阅读说明：本技术 印刷电路板用树脂组合物、预浸料、树脂片、层叠板、覆金属箔层叠板、印刷电路板和多层印刷电路板 (Resin composition for printed wiring board, prepreg, resin sheet, laminate, metal foil-clad laminate, printed wiring board, and multilayer printed wiring board ) 是由 山口翔平 大西展义 田所弘晃 古田亚衣子 高桥博史 于 2018-07-10 设计创作，主要内容包括：一种印刷电路板用树脂组合物,其含有：含硅聚合物(A),其包含下述键(a)、(b)、(c)和(d)；氰酸酯化合物(B)；环氧树脂(D)；和,填充材料(E)。(键(a)～(d)中,R选自碳数1～12的取代或无取代的1价的烃基。X表示包含环氧基的1价的有机基团。前述含硅聚合物(A)中的全部R和X均任选相同或不同。)<Image he="143" wi="700" file="DDA0002361043840000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A resin composition for a printed circuit board, comprising: a silicon-containing polymer (A) containing the following bonds (a), (b), (c), and (d); a cyanate ester compound (B); an epoxy resin (D); and, a filler material (E). (in the bonds (a) to (d), R is selected from a C1-12 substituted or unsubstituted hydrocarbon group having a valence of 1. X represents an epoxy-containing organic group having a valence of 1. all of R and X in the silicon-containing polymer (A) are optionally the same or different.))

1. A resin composition for a printed circuit board, comprising:

a silicon-containing polymer (A) containing the following bonds (a), (b), (c), and (d);

a cyanate ester compound (B);

an epoxy resin (D); and

a filler (E) for filling the inside of the container,

in the bonds (a) to (d), R is selected from substituted or unsubstituted C1-12 hydrocarbon groups with a valence of 1, X represents an organic group with a valence of 1 containing an epoxy group, and all R and X in the silicon-containing polymer (A) are optionally the same or different.

2. The resin composition for a printed circuit board according to claim 1, wherein the silicon-containing polymer (A) has an epoxy equivalent of 500 to 4000 g/eq.

3. The resin composition for a printed circuit board according to claim 1 or 2, wherein R in the bonds (a) to (d) is a methyl group or a phenyl group.

4. The resin composition for a printed circuit board according to any one of claims 1 to 3, wherein the ratio of substituted or unsubstituted phenyl groups in all R of the silicon-containing polymer (A) is 50 to 75 mol%.

5. The resin composition for a printed circuit board according to any one of claims 1 to 4, wherein the silicon-containing polymer (A) has a weight average molecular weight of 5000 to 20000.

6. The resin composition for a printed circuit board according to any one of claims 1 to 5, wherein the content of the silicon-containing polymer (A) is 9 to 25 parts by mass with respect to 100 parts by mass of a resin solid content.

7. The resin composition for a printed circuit board according to any one of claims 1 to 6, wherein the epoxy resin (D) has a naphthalene structure.

8. The resin composition for a printed circuit board according to any one of claims 1 to 7, wherein the epoxy resin (D) is a cresol/naphthol novolac type epoxy resin represented by the following formula (NE),

here, m and n represent integers of 1 or more.

9. The resin composition for a printed circuit board according to any one of claims 1 to 8, wherein the cyanate ester compound (B) is a naphthol aralkyl type cyanate ester compound represented by the following formula (CN),

here, R⁷Each independently represents a hydrogen atom or a methyl group, n⁷Represents an integer of 1 or more.

10. The resin composition for a printed circuit board according to any one of claims 1 to 9, further comprising a maleimide compound (C).

11. The resin composition for a printed circuit board according to any one of claims 1 to 10, wherein the filler (E) is contained in an amount of 100 to 1000 parts by mass per 100 parts by mass of the resin solid content.

12. The resin composition for a printed circuit board according to any one of claims 1 to 11, wherein the silicon-containing polymer (a) is terminated with a substituent selected from the group consisting of R, X and an alkoxy group.

13. A prepreg, having: a substrate; and the resin composition for a printed circuit board according to any one of claims 1 to 12 impregnated or coated on the base material.

14. A resin tablet having: a support body; and the resin composition for a printed wiring board according to any one of claims 1 to 12 disposed on the surface of the support.

15. A laminate comprising a plurality of one or more selected from the group consisting of the prepreg according to claim 13 and the resin sheet according to claim 14.

16. A metal-clad laminate comprising: one or two or more selected from the group consisting of the prepreg according to claim 13 and the resin sheet according to claim 14; and, a metal foil.

17. A printed circuit board is provided with: an insulating layer comprising the resin composition for a printed circuit board according to any one of claims 1 to 12; and a conductor layer formed on a surface of the insulating layer.

18. A multilayer printed circuit board having a plurality of insulating layers and a plurality of conductor layers,

the plurality of insulating layers includes: laminating at least 1 or more 1 st insulating layers formed of at least 1 selected from the group consisting of the prepreg according to claim 13 and the resin sheet according to claim 14; and a 2 nd insulating layer formed by laminating at least 1 or more sheets of at least 1 selected from the group consisting of the prepreg according to claim 13 and the resin sheet according to claim 14 in a direction of one surface of the 1 st insulating layer,

the plurality of conductor layers includes: a 1 st conductor layer disposed between the insulating layers; and a 2 nd conductor layer disposed on an outermost surface of the plurality of insulating layers.

Technical Field

The present invention relates to a resin composition for a printed wiring board, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.

Background

In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, and the like have been accelerated. Along with this, the characteristics required for the laminate for semiconductor package used in the printed wiring board have become more and more strict.

In order to improve various characteristics required for a laminate for semiconductor encapsulation, various techniques have been developed, and among them, a technique of using a silicon-containing compound in a resin composition for a printed wiring board has been developed. For example, patent document 1 (japanese patent application laid-open No. 2014-47348) and patent document 2 (japanese patent application laid-open No. 2015-147869) disclose the following techniques: a prepreg is produced from a resin composition containing both a branched polysiloxane having a specific structure and a thermosetting resin.

Disclosure of Invention

Problems to be solved by the invention

In recent years, in the use of a laminate for semiconductor packaging, there has been an increasing demand for a peel strength (hereinafter, sometimes referred to as "peel strength") against a metal layer such as a copper foil in addition to a reduction in the thermal expansion coefficient (hereinafter, sometimes simply referred to as "thermal expansion coefficient") of the laminate. In particular, from the viewpoint of peel strength, compatibility of each component in the resin composition (hereinafter, may be referred to as "varnish compatibility") is one of important factors. In the techniques described in patent documents 1 and 2, there is still room for improvement in terms of maintaining a good thermal expansion coefficient and improving peel strength.

In order to solve the above problem, an object of the present invention is to provide: a resin composition for printed wiring boards which has good varnish compatibility, can form printed wiring boards having a low thermal expansion rate and excellent peel strength to copper foil, and a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board and a multilayer printed wiring board using the same.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems. As a result, they found that: the present invention has been completed by the fact that the above-mentioned object can be achieved by using a silicon-containing polymer having a specific structure.

<1> a resin composition for a printed circuit board, comprising:

a silicon-containing polymer (A) containing the following bonds (a), (b), (c), and (d);

a cyanate ester compound (B);

an epoxy resin (D); and

and a filler (E).

(in the bonds (a) to (d), R is selected from a C1-12 substituted or unsubstituted hydrocarbon group having a valence of 1. X represents an epoxy-containing organic group having a valence of 1. all of R and X in the silicon-containing polymer (A) are optionally the same or different.)

<2> the resin composition for a printed circuit board according to <1>, wherein the silicon-containing polymer (A) has an epoxy equivalent of 500 to 4000 g/eq.

<3> the resin composition for a printed circuit board according to <1> or <2>, wherein R in the bonds (a) to (d) is a methyl group or a phenyl group.

<4> the resin composition for a printed circuit board according to any one of <1> to <3>, wherein a ratio of substituted or unsubstituted phenyl groups in all R groups of the silicon-containing polymer (A) is 50 mol% to 75 mol%.

<5> the resin composition for a printed circuit board according to any one of <1> to <4>, wherein the silicon-containing polymer (A) has a weight average molecular weight of 5000 to 20000.

<6> the resin composition for a printed circuit board according to any one of <1> to <5>, wherein the silicon-containing polymer (A) is contained in an amount of 9 to 25 parts by mass per 100 parts by mass of the resin solid content.

<7> the resin composition for a printed circuit board according to any one of <1> to <6>, wherein the epoxy resin (D) has a naphthalene structure.

<8> the resin composition for a printed circuit board according to any one of <1> to <7>, wherein the epoxy resin (D) is a cresol/naphthol novolac type epoxy resin represented by the following formula (NE).

(where m and n are integers of 1 or more.)

<9> the resin composition for a printed circuit board according to any one of <1> to <8>, wherein the cyanate ester compound (B) is a naphthol aralkyl type cyanate ester compound represented by the following formula (CN).

(Here, R is⁷Each independently represents a hydrogen atom or a methyl group. n is⁷Represents an integer of 1 or more. )

<10> the resin composition for a printed circuit board according to any one of <1> to <9>, which further comprises a maleimide compound (C).

<11> the resin composition for a printed wiring board as stated in <10>, wherein the content of the filler (E) is 100 to 1000 parts by mass per 100 parts by mass of the resin solid content.

<12> the resin composition for a printed circuit board according to any one of <1> to <11>, wherein the silicon-containing polymer (A) has a terminal group selected from the group consisting of R, X and an alkoxy group.

<13> a prepreg having: a substrate; and the resin composition for a printed wiring board according to any one of the items <1> to <12> impregnated or applied to the base material.

<14> a resin tablet comprising: a support body; and the resin composition for a printed wiring board according to any one of the items <1> to <12> disposed on the surface of the support.

<15> a laminated board comprising a plurality of one or more selected from the group consisting of the prepreg according to <13> and the resin sheet according to <14 >.

<16> a metal-clad laminate comprising: one or more selected from the group consisting of the prepreg according to <13> and the resin sheet according to <14 >; and, a metal foil.

<17> a printed wiring board, comprising: an insulating layer comprising the resin composition for a printed wiring board according to any one of the above <1> to <12 >; and a conductor layer formed on the surface of the insulating layer.

<18> a multilayer printed circuit board having a plurality of insulating layers and a plurality of conductor layers,

the plurality of insulating layers includes: at least 1 or more 1 insulating layers formed of at least 1 selected from the group consisting of the prepreg according to the above <13> and the resin sheet according to the above <14> are laminated; and a 2 nd insulating layer formed by laminating at least 1 or more sheets of at least 1 selected from the group consisting of the prepreg according to the <13> and the resin sheet according to the <14> in a direction of one surface of the 1 st insulating layer,

the plurality of conductor layers includes: a 1 st conductor layer disposed between the insulating layers; and a 2 nd conductor layer disposed on the outermost surface of the plurality of insulating layers.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a resin composition for printed wiring boards which has good varnish compatibility, can form printed wiring boards having a low thermal expansion rate and excellent peel strength to copper foil, and a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board and a multilayer printed wiring board using the same.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention.

Resin composition for printed wiring board

The resin composition for a printed wiring board of the present embodiment (hereinafter, may be simply referred to as "resin composition") contains: a silicon-containing polymer (A) containing the following bonds (a), (b), (c), and (d); a cyanate ester compound (B); an epoxy resin (D); and, a filler material (E).

(in the bonds (a) to (d), R is selected from a C1-12 substituted or unsubstituted hydrocarbon group having a valence of 1. X represents an epoxy-containing organic group having a valence of 1. all of R and X in the silicon-containing polymer (A) are optionally the same or different.)

The silicon-containing polymer (A) has a bond (d) in addition to the bonds (a), (b) and (c). The bonds (a) and (d) are trivalent bonding groups, and the silicon-containing polymer (a) can be formed into a three-dimensional structure. In general, a silicon-containing polymer including a structural unit of the bond (a) and the bond (b) has poor compatibility with other resin components, but the silicon-containing polymer includes: having a structural unit of "1-valent organic group containing an epoxy group", compatibility with other resin components is improved. In particular, a resin composition using a silicon-containing polymer (a) having a bond (d) which is a trivalent bonding group capable of forming a three-dimensional structure and has a structural unit having an organic group having a valence of 1 including an epoxy group is highly compatible with a varnish. When a prepreg or the like is produced by curing, the thermal expansion coefficient of the cured product is low as compared with a composition using a silicon-containing polymer having no bond (d), and excellent peel strength can be exhibited even when a metal foil-clad laminate or the like is formed.

(silicon-containing Polymer (A))

The silicon-containing polymer (A) contains bonds (a), (b), (c) and (d).

(in the bonds (a) to (d), R is selected from a C1-12 substituted or unsubstituted hydrocarbon group having a valence of 1. X represents an epoxy-containing organic group having a valence of 1. all of R and X in the silicon-containing polymer (A) are optionally the same or different.)

In the bonds (a) to (c), R is a substituted or unsubstituted C1-12 hydrocarbon group having a valence of 1, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, and the like; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenyl; aralkyl groups such as benzyl and phenethyl, and among them, methyl and phenyl are preferred. In the silicon-containing polymer (a), at least one R in the bonds (a) to (c) preferably has a substituted or unsubstituted phenyl group, and more preferably the bond (a) has a substituted or unsubstituted phenyl group. In the above case, the ratio of the substituted or unsubstituted phenyl groups in all R groups of the silicon-containing polymer (a) is preferably 50 to 75 mol% from the viewpoint of compatibility with other thermosetting resin components (thermosetting resin components other than the silicon-containing polymer (a)). Further, from the viewpoint of satisfying both the thermal expansion coefficient and the peel strength, the ratio of substituted or unsubstituted phenyl groups in all R groups of the silicon-containing polymer (a) is more preferably 70 mol% to 75 mol%.

In the bonds (c) and (d), X is a 1-valent organic group containing an epoxy group, and examples thereof include a 2, 3-epoxypropyl group, a 3, 4-epoxybutyl group, a 4, 5-epoxypentyl group, a 2-epoxypropoxyethyl group, a 3-epoxypropoxypropyl group, a 4-epoxypropoxybutyl group, a 2- (3, 4-epoxycyclohexyl) ethyl group, a 3- (3, 4-epoxycyclohexyl) propyl group and the like, and among them, a 3-epoxypropoxypropyl group is preferable.

The silicon-containing polymer (a) may have other bonds than the bonds (a) to (d). Examples of the other bond include bonds in which R or X in the bonds (a) to (d) is a hydrogen atom.

The terminal of the silicon-containing polymer (a) is not particularly limited, and may be a hydrogen atom, a phenoxy group or the like, in addition to the substituent selected from the group consisting of R, X, a hydroxyl group and an alkoxy group. From the viewpoint of storage stability of the polymer, the terminal of the silicon-containing polymer (a) is preferably R, X or an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

The epoxy equivalent of the silicon-containing polymer (A) is not particularly limited, but is preferably in the range of 500 to 4000g/eq, more preferably 1000 to 2500g/eq, and particularly preferably 1000 to 2000g/eq, from the viewpoint of improving varnish compatibility. The softening point of the silicon-containing polymer (a) is not particularly limited, but is preferably from 40 ℃ to 120 ℃, more preferably from 50 ℃ to 100 ℃, from the viewpoints of dispersibility of the silicon-containing polymer (a) and mechanical strength of a cured product of the obtained resin composition for a printed circuit board. The softening point of the silicon-containing polymer (a) can be appropriately adjusted depending on, for example, the molecular weight of the silicon-containing polymer (a), the content ratio of the constituent bond units (e.g., (a) to (d)), and the like.

From the viewpoint of reducing the elasticity of the resin composition and suppressing the occurrence of bleeding, the weight average molecular weight (Mw: in terms of polystyrene in Gel Permeation Chromatography (GPC) measurement) of the silicon-containing polymer (a) is preferably 3000 or more, more preferably 5000 to 20000, and particularly preferably 6500 to 16000. In addition, the silicon-containing polymer (a) is preferably a random copolymer.

The method for producing the silicon-containing polymer (a) is not particularly limited, and it can be produced by a known method. For example, the (co) hydrolysis and condensation reaction may be carried out by using an organochlorosilane, organoalkoxysilane, siloxane, or a partial hydrolysis condensate thereof capable of forming the above-mentioned bonds (a) to (d) by a hydrolysis and condensation reaction.

Examples of the compound capable of forming the bond (a) (hereinafter, may be referred to as "compound (a)") include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and allyltrimethoxysilane. Examples of commercially available products of these compounds include phenyltrimethoxysilane (KBM 103, product name of shin-Etsu chemical Co., Ltd.), phenyltriethoxysilane (KBE-103, product name of shin-Etsu chemical Co., Ltd.), and the like.

Examples of the compound capable of forming the bond (b) (hereinafter, may be referred to as "compound (b)") include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, and the like. Examples of commercially available products of these compounds include dimethyldimethoxysilane (product name: KBM-22, product name: shin-Etsu chemical Co., Ltd.), dimethyldiethoxysilane (product name: KBE-22, product name: shin-Etsu chemical Co., Ltd.), and the like.

Examples of the compound capable of forming the bond (c) (hereinafter, may be referred to as "compound (c)") include γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, and β - (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, and examples of commercially available products of these compounds include γ -glycidoxypropylmethyldiethoxysilane (shin-Etsu chemical Co., Ltd., product name: KBE-402), β - (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane (shin-Etsu chemical Co., Ltd., product name: KBM-402), and the like.

Examples of the compound capable of forming the bond (d) (hereinafter, may be referred to as "compound (d)") include γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

The bonds (a) to (d) in the silicon-containing polymer (a) can be roughly classified into: bonds (a) and (d) belonging to a trivalent bonding group, and bonds (b) and (c) belonging to a divalent bonding group. When the bonds (a) and (D) are "T units" and the bonds (b) and (c) are "D units", the respective amounts of the T units and the D units in the silicon-containing polymer (a) are preferably 50 or more and less than 100 [ simmol% ] and the D units are more than 0 and 50 or less [ simmol% ] with respect to the total 100 [ simmol% ] of the bonds (a) to (D) from the viewpoint of compatibility with other thermosetting resin components, and from the viewpoint of solubility in a solvent and low thermal expansion properties, the T units are more preferably 70 or more and 85 or less [ simmol% ], the D units are more than 15 and 30 or less [ simmol% ], and particularly the T units are more than 80 and 85 [ simmol% ] and the D units are more than 15 and 20 or less [ simmol% ]. The silicon-containing polymer (a) can be produced, for example, by using the above-mentioned compounds (a) to (d) in an arbitrary ratio so that each bond falls within the above-mentioned range.

The mol% of Si is a ratio of all Si moles, and the mol of Si means that the molecular weight is 1 mole in the case of a monomer and the number obtained by dividing the average molecular weight by 2 in the case of a dimer is 1 mole.

The silicon-containing polymer (a) may have other bonds within a range not hindering the effect of the present invention.

The silicon-containing polymer (a) can be synthesized by (co) hydrolyzing and condensing a raw material containing the compounds (a) to (d) (hereinafter, may be simply referred to as "a mixture of the compounds (a) to (d)") by a known method. For example, a mixture of the compounds (a) to (d) is (co) hydrolyzed in water having a pH of 1 to 7.5, preferably 2 to 7. In this case, metal oxide fine particles such as silica fine particles dispersed in water can be used. In order to adjust the pH and promote hydrolysis, the catalyst may be an organic acid or an inorganic acid such as hydrogen fluoride, hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, or toluenesulfonic acid, a solid acid catalyst such as a cation exchange resin having a carboxylic acid group or a sulfonic acid group on the surface, or water-dispersible metal oxide fine particles such as acidic water-dispersible silica fine particles. In addition, in the hydrolysis, metal oxide fine particles such as silica fine particles may be dispersed in water or an organic solvent.

In the hydrolysis, the amount of water used may be in the range of 20 to 3000 parts by mass of water with respect to 100 parts by mass of the total of the compounds (a) to (d), and may be 50 parts by mass or more and 150 parts by mass or less from the viewpoint of storage stability, scratch resistance, and crack resistance.

The aforementioned hydrolysis may be carried out as follows: adding dropwise or adding water to the mixture of the compounds (a) to (d), or adding dropwise or adding the mixture of the compounds (a) to (d) to water. In the above case, the synthesis may be carried out using an organic solvent or without an organic solvent. For example, if an organic solvent is used, the weight average molecular weight of the silicon-containing polymer (a) obtained by hydrolysis in terms of polystyrene tends to be small in GPC analysis.

To obtain the silicon-containing polymer (A), the condensation reaction is carried out immediately after the above hydrolysis. The condensation may be carried out continuously immediately after the hydrolysis, and is usually carried out at room temperature or under heating at 100 ℃ or lower from the viewpoint of suppressing gelation. Further, the alcohol generated in the hydrolysis is distilled off at 80 ℃ or higher, under normal pressure or reduced pressure, whereby the condensation can be promoted. Further, a condensation catalyst such as a basic compound, an acidic compound, and a metal chelate may be added for the purpose of promoting condensation. Before or during the condensation step, an organic solvent may be added for the purpose of adjusting the degree of progress and concentration of condensation, and fine metal oxide particles such as silica fine particles may be dispersed in water or the organic solvent. Since the silicon-containing polymer (a) generally has a higher molecular weight as it is condensed and gradually becomes less soluble in water or a product alcohol, it is preferable to use an organic solvent which is sufficiently soluble in the silicon-containing polymer (a) and has a boiling point of 80 ℃ or higher and a high polarity as the organic solvent to be added. Specific examples of such organic solvents include alcohols such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and diacetone alcohol; ketones such as methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; and esters such as propyl acetate, butyl acetate, and cyclohexyl acetate.

The content of the silicon-containing polymer (a) in the resin composition of the present embodiment is not particularly limited, and is preferably 9 to 25 parts by mass per 100 parts by mass of the resin solid content from the viewpoints of varnish compatibility, heat resistance, and chemical resistance. In the present embodiment, the term "resin solid content" refers to the total amount of components other than the solvent and the filler (E) in the resin composition, unless otherwise specified.

(cyanate ester Compound (B))

The resin composition in the present embodiment contains a cyanate ester compound (B). The cyanate ester compound (B) is not particularly limited as long as it has at least 1 aromatic moiety substituted with a cyanato group (cyanate group) in the molecule. When a cured product is formed using a resin composition containing a cyanate ester compound, the cured product has excellent properties such as a glass transition temperature, low thermal expansion properties, and plating adhesion.

Examples of the cyanate ester compound include, but are not limited to, those represented by the following formula (1).

In the formula (1), Ar₁Represents a benzene ring, a naphthalene ring or a compound in which 2 benzene rings are bonded independently. In the case of a plurality of the compounds, they are optionally the same as or different from each other. Ra independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a group in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded. The aromatic ring in Ra may have a substituent, Ar₁And the substituents in Ra may be optionally substituted. p represents a bond to Ar₁The number of the cyanato groups (a) is an integer of 1 to 3, independently of each other. q represents a bond to Ar₁Number of Ra of (A), Ar₁4-p in the case of benzene ring, 6-p in the case of naphthalene ring, and 8-p in the case of 2 bonded benzene rings. t represents an average repetition number in the range of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t. When there are a plurality of X, each independently represents a single bond, a 2-valent organic group having 1 to 50 carbon atoms (a hydrogen atom is optionally substituted by a heteroatom), a 2-valent organic group having 1 to 10 nitrogen atoms (for example, -N-R-N- (where R represents an organic group.), a carbonyl group (-CO-), a carboxyl group (-C (-O) O-), a carbonyl dioxide group (-OC (-O) O-), a sulfonyl group (-SO-)₂-) and 2 valentAny of sulfur atom(s) or oxygen atom(s) having a valence of 2.

The alkyl group in Ra in formula (1) may have any of a linear or branched chain structure and a cyclic structure (for example, cycloalkyl).

Further, the alkyl group in Ra and the hydrogen atom in the aryl group in Ra in the formula (1) are optionally substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group.

Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl.

Specific examples of the aryl group include, but are not limited to, phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl, and o-tolyl, m-tolyl, p-tolyl, and the like.

The alkoxy group is not limited to the following, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

Specific examples of the 2-valent organic group having 1 to 50 carbon atoms in X in the formula (1) are not limited to the following, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylmethylene group, a dimethylmethylene group, a phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalenediyl group. The hydrogen atom in the 2-valent organic group is optionally substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like.

Examples of the 2-valent organic group having 1 to 10 nitrogen atoms in X of the formula (1) include, but are not limited to, imino groups and polyimide groups.

Examples of the organic group of X in formula (1) include structures represented by formula (2) or formula (3).

(in the above formula (2), Ar₂Represents a phenyltetrayl group, a naphthyltetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different from each other. Rb, Rc, Rf and Rg each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group or an aryl group having at least 1 phenolic hydroxyl group. Rd and Re are independently selected from any one of hydrogen atom, alkyl with 1-6 carbon atoms, aryl with 6-12 carbon atoms, alkoxy with 1-4 carbon atoms or hydroxyl. u represents an integer of 0 to 5, and may be a mixture of compounds having different u. )

(in formula (3), Ar₃Represents a phenyltetrayl group, a naphthyltetrayl group or a biphenyltetrayl group, and when v is 2 or more, they are optionally the same or different from each other. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least 1 cyanato group. v represents an integer of 0 to 5, and may be a mixture of compounds having different v. )

Further, X in formula (1) may be a group having a valence of 2 as shown in the following formula.

(in the formula, z represents an integer of 4-7, Rk independently represents a hydrogen atom or an alkyl group having 1-6 carbon atoms.)

Ar as formula (2)₂And Ar of formula (3)₃Specific examples of (3) include a phenyltetrayl group having 2 carbon atoms represented by the formula (2) or 2 oxygen atoms bonded to the 1, 4-or 1, 3-positions represented by the formula (3), a biphenyltetrayl group having the 2 carbon atoms or 2 oxygen atoms bonded to the 4,4 ' -position, 2 ' -position, 2,3 ' -position, 3 ' -position, or 3,4 ' -position, and the formerThe tetranyl group having 2 carbon atoms or 2 oxygen atoms bonded to the 2,6-, 1,5-, 1,6-, 1, 8-, 1,3-, 1,4-, or 2, 7-positions.

The alkyl group and the aryl group in Rb, Rc, Rd, Re, Rf and Rg of the formula (2) and Ri, Rj of the formula (3) are the same as those of the formula (1).

Specific examples of the cyanato-substituted aromatic compound represented by the formula (1) include cyanatobenzene, cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, cyanato-2-, 1-cyanato-2-, 3-cyanato-2-, 2-cyanato-2-, 1-cyanato-2-, 3-cyano-4-cyanophenyl-2-, 2-cyano-2-, 3-cyano-or 1-cyanato-4-cyanophenyl-2- (4, 4-cyanophenyl) -2, 4-cyanophenyl) ethyl-4-cyanophenyl, cyanato-cyanophenyl-4-cyanophenyl-cyano-2, 2-cyanophenyl-cyano-4-cyanophenyl-cyano-2-cyanophenyl-4-cyanophenyl-cyano-2-cyano-2-3, 2-cyano-4-cyanophenyl-cyano-4-cyanophenyl-cyano-2-cyanophenyl-cyano-4-cyano-2-cyano-2-cyano-4-cyano-2-cyano-2, 2, 2-cyano-4-cyano-4-cyanophenyl-cyano-2, 2-cyano-2, 4-cyano-2, 2, 4-cyanophenyl-cyano-2, 4-cyanophenyl-cyano-2-4-cyanophenyl-2-cyano-4-cyano-2, 2, 4-cyanophenyl-cyano-2, 2, 2-cyano-4-cyano-2-cyano-2-cyano-2, 4-cyano-2-4-cyano-2-cyano-2, 4-cyano-2-3, 4-2, 2-4-cyano-2, 2, 4-cyano-2, 2,2, 4-cyano-2, 4-cyano-2, 3, 4-cyano-2, 1,3,3, 4-cyano-2, 3, 4-cyano-4-cyano-4-3, 4-cyano-2-4-cyano-4-cyano-4-cyano-2, 2, 4-2, 1, 4-2, 2, 4-cyano-4-cyano-cyanophenyl-2, 4-cyano-cyanophenyl-cyano-cyanophenyl-cyano-4-cyanophenyl-2, 4-cyanophenyl-2, 1,1, 4-cyanophenyl-2-cyanophenyl-2, 1,1, 4-cyanophenyl-2, 4-2, 1,3, 4-2-3, 3, 4-2, 4-2, 1,1,3, 4-2, 1,3,3, 1,1,1, 4-2, 4-cyanophenyl-4-cyanophenyl-4-3, 4-2, 4-cyanophenyl-2-4-cyanophenyl-3, 4-cyanophenyl-2, 1, 4-cyanophenyl-2, 4-cyanophenyl-3, 1,3, 4-cyanophenyl-3, 1, 4-cyanophenyl-4-cyanophenyl-3, 4-cyanophenyl-4-cyanophenyl-2, 4-2, 1, 4-cyanophenyl-2-cyanophenyl-2, 1,1,1, 4-cyanophenyl-3, 1,1,3,3, 4-3, 1,1, 4-cyanophenyl-2, 4-3, 1,1,1, 4-3, 4-2-cyanophenyl-3, 4-cyanophenyl-2-cyanophenyl-3, 1, 4-cyanophenyl-3, 4-cyanophenyl-3, 4-3, 1, 4-cyanophenyl-4-3, 4-cyanophenyl-3, 1, 4-cyanophenyl-3, 4-3, 1, 4-cyanophenyl-3, 1, 4-3, 1,1, 4-cyanophenyl-3, 4-3, 1, 4-cyanophenyl-3, 4-3, 1,1, 4-cyanophenyl-4-cyanophenyl-3, 4-cyanophenyl-3, 4-3, 1,1, 4-cyanophenyl-3, 2, 4-3, 1, 4-cyanophenyl-3, 4-3, 1,1, 4-3, 1,1, 4-3, 1, 4-2, 4-cyanophenyl-3, 4-3, 1,1, 4-cyanophenyl-3, 1,1,2,2, 1,1,3, 4-cyanophenyl-3, 4-3, 3, 1, 4-cyanophenyl-3, 4-3, 2, 4-3, 1, 4-cyanophenyl-4-3, 4-cyanophenyl-3, 2-4-cyanophenyl-3, 4-3, 1, 4-cyanophenyl-3, 1, 4-cyanophenyl-3, 1,1,1, 4-cyanophenyl-3, 1, 4-.

Other specific examples of the compound represented by the formula (1) are not limited to the following, and examples thereof include those obtained by cyanating the following resins in the same manner as described above: phenol novolac resins and cresol novolac resins (obtained by reacting phenol, alkyl-substituted phenol, halogen-substituted phenol, and formaldehyde compounds such as formalin and paraformaldehyde in an acidic solution by a known method), trisphenol novolac resins (obtained by reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), and fluorene novolaksA lacquer resin (obtained by reacting a fluorenone compound with 9, 9-bis (hydroxyaryl) fluorene in the presence of an acidic catalyst), a phenol aralkyl resin, a cresol aralkyl resin, a naphthol aralkyl resin, and a biphenyl aralkyl resin (Ar is reacted by a known method₄-(CH₂Y)₂(Ar₄Represents a phenyl group, and Y represents a halogen atom. The same applies to the following paragraphs. ) A substance obtained by reacting the above-mentioned bishalomethyl compound with a phenol compound with or without an acid catalyst, Ar₄-(CH₂OR)₂A substance obtained by reacting the bis (alkoxymethyl) compound with a phenol compound in the presence of an acidic catalyst, or Ar₄-(CH₂OH)₂The bis (hydroxymethyl) compound shown above is reacted with a phenol compound in the presence of an acidic catalyst to obtain a product, or is subjected to polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound to obtain a product), a phenol-modified xylene formaldehyde resin (by a known method, phenol resins such as xylene formaldehyde resins and phenol compounds obtained by reacting in the presence of an acidic catalyst), modified naphthalene formaldehyde resins (obtained by reacting a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclopentadiene resins, and phenol resins having a polynaphthylene ether structure (obtained by dehydrating and condensing a polyhydroxynaphthalene compound having 2 or more phenolic hydroxy groups in 1 molecule in the presence of a basic catalyst by a known method); and prepolymers thereof, and the like.

The cyanate ester compound may be used alone in 1 kind or in combination with 2 or more kinds.

Among the above cyanate ester compounds, bisphenol type cyanate ester compounds such as bisphenol a type cyanate ester compound, bisphenol E type cyanate ester compound and bisphenol F type cyanate ester compound, naphthol aralkyl type cyanate ester compounds and phenol novolac type cyanate ester compounds are preferable. That is, in the present embodiment, the cyanate ester compound preferably contains at least 1 selected from the group consisting of a bisphenol type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, and a phenol novolac type cyanate ester compound. Further, the cyanate ester compound more preferably contains a naphthol aralkyl type cyanate ester compound.

The naphthol aralkyl type cyanate ester compound may be a naphthol aralkyl type cyanate ester compound represented by the following formula (CN).

(Here, R is⁷Each independently represents a hydrogen atom or a methyl group. n is⁷Represents an integer of 1 or more. )

The content of the cyanate ester compound is not particularly limited, and is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 20 to 30 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of heat resistance and chemical resistance.

(Maleimide Compound (C))

The resin composition of the present embodiment may optionally contain a maleimide compound (C). The maleimide compound (C) is not particularly limited as long as it is a compound having 1 or more maleimide groups in the molecule, and examples thereof include: n-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, a maleimide compound represented by the following formula (4), a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound. Among them, at least 1 kind selected from the group consisting of 2, 2' -bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and a maleimide compound represented by the following formula (4) is preferable. By containing such a maleimide compound (C), the thermal expansion coefficient of the obtained cured product tends to be further lowered, and the glass transition temperature tends to be further excellent. From the same viewpoint, the maleimide compound (C) more preferably contains at least 1 selected from the group consisting of maleimide compounds represented by the following formula (4).

Here, in the formula (4), R₅Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (4), n₁Represents an integer of 1 or more, preferably an integer of 10 or less, more preferably an integer of 7 or less.

The content of the maleimide compound (C) in the present embodiment is preferably 10 to 50 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 20 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the maleimide compound (C) is within the above range, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

(epoxy resin (D))

The resin composition of the present embodiment contains an epoxy resin (D). As the epoxy resin (D), an epoxy resin having 2 or more epoxy groups in 1 molecule is preferable, and a known epoxy resin can be suitably used. The kind of the epoxy resin (D) is not particularly limited, and is different from the silicon-containing polymer (A). Specific examples of the epoxy resin (D) include: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene-based epoxy resins, naphthalene skeleton-modified novolac-based epoxy resins, phenol aralkyl-based epoxy resins, naphthol aralkyl-based epoxy resins, dicyclopentadiene-based epoxy resins, biphenyl-based epoxy resins, alicyclic epoxy resins, polyhydric alcohol-based epoxy resins, phosphorus-containing epoxy resins, glycidylamine, glycidylester, compounds obtained by epoxidizing double bonds of butadiene or the like, compounds obtained by reacting hydroxyl-containing organosilicon resins with epichlorohydrin, and the like. Among these epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in terms of flame retardancy and heat resistance. These epoxy resins may be used alone in 1 kind or in combination of 2 or more kinds.

Among them, as the epoxy resin (D), an epoxy resin having a naphthalene structure is preferable from the viewpoint of heat resistance, chemical resistance, and thermal expansion coefficient, and a cresol/naphthol novolac type epoxy resin represented by the following formula (NE) is particularly preferable. The compound represented by the following (NE) is a random copolymer of a structural unit of cresol novolac epoxy and a structural unit of naphthol novolac epoxy, and either of the cresol epoxy and the naphthol epoxy may be a terminal.

(where m and n are each an integer of 1 or more.)

M and n in the formula (NE) each represent an integer of 1 or more. The upper limit and the ratio of m to n are not particularly limited, and from the viewpoint of the thermal expansion coefficient, m: n (wherein m + n is 100) is preferably 30 to 50: 70 to 50, particularly preferably 45 to 55: 55-45.

The content of the epoxy resin (D) may be appropriately set according to the desired properties, and is not particularly limited, but is preferably 20 to 50 parts by mass, more preferably 25 to 45 parts by mass, and further preferably 30 to 40 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoints of flexibility, copper foil peel strength, chemical resistance, and stain removal resistance.

The resin composition of the present embodiment may further include 1 or more selected from the group consisting of a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group.

Phenolic resins

As the phenol resin, any generally known phenol resin having 2 or more hydroxyl groups in 1 molecule can be used. Specific examples thereof include, but are not particularly limited to, bisphenol a type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol a novolac type phenol resin, glycidyl ester type phenol resin, aralkyl type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton-modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic type phenol resin, polyhydric alcohol type phenol resin, phosphorus-containing phenol resin, hydroxyl group-containing silicone resin, and the like. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in terms of flame retardancy. These phenol resin can be used alone 1 or a combination of 2 or more.

-oxetane resins

As the oxetane resin, a generally known one can be used. Examples thereof include, but are not particularly limited to, an alkyl oxetane such as oxetane, 2-methyloxetane, 2-dimethyloxetane, 3-methyloxetane or 3, 3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toyo Seiya Synthesis), OXT-121 (trade name manufactured by Toyo Seiya Synthesis), and the like. These oxetane resins can be used in a mixture of 1 kind or 2 or more kinds.

-benzoxazine compounds

As the benzoxazine compound, a generally known one can be used as long as it has 2 or more dihydrobenzoxazine rings in 1 molecule. Examples thereof include, but are not limited to, bisphenol A type benzoxazine BA-BXZ (trade name of the product. These benzoxazine compounds may be used in 1 kind or 2 or more kinds by mixing.

Compounds having polymerizable unsaturated groups

As the compound having a polymerizable unsaturated group, a generally known compound can be used. Examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl, (meth) acrylic acid methyl ester, (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl ester, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other 1-or polyhydric alcohol (meth) acrylic acid esters, bisphenol a type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate and other epoxy (meth) acrylate esters, and benzocyclobutene resins, but are not particularly limited thereto. These compounds having an unsaturated group may be used in a mixture of 1 or 2 or more. The "(meth) acrylate" is a concept including an acrylate and a corresponding methacrylate.

(Filler (E))

The resin composition of the present embodiment contains a filler (E). Examples of the filler (E) include inorganic fillers and organic fillers. These may be used alone or in combination.

As the filler (E), a known filler can be suitably used, and the kind thereof is not particularly limited. In particular, a filler generally used for laminate applications can be suitably used as the filler (E).

Specific examples of the inorganic filler include, but are not limited to, natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, hollow silica and other silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide and other oxides, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide heat-treated products (products obtained by heat-treating aluminum hydroxide to reduce a part of crystal water), boehmite, magnesium hydroxide and other metal hydrates, molybdenum oxide, zinc molybdate and other molybdenum compounds, zinc borate, zinc stannate, aluminum oxide, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, and the like, D-glass, S-glass, M-glass G20, glass short fibers (glass fine powder including E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass. These inorganic fillers may be used alone in 1 kind or in combination of 2 or more kinds.

Among them, as the inorganic filler, 1 or 2 or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are suitable. By using these inorganic fillers, the properties of the resin composition, such as thermal expansion properties, dimensional stability, and flame retardancy, tend to be further improved.

The content of the filler (E) in the resin composition of the present embodiment may be appropriately set according to the desired characteristics, and is not particularly limited, but is preferably 40 to 1000 parts by mass, more preferably 100 to 1000 parts by mass, further preferably 100 to 750 parts by mass, and particularly preferably 100 to 300 parts by mass with respect to 100 parts by mass of the resin solid content, from the viewpoint of moldability of the resin composition. The content of the filler (E) is the total amount of the inorganic filler and the organic filler.

The content of the inorganic filler in the resin composition of the present embodiment may be appropriately set according to the desired characteristics, and is not particularly limited, but is preferably 40 to 1000 parts by mass, more preferably 100 to 750 parts by mass, and further preferably 100 to 300 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of moldability of the resin composition.

Specific examples of the organic filler include rubber powders of styrene type, butadiene type, acrylic type, and the like, core-shell type rubber powders, and silicone resin powders, silicone rubber powders, silicone composite powders, and the like.

When an organic filler is used, the resin composition tends to have further improved properties such as thermal expansion coefficient, flexibility, and flame retardancy.

The content of the organic filler in the resin composition of the present embodiment may be appropriately set according to the desired properties, and is not particularly limited, but is preferably 0 to 25 parts by mass, more preferably 10 to 25 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of properties such as thermal expansion coefficient, flexibility, and flame retardancy of the resin composition.

The resin composition of the present embodiment can use the filler (E) in combination with a silane coupling agent and a wetting dispersant, and the silane coupling agent is not particularly limited in kind, and examples thereof include, but are not limited to, aminosilicone-based ones such as γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, vinylsilane-based ones such as γ -glycidoxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, vinyl-tris (β -methoxyethoxy) silane, cationic silane-based ones such as N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyltrimethoxysilane hydrochloride, and phenylsilane-based silane coupling agents can be used alone or in combination of 1 or 2 or more, and examples thereof include, but are not limited in kind, as a wetting dispersant, substances used for general coating materials, and examples thereof are not particularly limited in kind, but basic copolymers can be used alone or in combination of 1 or 2 or more, and examples thereof can be used as wetting dispersants by99940, but commercially available as byw-100-BYK dispersants, and examples thereof can be used alone or in combination of by9910-100-BYK-100-BYK.

(curing accelerators)

The resin composition of the present embodiment may contain a curing accelerator for appropriately adjusting the curing speed. As the curing accelerator, those generally used as curing accelerators for cyanate ester compounds, epoxy resins and the like can be suitably used, and the kind thereof is not particularly limited. Specific examples of the curing accelerator include organic metal salts such as zinc octoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octoate, manganese octoate, phenol compounds such as xylenol, cresol, resorcinol, catechol, octylphenol, nonylphenol, alcohols such as 1-butanol, 2-ethylhexanol, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, imidazoles such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of carboxylic acids or acid anhydrides thereof of these imidazoles, derivatives such as, Amines such as dicyandiamide, benzyldimethylamine and 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds and bisphosphine compounds, epoxy-imidazole adduct compounds, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate and di-2-ethylhexyl peroxycarbonate, azo compounds such as azobisisobutyronitrile, and N, N-dimethylaminopyridine. The curing accelerator may be used alone in 1 kind or in combination of 2 or more kinds.

(other additives)

Further, the resin composition of the present embodiment may be used in combination with other thermosetting resins, thermoplastic resins and oligomers thereof, various polymer compounds such as elastomers, flame retardant compounds, various additives, and the like, as long as desired properties are not impaired. They are not particularly limited as long as they are generally used. Specific examples of the flame retardant compound include, but are not limited to, bromine compounds such as 4, 4' -dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and silicone compounds. The various additives are not limited to the following, and examples thereof include an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightener, a photosensitizing agent, a dye, a pigment, a thickener, a flow control agent, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a gloss agent, and a polymerization inhibitor. They may be used alone in 1 kind or in combination of 2 or more kinds, as desired.

(organic solvent)

The resin composition of the present embodiment may contain an organic solvent as needed. In the above case, the resin composition of the present embodiment may be used in a form (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible in an organic solvent. As the organic solvent, any known organic solvent can be suitably used as long as it can dissolve or compatibilize at least a part, preferably all, of the various resin components, and the kind thereof is not particularly limited. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ester solvents such as methyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate, polar solvents such as amides such as dimethylacetamide and dimethylformamide, and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. These can be used alone 1 or a combination of 2 or more.

The resin composition of the present embodiment can be produced by a conventional method, and the production method is not particularly limited as long as the resin composition containing the silicon-containing polymer (a), the cyanate ester compound (B), the epoxy resin (D), the filler (E), and the other optional components in the present embodiment can be obtained. For example, the resin composition of the present embodiment can be easily prepared by mixing the respective components of the present embodiment in order in a solvent and sufficiently stirring.

In the preparation of the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing the respective components may be performed. For example, when the filler (E) is uniformly dispersed, the dispersibility in the resin composition can be improved by performing a stirring dispersion treatment in a stirring tank equipped with a stirrer having an appropriate stirring ability. The stirring, mixing and kneading treatment can be suitably performed by using a known apparatus such as an apparatus for mixing purposes, e.g., a ball mill and a bead mill, or a revolution/rotation type mixing apparatus.

The resin composition of the present embodiment can be used as a constituent material of a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, a multilayer printed wiring board, and a semiconductor package. For example, a prepreg can be obtained by impregnating or applying a solution in which the resin composition of the present embodiment is dissolved in a solvent to a substrate and drying the solution.

A peelable plastic film is used as a substrate, and a solution in which the resin composition of the present embodiment is dissolved in a solvent is applied to the plastic film and dried to obtain a film for lamination or a dry film solder resist. Here, the solvent may be dried at a temperature of 20 to 150 ℃ for 1 to 90 minutes.

The resin composition of the present embodiment may be used in an uncured state in which only the solvent is dried, or may be used in a semi-cured (B-stage) state as needed.

Prepreg

The prepreg of the present embodiment will be described in detail below. The prepreg of the present embodiment has: a substrate; and the resin composition impregnated or coated on the substrate. The method for producing the prepreg of the present embodiment is not particularly limited as long as the method is a method for producing a prepreg by combining the resin composition of the present embodiment with a substrate. Specifically, the prepreg of the present embodiment can be produced by a method of impregnating or applying the resin composition of the present embodiment to a substrate, and then semi-curing the resin composition in a dryer at 120 to 220 ℃ for about 2 to 15 minutes. In this case, the amount of adhesion of the resin composition to the substrate, that is, the content of the resin composition (including the filler (E)) is preferably in the range of 20 to 99 mass% with respect to the total amount of the prepreg after semi-curing.

The base material used for producing the prepreg of the present embodiment may be any known material used for various printed circuit board materials. Examples of such a substrate include, but are not particularly limited to, glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass, inorganic fibers other than glass such as quartz, organic fibers such as polyimide, polyamide, and polyester, and woven fabrics such as liquid crystal polyester. As the shape of the base material, woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like are known, and any of them may be used. The substrate can be used alone of 1 or appropriate combination of 2 or more and use. Among woven fabrics, those subjected to a super-opening treatment and a closing treatment are particularly preferable from the viewpoint of dimensional stability. Further, a glass woven fabric surface-treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment is preferable from the viewpoint of moisture absorption and heat resistance. The liquid crystal polyester woven fabric is preferable in view of electrical characteristics. Further, the thickness of the substrate is not particularly limited, and is preferably in the range of 0.01 to 0.2mm in the case of the use as a laminate.

Resin sheet

The resin sheet of the present embodiment refers to a support and the resin composition layer (laminate sheet) disposed on the surface of the support, and further refers to only the resin composition layer (single-layer sheet) from which the support has been removed. That is, the resin sheet of the present embodiment includes at least the resin composition of the present embodiment. The laminate sheet can be obtained by applying a solution in which the resin composition is dissolved in the solvent to a support and drying the solution. The support used herein is not particularly limited, and examples thereof include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films having a release agent coated on the surface thereof, organic film substrates such as polyimide films, conductive foils such as copper foils and aluminum foils, and plate-like inorganic films such as glass plates, SUS plates, and FRPs. Examples of the coating method include the following methods: a solution in which the resin composition is dissolved in a solvent is applied to a support by a bar coater, die coater, doctor blade, Baker applicator, or the like, thereby producing a laminate sheet in which the support and the resin composition layer are integrated. The support may be peeled or etched from the resin sheet obtained by coating and then drying, thereby obtaining a single-layer sheet. The single-layer sheet can be obtained without using a support by supplying a solution in which the resin composition of the present embodiment is dissolved or compatible in a solvent into a mold having a sheet-like cavity, drying the solution, and molding the solution into a sheet-like shape.

In the production of the resin sheet or the single-layer sheet according to the present embodiment, the drying conditions for removing the solvent are not particularly limited, and the drying is preferably performed at a temperature of 20 to 200 ℃ for 1 to 90 minutes. When the temperature is 20 ℃ or higher, the solvent can be further prevented from remaining in the resin composition, and when the temperature is 200 ℃ or lower, the progress of curing of the resin composition can be suppressed. The thickness of the resin layer in the resin sheet or single-layer sheet of the present embodiment can be adjusted according to the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited. Among them, the thickness is preferably 0.1 to 500. mu.m. When the thickness of the resin layer is 500 μm or less, the solvent further hardly remains during drying.

The prepreg and the resin sheet may be used as a laminate having a plurality of one or two or more selected from the group consisting of these.

Metal foil clad laminate

The metal foil-clad laminate of the present embodiment has a structure in which at least 1 or more sheets of the prepreg or resin sheet are laminated; and a metal foil disposed on one or both surfaces of the prepreg or the resin sheet. Specifically, the prepreg or the resin sheet may be 1 sheet, or a plurality of sheets of the prepreg or the resin sheet may be stackedA metal foil of copper, aluminum or the like is disposed on one or both surfaces thereof, and laminated and molded. The metal foil used here is not particularly limited as long as it is a material used for printed wiring board materials, and a copper foil such as rolled copper foil and electrolytic copper foil is preferred. The thickness of the metal foil is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm. As the molding conditions, a method used in the production of a laminate plate or a multilayer plate for a printed wiring board in general can be used. For example, a multistage press, a multistage vacuum press, a continuous molding machine, or an autoclave molding machine is used, and the like is heated at a temperature of 180 to 350 ℃ for 100 to 300 minutes under a surface pressure of 20 to 100kg/cm²The metal foil-clad laminate of the present embodiment can be produced by performing lamination molding under the conditions of (1). Further, a multilayer board can be produced by combining the prepreg with a separately produced wiring board for an inner layer and laminating the prepreg and the wiring board. As a method for producing a multilayer board, for example, 35 μm copper foils are arranged on both surfaces of 1 sheet of the prepreg, and the prepreg is laminated under the above conditions to form an inner layer circuit, and the circuit is blackened to form an inner layer circuit board. Further, the inner layer circuit board and the prepreg are alternately arranged for 1 sheet each, and further, a copper foil is arranged on the outermost layer, and lamination molding is performed under the above-described conditions, preferably under vacuum. Thus, a multilayer board can be produced.

Printed circuit board

The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by further performing patterning. The printed circuit board can be manufactured according to a conventional method, and the manufacturing method thereof is not particularly limited. An example of a method for manufacturing a printed wiring board is described below. First, the metal foil-clad laminate is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as necessary, and then a required number of prepregs are stacked on the surface of the inner layer circuit. Further, a metal foil for an outer layer circuit is laminated on the outer side thereof, and the laminate is heated and pressed to be integrally molded. In this manner, a multilayer laminated board in which a base material and an insulating layer containing a cured product of the resin composition are formed between the metal foils for the inner layer circuit and the outer layer circuit is manufactured. Next, the multilayer laminated board is subjected to a drilling process for a through hole or a via hole, and then a plating film of a metal foil for conducting the inner layer circuit and the outer layer circuit is formed on the wall surface of the hole. Further, the metal foil for the outer layer circuit is subjected to etching treatment to form the outer layer circuit, whereby a printed wiring board can be manufactured.

The printed wiring board obtained in the above manufacturing example had: an insulating layer; and a conductor layer formed on a surface of the insulating layer, wherein the insulating layer has a structure including the resin composition of the present embodiment. That is, the prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or applied thereto) and the layer of the resin composition of the metal foil-clad laminate of the present embodiment (the layer including the resin composition of the present embodiment) are configured as an insulating layer including the resin composition of the present embodiment.

Multilayer printed wiring board

As described above, the printed wiring board of the present embodiment is preferably a printed wiring board having a plurality of insulating layers and a plurality of conductor layers, the plurality of insulating layers including: at least 1 or more first insulating layers of at least 1 selected from the group consisting of the prepreg and the resin sheet are laminated; and a 2 nd insulating layer formed of at least 1 selected from the group consisting of the prepreg and the resin sheet, wherein at least 1 sheet of the 2 nd insulating layer is laminated in a single-side direction of the 1 st insulating layer, and the plurality of conductor layers include: a 1 st conductor layer disposed between the insulating layers; and a 2 nd conductor layer disposed on the outermost surface of the plurality of insulating layers. According to the findings of the present inventors, a typical laminate is a multilayer printed wiring board in which another prepreg is laminated in both surface directions of one core substrate, but the prepreg of the present embodiment can be suitably used for manufacturing a coreless multilayer printed wiring board (multilayer coreless substrate) in which another prepreg having a 2 nd insulating layer is laminated only in one surface direction of one prepreg having a 1 st insulating layer. Such a multilayer printed wiring board may have a configuration in which, for example, 2 insulating layers 2 are stacked on 1 insulating layer 1 (that is, a configuration in which a plurality of insulating layers are 3 layers). The 1 st conductor layer and the 2 nd insulating layer may be 1 layer or 2 or more layers each.