bispentabromobenzene and 1,2-bis(2,4,6-tribromophenoxy)ethane. It should be noted that, for example, tris(tribromophenoxy)triazine, tribromophenol, and tetrabromobisphenol A, which are powders at 25°C, are soluble in organic solvents (e.g., aromatic hydrocarbon solvents such as toluene) and are not fillers.

[0233] (Total content of component (X1) and component (Y1))

[0234] In the resin composition of this embodiment, when the component (X) contains a (X1) filler flame retardant or the component (Y) contains a (Y1) filler flame retardant, the total content of the (X1) filler flame retardant and the (Y1) filler flame retardant is 25 parts by mass or less per 100 parts by mass of the solids in the resin composition. By limiting the content of the filler flame retardant to this range, the appearance of the laminated plate is improved significantly.

[0235] From the same viewpoint, in the resin composition of the present embodiment, the content of the filling flame retardant (X1) and the total content of the filling flame retardant (Y1) are preferably 0 to 20 parts by mass, more preferably 0 to 18 parts by mass, and even more preferably 0 to 15 parts by mass, relative to 100 parts by mass of the solid content in the resin composition. It can also be 1 to 25 parts by mass, 3 to 20 parts by mass, 5 to 20 parts by mass, 8 to 20 parts by mass, 10 to 20 parts by mass, 10 to 18 parts by mass, or 10 to 15 parts by mass.

[0236] (Ratio of the content of component (X1) to the content of component (Y1))

[0237] When the resin composition of the present embodiment contains both the content of the filling flame retardant (X1) and the filling flame retardant (Y1), the ratio of the content of the filling flame retardant (X1) to the content of the filling flame retardant (Y1) [(X1) / (Y1)] is not particularly limited. However, from the viewpoint of flame retardancy and the balance between low transmission loss and the appearance of the laminated board, the mass ratio is preferably 1 / 99 to 45 / 55, more preferably 5 / 95 to 40 / 60, and may be 5 / 95 to 35 / 65, 10 / 90 to 30 / 70, or 10 / 90 to 25 / 75. In addition, it may be 15 / 85 to 50 / 50, 20 / 80 to 45 / 55, or 25 / 75 to 45 / 55.

[0238] ((X2) compatible flame retardant and (Y2) compatible flame retardant)

[0239] In the resin composition of this embodiment, from the perspective of the appearance of the laminated board, the component (X) may contain a compatible flame retardant (X2), and preferably, the component (X) contains the compatible flame retardant (X2). Furthermore, in the resin composition of this embodiment, from the perspective of the appearance of the laminated board, the component (Y) may contain a compatible flame retardant (Y2), and preferably, the component (Y) contains the compatible flame retardant (Y2).

[0240] In the present disclosure, the so-called "compatibility" refers to the flame retardant that dissolves in the resin varnish when an organic solvent is added to the resin composition to prepare a resin varnish. As to whether it is dissolved in the resin varnish, 17 parts by mass of the flame retardant is added to 83 parts by mass of the resin varnish and stirred at 25°C for 30 minutes. The appearance of the flame retardant at this time is judged by visual confirmation. In the case where the flame retardant cannot be confirmed in the resin varnish, it is judged to be a compatible flame retardant. It should be noted that the above-mentioned organic solvent is the same as the organic solvent that the resin varnish described later may contain. The above-mentioned organic solvent may be, for example, an aromatic hydrocarbon solvent or toluene.

[0241] Here, the (Y2) compatible flame retardant is different from the (X2) compatible flame retardant because it is a flame retardant that is the (Y) component.

[0242] The compatible flame retardant (X2) is not particularly limited, and examples thereof include the aforementioned (Xi) phosphate compounds and (X-ii) phosphine oxide compounds. More specific examples include 1,3-phenylene-bis(di-2,6-dimethylphenyl phosphate) and triphenylphosphine oxide.

[0243] The compatible flame retardant (Y2) is not particularly limited, and examples thereof include the following halogen-based flame retardants.

[0244] [Chemistry 23]

[0245]

[0246] (Content of component (X2) and content of component (Y2))

[0247] In the resin composition of the present embodiment, when the component (X) contains the compatible flame retardant (X2), the content of the component (X2) is not particularly limited. However, from the viewpoint of reducing transmission loss, flame retardancy, and the appearance of the laminated board, the content is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the solid content in the resin composition.

[0248] In the resin composition of the present embodiment, when the component (Y) contains the compatible flame retardant (Y2), the content of the component (Y2) is not particularly limited. However, from the viewpoint of reducing transmission loss, flame retardancy, and the appearance of the laminate, the content is preferably 0.5 to 17 parts by mass, more preferably 1 to 15 parts by mass, further preferably 2 to 13 parts by mass, and may be 2 to 7 parts by mass, or may be 7 to 17 parts by mass, relative to 100 parts by mass of the solid content in the resin composition.

[0249] ((C) Inorganic filler)

[0250] The resin composition of the present embodiment contains an inorganic filler [hereinafter sometimes referred to as component (C)] as the component (C), whereby low thermal expansion, elastic modulus, heat resistance, and flame retardancy tend to be improved.

[0251] The component (C) may be used alone or in combination of two or more.

[0252] Examples of the component (C) include silica, alumina, titanium oxide, mica, beryllium oxide, 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 (calcined clay, etc.), molybdate compounds such as zinc molybdate, talc, aluminum borate, and silicon carbide. Among these, silica, alumina, mica, and talc are preferred from the viewpoint of low thermal expansion, elastic modulus, heat resistance, and flame retardancy, silica and alumina are more preferred, and silica is still more preferred.

[0253] Examples of silica include crushed silica, fumed silica, and fused silica.

[0254] The average particle size of the component (C) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm.

[0255] The shape of the component (C) may be, for example, spherical or crushed, but is not particularly limited. However, a spherical shape is preferred.

[0256] When the resin composition of the present embodiment contains component (C), the content of component (C) in the resin composition is not particularly limited. However, from the viewpoint of low thermal expansion, elastic modulus, and heat resistance, the content is preferably 5 to 70 parts by mass, more preferably 15 to 65 parts by mass, further preferably 20 to 60 parts by mass, particularly preferably 30 to 55 parts by mass, and most preferably 40 to 55 parts by mass, relative to 100 parts by mass of the solid content in the resin composition.

[0257] When the resin composition of this embodiment contains component (C), a coupling agent may be used to improve the dispersibility of component (C) and its adhesion to the organic component. As the coupling agent, a silane coupling agent is preferred. Examples of the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, and silicone oligomer coupling agents. One coupling agent may be used alone, or two or more may be used in combination.

[0258] When a coupling agent is used, the surface treatment method for component (C) may be a bulk blending method in which component (C) is blended into the resin composition and then the coupling agent is added, or a method in which component (C) is pre-surface-treated with a coupling agent in a dry or wet manner. Of these, pre-surface-treating component (C) with a coupling agent in a dry or wet manner is preferred from the viewpoint of more effectively bringing out the advantages of component (C).

[0259] In order to improve the dispersibility in the resin composition, the component (C) may be prepared in advance as a slurry dispersed in an organic solvent and then mixed with other components.

[0260] ((D) Curing accelerator)

[0261] The resin composition of the present embodiment contains a curing accelerator [hereinafter sometimes referred to as component (D)]. This component (D) tends to improve curability, and also improve elastic modulus, transmission loss reduction, heat resistance, and adhesion to conductors.

[0262] The component (D) may be used alone or in combination of two or more.

[0263] Examples of the component (D) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; isocyanate-blocked imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; tertiary amine compounds; quaternary ammonium salt compounds; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butyl peroxyisopropyl monocarbonate, and α,α'-bis(tert-butylperoxy)diisopropylbenzene; and carboxylates of manganese, cobalt, zinc, and the like.

[0264] Among them, from the viewpoint of heat resistance and storage stability, imidazole compounds, isocyanate-blocked imidazole compounds, organic peroxides, and carboxylates are preferred, organic peroxides are more preferred, and α,α′-bis(tert-butylperoxy)diisopropylbenzene is even more preferred.

[0265] When the resin composition of this embodiment contains component (D), the content of component (D) is not particularly limited. However, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, even more preferably 0.1 to 6 parts by mass, and particularly preferably 0.2 to 3 parts by mass, relative to 100 parts by mass of the resin component in the resin composition. When the content of component (D) is at least the lower limit, the elastic modulus, transmission loss reduction, heat resistance, and adhesion to conductors tend to be further improved. Furthermore, when the content of component (D) is at most the upper limit, the storage stability of the resin composition tends to be further improved.

[0266] (Other ingredients)

[0267] The resin combination of the present embodiment can further contain more than one of the additives selected from the resin material, antioxidant, flame retardant, flame retardant auxiliary, heat stabilizer, antistatic agent, ultraviolet light absorber, pigment, colorant, lubricant and them other than the above-mentioned components as required. They can each be used alone or in combination with more than two kinds. In addition, their usage amount is not particularly limited, as long as, as required, they are used in the scope of not hindering the effect of the present embodiment.

[0268] The resin composition of the present embodiment may be in a state of being dissolved or dispersed in an organic solvent, that is, in a state of a so-called “resin varnish.” Hereinafter, a resin composition containing an organic solvent may be referred to as a resin varnish.

[0269] Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; amide solvents such as N-methylpyrrolidone, formamide, N-methylformamide, and N,N-dimethylacetamide; and alcohol 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. The organic solvent may be used alone or in combination of two or more.

[0270] The solid content concentration in the resin varnish is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 35 to 60% by mass.

[0271] [Prepreg]

[0272] The prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured product of the above-mentioned resin composition.

[0273] The prepreg of this embodiment, for example, comprises the resin composition of this embodiment or a semi-cured product of such a resin composition and a sheet-like fiber base material. This prepreg is formed using the resin composition or resin film of this embodiment and a sheet-like fiber base material. For example, the prepreg can be obtained by impregnating or coating the sheet-like fiber base material with the resin composition or resin film of this embodiment, drying it, and, if necessary, semi-curing (B-staging). More specifically, the prepreg of this embodiment can be produced by, for example, heating and drying it in a drying oven at a temperature typically between 80°C and 200°C for 1 to 30 minutes to semi-cure (B-staging). In this disclosure, B-staging refers to a state in which the prepreg has reached the B-stage state defined in JIS K6900 (1994).

[0274] The amount of the resin composition used can be appropriately determined to achieve a solid content concentration of 30 to 90% by mass in the dried prepreg derived from the resin composition. By setting the solid content concentration within the above range, better formability tends to be achieved when the laminate is formed.

[0275] As the sheet-like fiber substrate of the prepreg, known sheet-like fiber substrates used in various laminates for electrical insulating materials can be used. While the sheet-like fiber substrate is not particularly limited, it is preferably a sheet-like fiber-reinforced substrate used for reinforcing the prepreg. Examples of materials for the sheet-like fiber substrate include inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber substrates may be in the form of, for example, woven fabrics, non-woven fabrics, rovings, chopped strand mats, or surface mats.

[0276] The thickness of the sheet-like fiber base material is not particularly limited, but for example, a sheet-like fiber base material having a thickness of 0.02 to 0.5 mm can be used.

[0277] In addition, from the viewpoints of resin composition impregnation, heat resistance, moisture absorption resistance, and processability when forming a laminate, the sheet-like fiber base material may be one surface-treated with a coupling agent or one mechanically fiber-opened.

[0278] As a method for impregnating or coating the sheet-like fiber base material with the resin composition, the following hot melt method or solvent method can be used.

[0279] The hot melt method is a method in which the resin composition does not contain an organic solvent and is (1) temporarily coated on a coating paper with good releasability from the resin composition and then laminated to a sheet-like fiber base material; or (2) a method in which the resin composition is coated on a sheet-like fiber base material using a die coater.

[0280] On the other hand, the solvent method is a method in which a sheet-like fiber base material is impregnated with an organic solvent contained in a resin composition, thereby impregnating the sheet-like fiber base material with the resin composition, and then drying the sheet-like fiber base material.

[0281] [Resin film]

[0282] The resin film of the present embodiment is a resin film containing the resin composition of the present embodiment or a semi-cured product of the above resin composition.

[0283] For example, the resin film of the present embodiment can be produced by applying a resin composition containing an organic solvent, that is, a resin varnish, to a support, drying it by heating, and semi-curing (B-staging) it as needed.

[0284] Examples of the support include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; films of polyesters such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthalate; and various plastic films such as polycarbonate and polyimide films. Furthermore, metal foils such as copper and aluminum foil, and release paper may also be used as the support. The support may be subjected to surface treatments such as matte treatment and corona treatment. Furthermore, the support may be subjected to release treatments using silicone resin release agents, alkyd resin release agents, fluororesin release agents, and the like.

[0285] The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

[0286] The method for coating the support with the resin varnish is not particularly limited, and coating apparatuses known to those skilled in the art such as a comma-type knife coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used. These coating apparatuses can be appropriately selected according to the film thickness.

[0287] The drying temperature and drying time can be appropriately determined based on the amount of organic solvent used and the boiling point of the organic solvent used. For example, in the case of a resin varnish containing about 40 to 60% by mass of an organic solvent, a resin film can be appropriately formed by drying at 50 to 150°C for about 3 to 10 minutes.

[0288] [Laminated board]

[0289] The laminated plate of the present embodiment comprises one or more selected from the group consisting of a cured product of the resin composition of the present embodiment, a cured product of a prepreg, and a cured product of a resin film, and a metal foil.

[0290] For example, the laminated plate of the present embodiment can be manufactured by placing metal foil on one or both sides of a single prepreg of the present embodiment, or by placing metal foil on one or both sides of a prepreg obtained by stacking two or more prepregs of the present embodiment (preferably 2 to 30, more preferably 3 to 15), and then performing heat and pressure molding.

[0291] In the laminated sheet produced by this manufacturing method, the prepreg of this embodiment has been C-staged. In this disclosure, C-staged refers to a state defined as C-stage in JIS K6900 (1994). Laminated sheets with metal foil are sometimes referred to as metal-clad laminated sheets.

[0292] The metal of the metal foil is not particularly limited, but from the perspective of conductivity, it can be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium or an alloy containing one or more of these metal elements, preferably copper and aluminum, more preferably copper.

[0293] The conditions for heat press molding are not particularly limited, and can be carried out, for example, at a temperature of 100 to 300°C, a pressure of 0.2 to 10 MPa, and a time of 0.1 to 5 hours. Alternatively, heat press molding can be performed by maintaining a vacuum state for 0.5 to 5 hours using a vacuum press or the like.

[0294] [Printed circuit board]

[0295] The printed wiring board of the present embodiment has one or more of a cured product of a resin composition of the present embodiment, a cured product of a prepreg, and a laminate of the present embodiment. Using one or more of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminate of the present embodiment, a circuit forming process such as hole opening processing, metal plating processing, and etching based on metal foil is performed using a known method, thereby manufacturing the printed wiring board of the present embodiment, and further multilayer bonding processing can be performed as needed to manufacture a multilayer printed wiring board. In the printed wiring board of the present embodiment, the prepreg of the present embodiment and the resin film of the present embodiment are C-staged.

[0296] [Semiconductor Package]

[0297] The semiconductor package of this embodiment is a semiconductor package having a printed wiring board and a semiconductor element. The semiconductor element, such as a semiconductor chip or memory, is mounted at a predetermined position on the printed wiring board of this embodiment and the semiconductor element is sealed with a sealing resin or the like, thereby manufacturing the semiconductor package of this embodiment.

[0298] The resin composition, prepreg, resin film, laminate, printed wiring board, and semiconductor package of this embodiment can be suitably used in electronic devices that process high-frequency signals of 10 GHz or higher. In particular, the printed wiring board is useful as a printed wiring board for millimeter-wave radar.

[0299] Example

[0300] The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited to the following examples.

[0301] In addition, in each example, the number average molecular weight and the weight average molecular weight (Mw) were measured by the following procedure.

[0302] (I. Method for Determining Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw))

[0303] The number-average molecular weight and weight-average molecular weight were calculated using gel permeation chromatography (GPC) using a calibration curve using standard polystyrene. The calibration curve was approximated using a cubic equation using standard polystyrene: TSK standard POLYSTYRENE (Types: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by TOSOH Corporation]. The GPC measurement conditions are shown below.

[0304] Device: High-speed GPC device HLC-8320GPC

[0305] Detector: UV-8320 ultraviolet absorption detector [manufactured by TOSOH Corporation]

[0306] Chromatographic column: Guard column; TSK Guardcolumn SuperHZ-L + Chromatographic column; TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all manufactured by TOSOH Corporation, trade names)

[0307] Column dimensions: 4.6 × 20 mm (guard column), 4.6 × 150 mm (chromatographic column), 6.0 × 150 mm (reference column)

[0308] Eluent: tetrahydrofuran

[0309] Sample concentration: 10mg / 5mL

[0310] Injection volume: 25 μL

[0311] Flow rate: 1.00mL / min

[0312] Measurement temperature: 40°C

[0313] (II. Measurement of vinyl modification rate)

[0314] The value determined by the following method was defined as the vinyl group modification ratio of the modified conjugated diene polymer B1-1 prepared in Production Example 1.

[0315] GPC measurements were performed on the liquid containing components (b1) and (b2) before the reaction and the liquid containing the modified conjugated diene polymer obtained after the reaction using the same method as described above. The rate of decrease in the peak area attributed to component (b2) before and after the reaction was calculated as (peak area attributed to component (b2) before the reaction - peak area attributed to component (b2) after the reaction) × 100 / (peak area attributed to component (b2) before the reaction). The resulting value was defined as the vinyl group modification rate.

[0316] Production Example 1 (Production of Modified Conjugated Diene Polymer B1-1)

[0317] Into a 2 L glass flask container capable of heating and cooling and equipped with a thermometer, a reflux condenser, and a stirring device, were placed the components (b1) and (b2) in the amounts shown in Table 1, an organic peroxide, and toluene as an organic solvent. The mixture was reacted under a nitrogen atmosphere at 90 to 100° C. for 5 hours while stirring to obtain a liquid containing a modified conjugated diene polymer B1-1 (toluene-diluted liquid, solid content concentration: 35% by mass).

[0318] Table 1 shows the modification rate of the vinyl group and the number average molecular weight of the obtained modified conjugated diene polymer B1-1.

[0319]

[0320] In addition, the details of each component described in Table 1 are as follows.

[0321] [(b1) Component]

[0322] Polybutadiene 1: 1,2-polybutadiene homopolymer, number average molecular weight = 1200, vinyl content = 85% or more

[0323] [(b2) ingredient]

[0324] Bismaleimide compound 1: 4,4'-diphenylmethane bismaleimide

[0325] [Reaction catalyst]

[0326] Organic peroxide: α,α'-bis(tert-butylperoxy)diisopropylbenzene

[0327] Examples 1 to 6, Comparative Examples 1 to 3

[0328] (Preparation of Resin Composition and Resin Varnish)

[0329] The components listed in Table 2 were blended in the amounts shown in Table 2 (the amounts listed in Table 2 are in parts by mass of solid content) and mixed in toluene to produce a resin composition (resin varnish) having a non-volatile content (solid content concentration) of 50% by mass. In Table 2, the amounts of the components are expressed in parts by mass. In the case of solutions or dispersions, these amounts are expressed in parts by mass based on the solid content.

[0330] (Prepreg production)

[0331] The resin varnish prepared in each example was impregnated into glass cloth (Nitto Bosho Co., Ltd., Type #1078 and Type #2116), then dried by heating at 120°C for 5 minutes to produce prepregs. The prepreg using Type #1078 glass cloth (for transmission loss and appearance evaluation) contained 66% by mass of the resin composition, while the prepreg using Type #2116 glass cloth (for flame retardancy evaluation) contained 57% by mass of the resin composition.

[0332] The flame retardancy of the prepreg using the #2116 type glass cloth was evaluated according to the measuring method described below.

[0333] (Production of double-sided copper-clad laminates)

[0334] On both sides of six stacked prepregs (prepregs using #1078 glass cloth) were layered with 12μm-thick electrolytic copper foil "3EC-M3-VLP-18" (trade name, manufactured by Mitsui Mining & Smelting Co., Ltd.) so that the adhesive surface was in contact with the prepreg. Heat and pressurization were then applied for 60 minutes under vacuum pressing conditions at 180°C and 3 MPa to produce a double-sided copper-clad laminate.

[0335] The transmission loss and appearance of the obtained double-sided copper-clad laminate were evaluated according to the following measurement methods. The results are shown in Table 2.

[0336] [Measurement method]

[0337] (1) Dielectric loss tangent (Df) measurement method - transmission loss

[0338] The double-sided copper-clad laminate obtained in each example was immersed in a 10 mass % ammonium persulfate solution as a copper etching solution to remove the copper foil. From the obtained evaluation substrate, a 2 mm×50 mm evaluation substrate was prepared.

[0339] The dielectric loss tangent (Df) of the evaluation substrate was measured in a 10 GHz frequency band at an ambient temperature of 25° C. using a cavity resonator perturbation method.

[0340] The dielectric loss tangent (Df) is preferably 0.0020 or less, more preferably 0.0018 or less, and even more preferably 0.0017 or less.

[0341] (2) Burning time-flame retardancy

[0342] The prepregs obtained in each example (prepregs using #2116 glass cloth) were stacked to a thickness of 1.6 mm. Electrolytic copper foil "3EC-M3-VLP-18" (trade name, manufactured by Mitsui Kinzoku Co., Ltd.) was placed on top and bottom, with the adhesive surfaces facing the prepregs. The laminates were then heated and pressed under vacuum conditions at 180°C and 3 MPa for 60 minutes to produce double-sided copper-clad laminates. The resulting double-sided copper-clad laminates were immersed in a 10% by mass solution of ammonium persulfate as a copper etchant to remove the copper foil. The laminates were then cut to produce five evaluation boards measuring 1.3 cm x 12.5 cm each. The five evaluation boards were subjected to a vertical flame test (UL94 flammability test). Each board was exposed to flame twice, and the burning time of the first and second flame exposures was measured. The average burning time of the five evaluation boards was then calculated. The average burning time of both the first flame contact and the second flame contact is preferably 10 seconds or less, more preferably 7 seconds or less, and even more preferably 5 seconds or less.

[0343] (3) Appearance

[0344] The double-sided copper-clad laminate obtained in each example was immersed in a 10 mass % ammonium persulfate solution as a copper etching solution to remove the copper foil. The obtained evaluation substrate was visually observed and evaluated according to the following evaluation criteria.

[0345] A: There are no visible scratches anywhere on the surface.

[0346] B: Scratches were observed only at the end portions.

[0347] C: Scratches were observed at least in the central portion.

[0348]

[0349] Note that the details of the components in Table 2 are as follows.

[0350] [(A) Ingredient]

[0351] Maleimide compound A-1: ​​Aromatic bismaleimide containing an indane ring (number average molecular weight: 1200)

[0352] ・Maleimide compound having a biphenyl aralkyl skeleton "MIR-3000" (manufactured by Nippon Kayaku Co., Ltd., trade name)

[0353] [(B) ingredient]

[0354] Modified conjugated diene polymer B1-1: Modified conjugated diene polymer B1-1 obtained in Production Example 1

[0355] Styrene elastomer B2-1: hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene content: 30% by mass, weight-average molecular weight: 115,200

[0356] [(X) ingredient]

[0357] Component (X1): Filling flame retardant X1-1: aluminum tris(diethylphosphinate) (see the following structural formula);

[0358] [Chemistry 24]

[0359]

[0360] Component (X2); compatible flame retardant X2-1: a phosphorus compound flame retardant having the following structure

[0361] [Chemistry 25]

[0362]

[0363] [(Y) component]

[0364] ・(Y1) ingredient: Filler flame retardant Y1-1: decabromodiphenylethane (see the structural formula below);

[0365] [Chemistry 26]

[0366]

[0367] Component (Y2): Compatible flame retardant Y2-1: a halogen-based flame retardant having the following structure:

[0368] [Chemistry 27]

[0369]

[0370] [Component (C)]

[0371] Inorganic filler C-1: Silane-coupled fused spherical silica, average particle size 0.5 μm

[0372] [Component (D)]

[0373] Curing accelerator D-1: α,α'-bis(tert-butylperoxy)diisopropylbenzene

[0374] As is clear from Table 2, the double-sided copper-clad laminates obtained in the respective Examples have low dielectric loss tangent (Df), thereby reducing transmission loss, and are also excellent in flame retardancy and appearance.

[0375] On the other hand, the double-sided copper-clad laminate of Comparative Example 1 had a high dielectric loss tangent (Df), inferior flame retardancy compared to the examples, and poor appearance. In Comparative Example 2, while the dielectric loss tangent (Df) improved and flame retardancy improved, the appearance was poor. In Comparative Example 3, while the dielectric loss tangent (Df) was relatively good and flame retardancy was excellent, the appearance was poor. This demonstrates that achieving low transmission loss, excellent flame retardancy, and a good appearance in a laminate is not easy.

Claims

1. A resin composition comprising: A thermosetting resin, B polymers having hydrocarbon chains or polyether chains, X phosphorus compound flame retardant, and Flame retardants other than the phosphorus compound flame retardant described in Y, The X component does not contain an X1 filling flame retardant, and the Y component does not contain a Y1 filling flame retardant, or When the X component contains an X1 filling flame retardant or the Y component contains a Y1 filling flame retardant, the total content of the X1 filling flame retardant and the Y1 filling flame retardant is 25 parts by mass or less per 100 parts by mass of the solid content in the resin composition.

2. The resin composition according to claim 1, wherein The X component contains an X2 compatible flame retardant.

3. The resin composition according to claim 1, wherein The Y component contains a Y2 compatible flame retardant.

4. The resin composition according to claim 1, wherein The component A comprises at least one selected from epoxy resins, maleimide compounds, phenolic resins, polyimide 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 is at least one selected from the group consisting of a conjugated diene polymer, a styrene-based elastomer, and modified products thereof. The resin composition according to claim 1 , wherein The component X comprises at least one selected from the group consisting of Xi's phosphate ester compounds, X-ii's phosphine oxide compounds, X-iii's phosphaphenanthrene compounds, X-iv's metal salts of phosphinic acid, and Xv's organic nitrogen-containing phosphorus compounds.

7. The resin composition according to claim 1, wherein The component X has two or more phosphorus atoms in one molecule.

8. The resin composition according to claim 1, wherein The component Y is a halogen flame retardant. 9 . The resin composition according to claim 1 , further comprising a C inorganic filler. 10 . The resin composition according to claim 1 , further comprising a curing accelerator (D). 11 . A prepreg comprising the resin composition according to claim 1 or a semi-cured product of the resin composition. 12 . A resin film comprising the resin composition according to claim 1 or a semi-cured product of the resin composition. 13 . A laminate comprising a cured product of the resin composition according to claim 1 or a cured product of the prepreg according to claim 11 and a metal foil. 14 . A printed wiring board comprising a cured product of the resin composition according to claim 1 . 15 . A semiconductor package comprising the printed wiring board according to claim 14 and a semiconductor element.

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