TW201903058A - Resin composition, prepreg, resin sheet, metal foil-clad laminate, printed circuit board, and resin composition manufacturing method - Google Patents

Abstract

A resin composition containing an aromatic compound (A) in which a monovalent substituent represented by formula (1a) set forth below and a monovalent substituent represented by formula (1b) set forth below bind directly to an aromatic ring, and a maleimide compound (B). CH2=CR<SP>a</SP>CH2- (1a) R<SP>b</SP>O- (1b) (In formula (1a), R<SP>a</SP> represents a hydrogen atom or a monovalent organic group, and in figure (1b), R<SP>b</SP> represents a monovalent organic group.).

Description

Resin composition, prepreg, resin sheet, metal foil-clad laminate, printed circuit board, and method for producing resin composition

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

In recent years, advances have been made in the performance and miniaturization of semiconductor packages that are widely used in electronic equipment, communication equipment, and personal computers. The high integration and high-density mounting of various components used in semiconductor packages have been accelerating in recent years. Accordingly, the warpage of the semiconductor plastic package caused by the difference in the thermal expansion rate between the semiconductor element and the printed circuit board for the semiconductor plastic package becomes a problem, and various countermeasures have been proposed.

As a countermeasure, it has been considered to increase the glass transition temperature (higher Tg) of a laminated board in a printed circuit board by using a combination of diallyl bisphenol A and a maleimide compound (for example, refer to Patent Document 1). ). [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 02-097561

(Problems to be Solved by the Invention)

However, according to a detailed study by the inventors of the present invention, in the above-mentioned conventional technology, the formability of the printed circuit board is insufficient. In addition, there is room for further improvement in the storage stability of the prepreg, which is a raw material for printed circuit boards. It is hoped that further improvements can be made.

The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a resin composition, a prepreg, a resin sheet, a metal foil-clad laminate, a printed circuit board, and a resin having excellent formability of a printed circuit board and storage stability of the prepreg. Manufacturing method of composition. (The way to solve the problem)

The inventors of the present case have worked hard to achieve the above-mentioned object. As a result, the conventional moldability of printed circuit boards has room for improvement because the prepreg used as the raw material has a high melt viscosity. When this prepreg is laminated and hardened, the resin composition contained in the prepreg has a high melt viscosity. Poor mobility. In addition, it was found that the prepreg has a high melt viscosity and there is room for improvement in storage stability, because, for example, diallyl bisphenol A has an allyl group in the aromatic ring (which may also be substituted. The same applies to the following paragraphs. ) The reason why allyl groups in aromatic compounds with phenolic hydroxyl groups easily react with maleimide groups in maleimide compounds. As a result of further research, it was found that a method for appropriately hindering the reaction between an allyl group and a maleimide group can be used to obtain a resin composition having excellent formability of a printed circuit board and excellent storage stability of a prepreg. this invention.

That is, the present invention is as follows. [1] A resin composition comprising: an aromatic compound (A) in which a monovalent substituent represented by the following formula (1a) and a monovalent substituent represented by the following formula (1b) are directly bonded to an aromatic ring; and Maleimide compound (B); CH ₂ = CR ^a CH _2- (1a) R ^b O- (1b) In formula (1a), R ^a represents a hydrogen atom or a monovalent organic group, in formula (1b) R ^b represents a monovalent organic group. [2] The resin composition according to [1], wherein in the aromatic compound (A), the carbon atom in the aromatic ring bonded to the monovalent substituent represented by the formula (1a) is in the aromatic ring The carbon atoms bonded to the monovalent substituent represented by the formula (1b) are adjacent to each other. [3] The resin composition according to [1] or [2], wherein the monovalent substituent represented by the formula (1b) is a monovalent substituent represented by the following formulae (2), (3), and (4) Any one of In formulae (2), (3), and (4), R ¹ represents a linear or branched alkyl or aryl group having 1 or more carbon atoms which may have a substituent. [4] The resin composition according to [3], wherein R ¹ is a substituent represented by the following formula (5); In formula (5), R ² represents a hydrogen atom or a monovalent organic group. [5] The resin composition according to any one of [1] to [4], wherein the aromatic compound (A) includes a compound represented by the following formula (6); In formula (6), two R ³ each independently represent a hydroxyl group or any of the substituents represented by the following formulae (2), (3), and (4), and at least one of them represents the following formulae (2), (3 ) And (4), each of R ⁴ represents a single bond, an alkylene group, a phenylene group, a phenylene group, or a naphthyl group, and R ⁵ each independently represents a hydrogen atom, an alkyl group, or a phenyl group. , Biphenyl, or naphthyl; [Chem 4] In formulae (2), (3), and (4), R ¹ represents a linear or branched alkyl or aryl group having 1 or more carbon atoms which may have a substituent. [6] The resin composition according to any one of [1] to [5], wherein the maleimide compound (B) is selected from the group consisting of bis (4-maleimidephenyl) methane, 2 , 2-bispyrene 4- (4-maleimide phenoxy) -phenylpyrene propane, bis (3-ethyl-5-methyl-4-maleimide phenyl) methane, poly At least one member of the group consisting of cyclobutane oxide-bis (4-maleimide iminobenzoate) and a maleimide compound represented by the following formula (7); [Chem. 5] In formula (7), R ⁶ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. [7] The resin composition according to any one of [1] to [6], further comprising a group selected from the group consisting of an epoxy resin, a cyanate compound, and nadiimide substituted with an alkenyl group. At least one of them. [8] The resin composition according to any one of [1] to [7], further including an inorganic filler (C). [9] The resin composition according to [8], wherein the inorganic filler (C) includes at least one selected from the group consisting of silica, alumina, and boehmite. [10] The resin composition according to [8] or [9], wherein the content of the inorganic filler (C) is 30 to 500 parts by mass relative to 100 parts by mass of the resin solid content. [11] A prepreg comprising: a substrate; and the resin composition according to any one of [1] to [10] impregnated or coated on the substrate. [12] A resin sheet comprising: a support; and the resin composition according to any one of [1] to [10] applied to the support. [13] A laminated board made by stacking at least one of at least one selected from the group consisting of a prepreg such as [11] and a resin sheet such as [12]. The cured product of the resin composition in at least one of the group consisting of the prepreg and the resin sheet is free. [14] A metal foil-clad laminate having at least one selected from the group consisting of a prepreg as in [11] and a resin sheet as in [12], and disposed in a group selected from the prepreg And at least one kind of single-sided or double-sided metal foil in the group consisting of the resin sheet and the resin composition contained in at least one kind selected from the group consisting of the prepreg and the resin sheet Hardened. [15] A printed circuit board comprising an insulating layer and a conductor layer formed on a surface of the insulating layer, the insulating layer containing the resin composition according to any one of [1] to [10]. [16] A method for producing a resin composition, comprising the following steps: an aromatic compound (A1) in which a monovalent substituent represented by the following formula (1a) and a phenolic hydroxyl group are directly bonded to an aromatic ring; A phenolic hydroxyl-reactive compound is reacted to obtain an aromatic compound (A) in which a monovalent substituent represented by the following formula (1a) and a monovalent substituent represented by the following formula (1b) are directly bonded to an aromatic ring; A step of blending the aromatic compound (A) and the maleimide compound (B); CH ₂ = CR ^a CH _2- (1a) R ^b O- (1b) In the formula (1a), R ^a represents hydrogen An atom or a monovalent organic group. In the formula (1b), R ^b represents a monovalent organic group. (Effect of the invention)

According to the present invention, it is possible to provide a resin composition, a prepreg, a resin sheet, a metal-clad laminate, a printed circuit board, and a resin composition that are excellent in formability of a printed circuit board and storage stability of the prepreg. method.

Hereinafter, this embodiment (hereinafter simply referred to as "this embodiment") will be described in detail, but the present invention is not limited to the following this embodiment. The present invention may be modified in various ways without departing from the spirit thereof.

(Resin composition) The resin composition of this embodiment includes a monovalent substituent represented by the following formula (1a) (hereinafter referred to as "substituted allyl group") and a monovalent substituent represented by the following formula (1b) (hereinafter (Referred to as "substituted hydroxy") an aromatic compound (A) directly bonded to an aromatic ring; and a maleimide compound (B). Here, the aromatic ring is, for example, a benzene ring, a naphthalene ring, and an anthracene ring, preferably a benzene ring and a naphthalene ring, and more preferably a benzene ring. CH ₂ = CR ^a CH _2- (1a) R ^b O- (1b) Here, in the formula (1a), R ^a represents a hydrogen atom or a monovalent organic group, and the number of carbon atoms is preferably 1 ~ 60. R ^{a is more} preferably a hydrogen atom or an alkyl group or an aryl group having 1 to 60 carbon atoms, and is more preferably a hydrogen atom or an alkyl group or an aryl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or a methyl group. Is a hydrogen atom. On the other hand, in formula (1b), R ^b represents a monovalent organic group, and its carbon number is preferably from 3 to 60. The carbon number of R ^b is more preferably 3 to 45, and even more preferably 4 to 43.

In this resin composition, the aromatic compound (A) has a substituted hydroxyl group which has a greater steric hindrance than the phenolic hydroxyl group with respect to the substituted allyl group. Therefore, the progress of the reaction of the substituted allyl group with the maleimide group in the maleimide compound is moderately hindered by the substituted hydroxyl group. As a result, the melt viscosity of the prepreg using the resin composition of the present embodiment can be lower than that of the conventional techniques. As a result, when this prepreg is laminated and hardened, the fluidity of the resin composition is good, and the laminate, the metal foil-clad laminate, and the printed circuit board are excellent in moldability. In addition, by moderately hindering the progress of the above-mentioned reaction, an increase in the viscosity of the prepreg over time is also suppressed, and its storage stability becomes excellent. But the factors to consider are not limited to this.

(Aromatic compound (A)) The aromatic compound (A) according to this embodiment is obtained by directly bonding a substituted allyl group and a substituted hydroxyl group to an aromatic ring. As for the substituted hydroxyl group, it is preferable that R ^b has a hydroxyl group, and R ^b is more preferably a group represented by the following formula (1c). R ^c -CH (OH) -CH _2- (1c) Here, R ^c represents a linear or branched alkyl or aryl group having a carbon number of 1 or more, which may have a substituent or may have oxygen in the chain. . The carbon number of the alkyl group is preferably 4 to 14, and the carbon number of the aryl group is preferably 6 to 12.

More specifically, the substituted hydroxy group may be any monovalent substituent represented by the following formulae (2), (3), and (4). In consideration of the viewpoint of more effectively and surely exerting the effect obtained by the present invention, it is preferably any of the monovalent substituents represented by the following formulae (2), (3), and (4).

[Chemical 6] Here, in formulae (2), (3), and (4), R ¹ represents a linear or branched alkyl or aryl group having 1 or more carbon atoms which may have a substituent. The carbon number of the alkyl group is preferably 4 to 12, and the carbon number of the aryl group is preferably 6 to 12. Among these, from the viewpoint of more effectively and surely exerting the effect obtained by utilizing the present invention, an aryl group having a substituent is preferable, and a phenyl group, a biphenyl group, or a naphthyl group having a substituent is more preferable. The phenyl group which may have a substituent represented by the following formula (5) is more preferable. [Chemical 7] Here, in formula (5), R ² represents a hydrogen atom or a monovalent organic group, and when it is a monovalent organic group, its carbon number is 1 or more.

The substituent in R ¹ is, for example, a monovalent organic group. More specifically, this monovalent organic group and the monovalent organic group of R ² include a monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. The monovalent saturated or unsaturated alicyclic hydrocarbon group having 1 to 40 carbon atoms having a substituent, and the monovalent aromatic hydrocarbon group having 1 to 40 carbon atoms having a substituent may be used. The hydrocarbon group may have one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. As a monovalent saturated or unsaturated straight-chain or branched hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1 to 40 carbon atoms represented by second butyl, third butyl, pentyl, and decyl, alkyl, methoxy, ethoxy, and 3-methylmethoxy represented by carbon 1 ~ 40 of alkoxy and vinyl. It may also have a monovalent saturated or unsaturated alicyclic hydrocarbon group having 1 to 40 carbon atoms, such as cyclopropyl, 2,2-dimethylcyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl. Base, cyclodecyl, menthol, and cyclododecyl. It may also have a monovalent aromatic hydrocarbon group having 1 to 40 carbon atoms, such as 4- (third butyl) phenyl, 2-methylphenyl, 4-methylphenyl, and 4-methoxy. The phenyl group is typified by a phenyl group which may be substituted, and the phenoxy group is typified by a phenoxy group which may be substituted. In addition, the number of carbons in each of the above-mentioned hydrocarbon groups is preferably 3 to 20 in view of the viewpoint of more effectively and surely exerting the effect obtained by utilizing the present invention. When R ² is a monovalent organic group, the number of carbon atoms is preferably 1 to 9. Examples of such a monovalent organic group include those having 1 to 9 carbon atoms in the groups exemplified above.

Specific examples of the aromatic compound (A) include compounds represented by the following formula (6). This compound is preferable from the viewpoint of more effectively and surely exerting the effect obtained by utilizing the present invention. The aromatic compound (A) may be used singly or in combination of two or more kinds.

[Chemical 8] Here, in the formula (6), two R ³ each independently represent a hydroxyl group or any of the substituents represented by the above formulae (2), (3), and (4), and at least one of them represents the above formula (2) , (3) and (4), each of R ⁴ represents a single bond, an alkylene group, a phenylene group, a biphenylene group, or a naphthyl group, and R ⁵ each independently represents a hydrogen atom or an alkyl group. , Phenyl, biphenyl, or naphthyl. Examples of the alkyl group in R ⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, and decyl. R ^{4 is} , for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, or bisphenol. Divalent groups in which two aromatic rings in M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z are bonded. Among these, R ^{4 is} preferably a divalent group in which two aromatic rings in bisphenol A are bonded, that is, isopropylidene (> C (CH ₃ ) ₂ ).

In the aromatic compound (A) of this embodiment, the carbon atom of the aromatic ring bonded by the substituted allyl group and the carbon atom of the aromatic ring bonded by the substituted hydroxyl group are preferably adjacent to each other. Thereby, the reaction between the substituted allyl group in the aromatic compound (A) and the maleimide group in the maleimide compound (B) can be more moderately suppressed. As a result, the moldability of the printed circuit board of the resin composition of this embodiment and the storage stability of the prepreg are more excellent.

The aromatic compound (A) can be produced by a conventional method, or a commercially available product can be obtained. The method for producing the aromatic compound (A) includes, for example, the steps for obtaining the aromatic compound (A) in the method for producing the resin composition of the present embodiment described later, and the method for producing as described in the examples.

In the resin composition of this embodiment, the content of the aromatic compound (A) is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 8 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the resin solid content. When the content of the aromatic compound (A) is within the above range, the moldability of the printed circuit board and the storage stability of the prepreg become more excellent. In addition, in this embodiment, "resin solid content" means a component other than a solvent and a filler in a resin composition unless otherwise specified, and "100 parts by mass of a resin solid content" means a solvent in the resin composition. The total of components other than the filler is 100 parts by mass.

(Maleimide compound (B)) The maleimide compound (B) of this embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bisamidine 4- (4 -Maleimide phenoxy) -phenylammonium propane, bis (3,5-dimethyl-4-maleimide phenyl) methane, bis (3-ethyl-5-methyl- 4-maleimide phenyl) methane, bis (3,5-diethyl-4-maleimide phenyl) methane, a maleimide compound represented by the following formula (7), etc. Prepolymer of maleimide compound, or prepolymer of maleimide compound and amine compound. One of them may be used or two or more of them may be appropriately mixed and used.

Among them, bis (4-maleimideiminophenyl) methane, 2,2-bisammonium 4- (4-maleimimidephenoxy) -phenylarsinepropane, and bis (3-ethyl-5 -Methyl-4-maleimide phenyl) methane and a maleimide compound represented by the following formula (7) are preferred, and a maleimide compound represented by the following formula (7) is particularly preferred. By containing such a maleimidine imine compound, the heat resistance and the elastic modulus maintenance ratio of the obtained hardened product tend to be more excellent. [Chemical 9] Here, in the formula (7), R ⁶ each independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In the formula, n ₁ represents an integer of 1 or more. The upper limit 値 of n ₁ is preferably 10, and more preferably 7.

In the resin composition of this embodiment, the content of the maleimide compound (B) is preferably 5 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the resin solid content, and more preferably 10 parts by mass or more and 50 parts by mass or less. . When the content of the maleimide compound (B) is within the above range, the formability of the printed circuit board and the storage stability of the prepreg are more excellent, and the thermal expansion rate of the hardened product obtained is further reduced and the heat resistance is more improved. Good tendency.

When the compound having an alkenyl group contained in the resin composition of this embodiment is only the aromatic compound (A), the number of alkenyl groups (α) in the aromatic compound (A) and the maleimide compound ( The ratio ((β) / (α)) of the maleimidine imine group (B) in B) should be 0.9 ~ 4.3, more preferably 1.5 ~ 4.0. This ratio ((β) / (α)) is in the above range, and the formability of the printed circuit board and the storage stability of the prepreg are better, and low thermal expansion, thermoelastic modulus, heat resistance, absorption Printed circuit board with better wet heat resistance, deslagging resistance, chemical resistance, and easy hardening.

(Optional component) The resin composition of the present embodiment preferably further contains at least one selected from the group consisting of an epoxy resin, a cyanate compound, and a nadiimide substituted with an alkenyl group. Among these, from the viewpoint of more effectively and surely exerting the effect obtained by utilizing the present invention, it is more preferable that the resin composition of the present embodiment contains an alkenyl-substituted nadicarium imine.

There is no particular limitation on the nadic acid imidate substituted with alkenyl in this embodiment, as long as it is a compound having at least one nadic acid imidate substituted with alkenyl in the molecule. Specific examples thereof include compounds represented by the following formula (8). [Chemical 10] Here, in formula (8), R ⁷ each independently represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R ⁸ represents an alkylene group having 1 to 6 carbon atoms, phenylene group, phenylene group, and phenylene group. Naphthyl, or a group represented by the following formula (9) or (10). [Chemical 11] Here, in formula (9), R ⁹ represents a substituent represented by methylene, isopropylidene, CO, O, S, or SO ₂ . [Chemical 12] Here, in the formula (10), R ¹⁰ represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms which are independently selected.

In addition, a commercially available product may be used as the aldiyl-substituted nadicarium imine represented by the formula (8). Commercial products are not particularly limited, and examples include a compound represented by the following formula (11) (BANI-M (Maruzen Petrochemical Co., Ltd.)) and a compound represented by the following formula (12) (BANI-X (Maruzen Petrochemical ( Share) system)). These may be used individually by 1 type, and may use 2 or more types together. [Chemical 13] [Chemical 14]

In the resin composition of this embodiment, the content of the aldiyl-substituted nadicarium imine is preferably from 10 to 60 parts by mass, and more preferably from 20 to 40 parts by mass, relative to 100 parts by mass of the resin solid content. When the content of the aldiyl-substituted nadicarium imine is within such a range, the moldability when the inorganic filler is filled is excellent. Further, a printed circuit board excellent in hardening properties such as a flexural modulus at 250 ° C, a thermoelastic modulus such as a flexural modulus at a solder reflow temperature, a slag resistance, and a chemical resistance can be obtained. However, from the viewpoint of higher formability of the printed circuit board, it is preferable that the resin composition does not contain nadicarium imine substituted with an alkenyl group.

In addition, when the resin composition of the present embodiment contains, in addition to the aromatic compound (A), any component having an alkenyl group such as nadicarium imine substituted with an alkenyl group, the alkenyl group of each component in the resin composition The ratio of the sum of the numbers (αt) to the number of maleimide groups (β) in the maleimide compound (B) ((β) / (αt)) should be 0.9 ~ 4.3, 1.5 ~ 4.0 more ideal. When the ratio ((β) / (αt)) is within the above range, the formability of the printed circuit board and the storage stability of the prepreg can be obtained better, and the low thermal expansion, thermoelastic modulus, heat resistance, absorption Printed circuit board with better wet heat resistance, deslagging resistance, chemical resistance, and easy hardening.

(Cyanate ester compound) The resin composition according to this embodiment may further contain a cyanate ester compound. The cyanate compound is not particularly limited, and examples thereof include a naphthol aralkyl cyanate represented by the following formula (13), a novolac cyanate represented by the following formula (14), and a biphenylaralkyl cyanate , Bis (3,5-dimethyl 4-cyanooxyphenyl) methane, bis (4-cyanooxyphenyl) methane, 1,3-dicyanooxybenzene, 1,4-dicyanooxy Benzene, 1,3,5-tricyanooxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene, 1,8-dicyanocyanine Oxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4'-dicyanoxybiphenyl, bis ( 4-cyanooxyphenyl) ether, bis (4-cyanoxyphenyl) sulfide, bis (4-cyanoxyphenyl) fluorene, and 2,2'-bis (4-cyanoxyphenyl) ) Propane; prepolymers of these cyanates. These cyanate ester compounds can be used individually by 1 type or in combination of 2 or more types.

[Chemical 15] Here, in the formula (13), R ¹¹ each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred. In formula (13), n ₂ represents an integer of 1 or more. The upper limit 値 of n ₂ is usually 10, and preferably 6.

[Chemical 16] Here, in Formula (14), R ¹² each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred. In formula (14), n ₃ represents an integer of 1 or more. The upper limit 値 of n ₃ is usually 10, preferably 7.

Among these, the cyanate compound preferably includes a naphthol aralkyl type cyanate represented by the formula (13), a novolac type cyanate represented by the formula (14), and a biphenylaralkyl type cyanate One or more members of the group consisting of acid esters are preferred, and are selected from the group consisting of naphthol aralkyl cyanates represented by formula (13) and novolac cyanates represented by formula (14) More than one of them is preferable. By using such a cyanate ester compound, there is a tendency that a hardened product having better flame retardancy, higher hardenability, and a lower thermal expansion coefficient can be obtained.

The manufacturing method of these cyanate ester compounds is not specifically limited, A well-known method can be used as a synthesis method of a cyanate ester compound. The known method is not particularly limited, for example, a method in which a phenolic resin and a cyanogen halide are reacted in a passive organic solvent in the presence of a basic compound, and a salt of the phenolic resin and the basic compound is formed in an aqueous solution. Then, the method of reacting the obtained salt with cyanogen halide at the interface of the 2-phase system.

The phenol resin used as a raw material of these cyanate compounds is not particularly limited, and examples thereof include a naphthol aralkyl phenol resin, a novolac phenol resin, and a biphenylaralkyl phenol resin represented by the following formula (15). [Chem. 17] Here, in Formula (15), R ¹¹ each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred. In formula (15), n ₄ represents an integer of 1 or more. The upper limit 値 of n ₄ is usually 10, preferably 6.

The naphthol aralkyl type phenol resin represented by the formula (15) can be obtained by condensing a naphthol aralkyl resin and cyanic acid. The naphthol aralkyl-type phenol resin is not particularly limited. For example, naphthols such as α-naphthol and β-naphthol, and p-xylylene glycol and α, α'-dimethoxy-p-xylene are used. , And 1,4-bis (2-hydroxy-2-propyl) benzene and other benzenes. The naphthol aralkyl cyanate can be selected from those obtained by condensing a naphthol aralkyl resin obtained as described above and cyanic acid.

The content of the cyanate ester compound is preferably 0.5 to 45 parts by mass, more preferably 5 to 20 parts by mass based on 100 parts by mass of the resin solid content. When the content of the cyanate ester compound is within the above range, the heat resistance and chemical resistance of the obtained cured product tend to be better.

(Epoxy resin) The resin composition of this embodiment may further contain an epoxy resin. The epoxy resin is not particularly limited as long as it is a resin having two or more epoxy groups in one molecule, for example, bisphenol A epoxy resin, bisphenol E epoxy resin, and bisphenol F epoxy resin. Bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, anthracene Epoxy resin, trifunctional phenol epoxy resin, 4-functional phenol epoxy resin, propylene oxide epoxy resin, phenol aralkyl epoxy resin, biphenylaralkyl epoxy resin, aromatic Alkyl novolac epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, polyol epoxy resin, isocyanurate ring containing epoxy resin, or the like Of the halide. Among these, a biphenylaralkyl-type epoxy resin is preferable.

The content of the epoxy resin is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass based on 100 parts by mass of the resin solid content. When the content of the epoxy resin is within the above range, the softness of the obtained cured product, copper foil peeling strength, chemical resistance, and slag resistance tend to be better.

(Inorganic Filler (C)) The resin composition of this embodiment may further contain an inorganic filler (C). The inorganic filler (C) is not particularly limited, for example: natural silicon dioxide, fused silicon dioxide, synthetic silicon dioxide, amorphous silicon dioxide, aerosil, hollow silicon dioxide, and other silicon dioxide; silicon such as white carbon Compounds; titanium oxide, zinc oxide, magnesium oxide, zirconia and other metal oxides; boron nitride, condensed boron nitride, silicon nitride, boehmite and other metal nitrides; metal sulfates such as barium sulfate; aluminum hydroxide, Aluminum hydroxide heat-treated products (heating aluminum hydroxide and reducing some crystal water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate and stannic acid Zinc compounds such as zinc; alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S -Glass, M-glass G20, glass short fibers (including glass micropowders such as E glass, T glass, D glass, S glass, and Q glass.), Hollow glass, and spherical glass. The inorganic filler (C) may be used individually by 1 type, and may use 2 or more types together.

Among them, the inorganic filler (C) includes a group selected from the group consisting of silicon dioxide, aluminum oxide, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and boehmite. At least one member in the group is preferred, and at least one member selected from the group consisting of silica, alumina, and boehmite is more preferred. By using such an inorganic filler (C), the hardened | cured material obtained will tend to become high rigidity and low warpage.

The content of the inorganic filler (C) is preferably 30 to 500 parts by mass, more preferably 100 to 400 parts by mass, and still more preferably 150 to 300 parts by mass with respect to 100 parts by mass of the resin solid content. When the content of the inorganic filler (C) is within the above range, the obtained hardened product tends to have higher rigidity and lower warpage.

(Silane coupling agent and wetting and dispersing agent) The resin composition according to this embodiment may further contain one or more members selected from the group consisting of a silane coupling agent and a wetting and dispersing agent. When the resin composition contains a silane coupling agent and a wetting and dispersing agent, the dispersibility of the inorganic filler (C), the resin component, the inorganic filler (C), and the adhesive strength of the substrate described later tend to be better.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of inorganic substances, for example: γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ- Aminosilane compounds such as aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; silane-based epoxy compounds; γ-acrylic acid propyltrimethoxysilane; acrylic groups Silane-based compounds; cationic silane-based compounds such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane-based compounds. The silane coupling agent may be used singly or in combination of two or more kinds.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used in coatings, for example, DISPERBYK-110, 111, 118, 180, 161, BYK-W996, W9010, W903, etc., manufactured by BYK Chemie Japan.

(Other resins, etc.) The resin composition of this embodiment may further contain, if necessary, a material selected from the group consisting of phenol resin, oxetane resin, and benzofluorene. One or two or more of the group consisting of a compound and a compound having a polymerizable unsaturated group. By containing such other resins, the resin composition tends to have better copper foil peel strength, flexural strength, flexural modulus, and the like of the hardened material obtained.

(Phenolic resin) The phenolic resin may be a phenolic resin having two or more hydroxyl groups in one molecule, and generally known ones can be used, and its type is not particularly limited. Specific examples thereof include 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 phenol resin, and propylene oxide Ester-type phenolic resin, aralkyl novolac-type phenolic resin, biphenylaralkyl-type phenolic resin, cresol novolac-type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol Resin, anthracene phenolic resin, naphthalene skeleton modified novolac phenolic resin, phenol aralkyl phenolic resin, naphthol aralkyl phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, grease There are no special restrictions on cyclic phenol resins, polyhydric alcohol phenol resins, phosphorus-containing phenol resins, and hydroxyl-containing polysiloxane resins. These phenol resins can be used individually by 1 type or in combination of 2 or more types. By containing such a phenol resin, the resin composition tends to be more excellent in adhesiveness and flexibility of the obtained hardened material.

The content of the phenolic resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. When the content of the phenol resin is within the above range, the adhesiveness and flexibility of the obtained hardened product tend to be more excellent.

(Oxetane resin) As the oxetane resin, generally known ones can be used, and the kind thereof is not particularly limited. Specific examples include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyl Alkyloxetane such as oxetane, 3-methyl-3-methoxymethyloxetane, 3,3'-bis (trifluoromethyl) perfluorooxane Butane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toa Synthetic), And OXT-121 (trade name of East Asia Synthesis). These oxetane resins can be used singly or in combination of two or more kinds. The resin composition containing such an oxetane resin tends to be more excellent in adhesiveness, flexibility, and the like of the hardened material obtained.

The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass, relative to 100 parts by mass of the resin solid content. When the content of the oxetane resin is within the above range, the adhesiveness and flexibility of the obtained cured product tend to be more excellent.

(Benzopyrene Compound) Benzopyrene As long as the compound is two or more dihydrobenzofluorenes in one molecule A ring compound is sufficient, and generally known ones can be used, and there is no particular limitation on the kind. Specific examples thereof include bisphenol A benzofluorene BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F benzopyrene BF-BXZ (trade name of Konishi Chemical Co., Ltd.) and bisphenol S benzopyrene BS-BXZ (trade name of Konishi Chemical Co., Ltd.). Benzopyrene The compounds may be used singly or in combination of two or more. The resin composition contains such a benzofluorene The compound tends to be more excellent in flame retardancy, heat resistance, low water absorption, and low dielectric properties of the obtained cured product.

Benzopyrene The content of the compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. Benzopyrene When the content of the compound is within the above range, the heat resistance of the obtained hardened product tends to be more excellent.

(Compounds Having Polymerizable Unsaturated Groups) Compounds having polymerizable unsaturated groups can be generally known, and their types are not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (meth) 2-hydroxypropyl acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentaerythritol tetra (methyl) (Meth) acrylates, dipentaerythritol hexa (meth) acrylates and other mono- or polyhydric alcohols (meth) acrylates; bisphenol A epoxy (meth) acrylates, bisphenol F epoxy Epoxy (meth) acrylates such as (meth) acrylates; and benzocyclobutene resins. These unsaturated compounds can be used singly or in combination of two or more kinds. A resin composition containing such a polymerizable unsaturated group-containing compound tends to have better heat resistance, heat resistance, and the like of the obtained hardened material.

The content of the polymerizable unsaturated group-containing compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass, relative to 100 parts by mass of the solid content of the resin. When the content of the compound having a polymerizable unsaturated group is within the above range, the heat resistance and heat resistance of the obtained hardened product tend to be more excellent.

(Hardening Accelerator) The resin composition of this embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, for example: imidazoles such as triphenylimidazole; benzamidine peroxide, laurel oxide, acetamidine peroxide, benzamidine peroxychloride, and diperoxyphthalate Organic peroxides such as tributyl ester; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N -Dimethylpyridine, 2-N-ethylaniline ethanol, tri-n-butylamine, pyridine, quinoline, N-methyl Tertiary amines such as phosphine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol ; Organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron ethylacetonate; etc. Organic metal salts prepared by dissolving hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; dioctyl tin oxide, other alkyl tin, and alkyl oxides Organotin compounds such as tin. Among these, triphenylimidazole is particularly preferable because it promotes a hardening reaction and tends to have excellent glass transition temperature and thermal expansion coefficient.

(Solvent) The resin composition of the present embodiment may further contain a solvent. When the resin composition contains a solvent, the viscosity of the resin composition during preparation is lowered, the handleability is better, and the impregnation property to the substrate described later tends to be better.

The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition, for example, ketones such as acetone, methyl ethyl ketone, and methylcythreon; aromatic hydrocarbons such as toluene and xylene; Methylamines such as methylamine; and propylene glycol monomethyl ether and its acetate. The solvents may be used singly or in combination of two or more kinds.

(Manufacturing method of resin composition) The manufacturing method of the resin composition of this embodiment is not particularly limited. For example, the method includes the following steps: an aromatic compound (A1) in which a substituted allyl group and a phenolic hydroxyl group are directly bonded to an aromatic ring; ), An aromatic compound (A) obtained by reacting a compound that reacts with a phenolic hydroxyl group to obtain a substituted allyl group and a substituted hydroxyl group directly bonded to an aromatic ring; and an aromatic compound (A) and maleimide A step of compound (B) blending.

The aromatic compound (A1) is a substituted allyl group and a phenolic hydroxyl group directly bonded to an aromatic ring. Such an aromatic compound (A1) is not particularly limited, and for example, a compound represented by the following formula (16). [Chemical 18] Here, in formula (16), R ⁴ and R ⁵ are synonymous with those in formula (6).

Moreover, as a compound which reacts with a phenolic hydroxyl group, a monofunctional epoxy compound is mentioned, for example. As the monofunctional epoxy compound, for example, any of the compounds represented by the following formulae (17), (18), and (19), considering the viewpoint of more effectively and reliably exerting the effects obtained by utilizing the present invention, such compounds are preferred. Better. [Chemical 19] Here, in the formulae (17), (18), and (19), R ¹ is synonymous with the formulae (2), (3), and (4). Regarding R ¹ , considering the viewpoint of more effectively and surely exerting the effect obtained by utilizing the present invention, an aryl group which may have a substituent is more preferable, and a phenyl group, a biphenyl group, or a naphthyl group which has a substituent is more preferable. Preferably, a phenyl group which may also have a substituent represented by the above formula (5) is preferred.

In the aromatic compound (A1) of this embodiment, it is preferable that carbon atoms in an aromatic ring bonded by an allyl group and carbon atoms in an aromatic ring bonded by a phenolic hydroxyl group are adjacent to each other. Thereby, the progress of the reaction between the substituted allyl group in the aromatic compound (A) and the maleimide group in the maleimide compound (B) can be more appropriately suppressed. As a result, the moldability of the printed circuit board of the resin composition of this embodiment and the storage stability of the prepreg are more excellent.

In the step of obtaining the aromatic compound (A), a hardening accelerator may be appropriately added if necessary. Examples of the hardening accelerator include the above. The addition amount of the hardening accelerator is not particularly limited as long as the amount of the aromatic compound (A) can be obtained, and it is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the aromatic compound (A) to be obtained, and is 0.01. More preferably, it is more than 1 mass part.

In the step of obtaining the aromatic compound (A), the reaction temperature is not particularly limited as long as the temperature at which the aromatic compound (A) can be obtained, and it is preferably 50 ° C or higher and 160 ° C or lower, and more preferably 100 ° C or higher and 140 ° C or lower.

Then, the aromatic compound (A) and the maleimide compound (B) are blended. In this step, not only the aromatic compound (A) and the maleimide compound (B), but also other components contained in the resin composition are sequentially blended into the solvent and stirred sufficiently to obtain the resin composition. Thing. In this case, in order to dissolve or disperse each component uniformly, a known treatment such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the inorganic filler (C) with respect to the resin composition can be improved by performing the stirring and dispersing treatment by using a stirring tank equipped with a stirrer having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, a device for mixing, such as a ball mill and a bead mill, or a known device such as a revolving or self-converting mixing device.

Moreover, when preparing the resin composition of this embodiment, an organic solvent and / or a hardening accelerator can be used as needed. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples are as described above. The type of the hardening accelerator is not particularly limited as long as it can harden the resin composition. Specific examples are as described above.

(Use) (Prepreg) The prepreg according to this embodiment includes: a substrate; and the resin composition impregnated or coated on the substrate. The manufacturing method of the prepreg can be carried out according to a conventional method, and there is no particular limitation. For example, the resin component in this embodiment can be impregnated or coated on a substrate, and then heated in a dryer at 100 to 200 ° C for 1 to 30 minutes, etc., and then semi-hardened (B-staged) to produce this product. The prepreg of the embodiment.

The content of the resin composition (including the inorganic filler) is not particularly limited, and is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and still more preferably 40 to 80% by mass relative to the total mass of the prepreg. . When the content of the resin composition is within the above range, the moldability tends to be better. Considering the same viewpoint, the content of the substrate is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and still more preferably 20 to 60% by mass relative to the total mass of the prepreg.

The substrate is not particularly limited, and known products used in various printed circuit board materials may be appropriately selected depending on the intended use and performance. Specific examples thereof are not particularly limited, for example: glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass; inorganic fibers other than glass such as quartz; polyparaphenylene Amides terephthalamide (KEVLAR (registered trademark), Dupont (shares) Corporation), copoly-p-phenylene - 3,4 '- (oxybis trademark phenylene terephthalamide Amides (TECHNORA,) , Teijin Technoproducts, etc.) Fully aromatic polyamines; 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (VECTRAN (registered trademark), Kuraray (stock) company), Zxion (registered trademark, KB Seiren) and other polyesters; polyparaphenylene benzobisoxazole (Zylon (registered trademark), Toyobo Co., Ltd.), organic fibers such as polyimide. Among these, from the viewpoint of low thermal expansion, E glass, T glass, S glass, Q glass, and organic fibers are preferred. These substrates may be used alone or in combination of two or more.

The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, cut strand felts, and surface felts. The weaving method of the woven fabric is not particularly limited. For example, a plain weave, a basket weave, a twill weave, etc. are known, and can be appropriately selected from these known products depending on the purpose and performance of the purpose. Further, it is preferable to use a glass woven fabric that has been fiber-opened and surface-treated with a silane compound such as a silane coupling agent. The thickness and quality of the substrate are not particularly limited, and generally a substrate having a thickness of about 0.01 to 0.3 mm is preferably used. In particular, from the viewpoint of strength and water absorption, it is preferable that the substrate is a glass woven fabric having a thickness of 200 μm or less and a mass (weight per unit area) of 250 g / m ² or less. A woven fabric (cloth) of one or more kinds of fibers in a group composed of glass fiber and organic fiber of glass is more preferable.

The prepreg according to this embodiment is excellent in storage stability by being provided with the resin composition. It is considered that the reason is that the reaction of the above-mentioned substituted allyl group in the aromatic compound (A) with the maleimide group in the maleimide compound proceeds due to the above-mentioned substituent in the aromatic compound (A). However, it moderately hindered, and as a result, the increase in the viscosity of the prepreg over time was suppressed.

(Resin sheet) The resin sheet according to this embodiment includes a support (sheet substrate) and the resin composition coated on the sheet substrate, and the resin composition is laminated on one or both sides of the sheet substrate. The resin sheet is used as a thin-formed member. For example, a thermosetting resin (including an inorganic filler) used in a prepreg or the like can be directly coated on a support such as a metal foil, a film, and dried.

The sheet substrate is not particularly limited, and known products used in various printed circuit board materials can be used. Sheet substrates, such as: polyimide film, polyimide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polymer Acrylic (PP) film, polyethylene (PE) film, aluminum foil, copper foil and gold foil. Among them, electrolytic copper foil and PET film are preferred.

The coating method is, for example, a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a sheet substrate with a coating rod, a die coater, a doctor blade, a Baker applicator, or the like.

The resin sheet is preferably one in which the above-mentioned resin composition is applied to a support (sheet substrate) and then semi-hardened (B-staged). As a method of obtaining such a resin sheet, specifically, after coating the said resin composition on a sheet base material, such as a copper foil, and heating it in a dryer at 100-200 degreeC for 1-60 minutes, etc., are mentioned. Semi-hardened method for manufacturing resin sheet. The adhesion amount of the resin composition to the support is preferably in the range of 1 to 300 μm based on the resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a build-up material for a printed circuit board.

(Laminated sheet and metal-clad laminated sheet) The laminated sheet of this embodiment is formed by stacking at least one sheet selected from the group consisting of the above-mentioned prepreg and resin sheet. The cured product of the resin composition contained in at least one of the group consisting of the prepreg and the resin sheet is free. This laminated board can be obtained, for example, by laminating one or more sheets of at least one selected from the group consisting of the above-mentioned prepreg and a resin sheet, and curing them. The metal foil-clad laminate according to this embodiment has at least one selected from the group consisting of the prepreg and the resin sheet, and has a structure selected from the group consisting of the prepreg and the resin sheet. At least one type of single-sided or double-sided metal foil includes a hardened product of a resin composition contained in at least one selected from the group consisting of the above-mentioned prepreg and a resin sheet. The metal foil-clad laminate can be formed by laminating at least one or more types selected from the group consisting of the above-mentioned prepreg and resin sheet, and arranging metal foils on one or both sides to form a laminate. . More specifically, one or more of the aforementioned prepregs and / or resin sheets may be stacked, and metal foils such as copper and aluminum may be disposed on one or both sides of the prepregs, as appropriate, and laminated as necessary. A metal foil-clad laminate was prepared. The metal foil used here is not particularly limited as long as it is a user in a printed circuit board material, and is preferably a known copper foil such as a rolled copper foil or an electrolytic copper foil. The thickness of the metal foil is not particularly limited, but is preferably 1 to 70 μm, and more preferably 1.5 to 35 μm. The method and conditions for forming the metal foil-clad laminated board are also not particularly limited, and methods and conditions for general laminated boards and multilayer boards for printed circuit boards can be used. For example, multi-stage presses, multi-stage vacuum presses, continuous forming machines, and autoclave forming machines can be used when forming metal-clad laminates. In addition, the formation of a metal foil-clad laminate generally has a temperature of 100 to 300 ° C., a pressure of 2 to 100 kgf / cm ² , and a heating time in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing may be performed at a temperature of 150 to 300 ° C. Furthermore, a multilayer board can be produced by combining the above-mentioned prepreg and a wiring board for an inner layer which is separately produced, and forming the multilayer board.

(Printed circuit board) The printed circuit board of this embodiment includes an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer contains the resin composition. The conductor layer that becomes a circuit can be formed from the metal foil in the metal foil-clad laminate described above. Alternatively, the conductor layer may be formed by electroless plating on the surface of the insulating layer. This printed circuit board is excellent in chemical resistance, scum resistance, and insulation reliability, and can be particularly effectively used as a printed circuit board for such a semiconductor package.

Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the above-mentioned metal-clad laminate (copper-clad laminate, etc.) is prepared. The surface of the metal foil-clad laminate is etched to form an inner-layer circuit, and an inner-layer substrate is produced. The inner layer circuit surface of the inner layer substrate is optionally subjected to a surface treatment for improving the adhesive strength. Next, a predetermined number of the above-mentioned prepregs are stacked on the surface of the inner-layer circuit, and a metal foil for the outer-layer circuit is laminated on the outer side of the inner-layer circuit, heated and pressurized, and integrally formed. In this way, a multilayer laminated board in which a base material and an insulating layer made of a cured product of a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit can be manufactured. Secondly, the multilayer laminated board is subjected to an opening process for through holes and interlayer holes. Thereafter, a slag removal process, that is, a slag removal process, is performed to remove residues of the resin from the resin component contained in the hardened layer, that is, a slag removal process. A plating metal film is formed on the wall surface of the hole to make the inner layer circuit and the outer layer metal foil conductive, and then the metal foil for the outer layer circuit is etched to form the outer layer circuit, so that a printed circuit board is manufactured.

For example, the prepreg (the substrate and the resin composition attached to the substrate), the resin composition layer (the layer constituting the resin composition) of the metal foil-clad laminate, and the resin composition layer containing the resin composition Insulation.

When a metal foil-clad laminate is not used, a printed circuit board can be formed by forming a conductor layer for a circuit on the prepreg or the resin sheet. In this case, the formation of the conductive layer can also be performed by electroless plating.

According to this embodiment, the reaction of the substituted allyl group in the aromatic compound (A) with the maleimide group in the maleimide compound proceeds through the above-mentioned substitution in the aromatic compound (A). Base and moderate obstruction. As a result, the melt viscosity of the prepreg is lower than that of a conventional art. Therefore, when this prepreg is laminated and cured, the resin composition has good fluidity, and the printed circuit board has excellent moldability. Examples

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

(Synthesis example 1) Synthesis of α-naphthol aralkyl cyanate resin. Α-naphthol aralkyl phenol resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd. 300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol; 1.5 mol with respect to 1 mol of hydroxyl group) of triethylamine were dissolved in 1800 g of methylene chloride, and this was used as solution 1. 125.9 g of cyanogen chloride (2.05 mol; 1.6 mol relative to 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g of 36% hydrochloric acid (1.92 mol; 1.5 mol relative to 1 mol of hydroxyl group), and 1205.9 g of water were kept under stirring. In the state of liquid temperature of -2 ~ -0.5 ℃, it takes 30 minutes to fill solution 1. After the addition of solution 1 was completed, after stirring at the same temperature for 30 minutes, a solution of 65 g of triethylamine (0.64 mol; 0.5 mol relative to 1 mol of hydroxyl group) in 65 g of dichloromethane was added over 10 minutes (solution 2). . After the addition of solution 2 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction. After that, the reaction solution was allowed to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater that was washed for the fifth time was 5 μS / cm, and it was confirmed that the ionic compounds that can be removed were sufficiently removed by water washing. After washing with water the organic phase was concentrated under reduced pressure, finally allowed 1 hour and concentrated to dryness at 90 ℃, to obtain the naphthol aralkyl type cyanate ester compound R (in the formula represented by the above formula (13) are ¹¹ It is a hydrogen atom. SN495V-CN, cyanate group equivalent: 261 g / eq., Orange sticky substance) 331 g. The infrared absorption spectrum of the obtained SN495V-CN showed an absorption of 2250 cm ^-1 (cyanate group) and did not show an absorption of a hydroxyl group.

(Synthesis Example 2) Synthesis of aromatic compound (A) In the reactor, diallyl bisphenol A (DABPA, manufactured by Daiwa Chemical Industry Co., Ltd.) equivalent to the aromatic compound (A1), hydroxyl equivalent: 154 g / eq.) 5.0 parts by mass and 7.5 parts by mass of a monofunctional epoxy compound (product name "ED-509E", manufactured by ADEKA) equivalent to a compound that reacts with a phenolic hydroxyl group, and an imidazole-based hardening accelerator (2, 4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) 0.05 parts by mass was mixed. This mixture was heated at 135 ° C. for 1 hour or more until the reaction was completed to obtain a compound represented by the formula (21) corresponding to the aromatic compound (A). The completion of the reaction was confirmed by GPC (gel permeation chromatography). [Chemical 20]

(Synthesis Example 3) Synthesis of aromatic compound In the reactor, diallyl bisphenol A (DABPA, manufactured by Daiwa Chemical Industry Co., Ltd., hydroxyl equivalent weight: 154 g / eq.) Corresponding to the aromatic compound (A1). 5.3 parts by mass, monofunctional epoxy compound (product name "YED-188", manufactured by Mitsubishi Chemical Corporation), 7.1 parts by mass, and imidazole-based hardening accelerator (2,4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd. Manufactured))) 0.05 parts by mass are mixed. This mixture was heated at 135 ° C for 1 hour or more until the reaction was completed to obtain a compound represented by the formula (22) corresponding to the aromatic compound (A). The completion of the reaction was confirmed by GPC (gel permeation chromatography). [Chemical 21]

(Example 1) 10.0 parts by mass of an α-naphthol aralkyl-type cyanate resin obtained in Synthesis Example 1, a novolac-type maleimide compound (BMI-2300, manufactured by Yamato Chemical Industries, Ltd., functional Group equivalent: 186 g / eq.) 45.0 parts by mass, bisallyl nadic acid imine (BANI-M, manufactured by Maruzan Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.) 25.0 parts by mass, Synthesis Example 2 12.5 parts by mass of the compound represented by the above formula (21), 7.0 parts by mass of biphenylaralkyl-type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.), And silane Coupling agent (Z-6040, Toray Dow Corning Co., Ltd.) 6.9 parts by mass, wetting dispersant (DISPERBYK-111, BYK Chemie Japan (product)) 1.0 part by mass, and wetting dispersant DISPERBYK-161, BYK Chemie Japan (Manufactured) 1.0 part by mass, imidazole-based hardening accelerator (2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)) 0.5 part by mass, and fused silica (SC-4053SQ, Admatechs (Co., Ltd.) 200 parts by mass were mixed and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric (thickness: 95 μm, mass (weight per unit area): 108 g / m ^2. The same applies hereinafter), and dried at 130 ° C. for 3 minutes to obtain a resin composition content of 45% by mass. Prepreg.

(Example 2) 10.0 parts by mass of an α-naphthol aralkyl-type cyanate resin obtained in Synthesis Example 1, a novolac-type maleimide compound (BMI-2300, manufactured by Yamato Chemical Industries, Ltd., functional Base equivalent: 186 g / eq.) 45.0 parts by mass, bisallyl nadic acid imine (BANI-M, manufactured by Maruzan Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.) 25.0 parts by mass, Synthesis Example 3 13.0 parts by mass of the compound represented by the above formula (22), 7.0 parts by mass of biphenylaralkyl-type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.), And silane Coupling agent (Z-6040, Toray Dow Corning Co., Ltd.) 6.9 parts by mass, moist dispersant (DISPERBYK-111, BYK Chemie Japan), 1.0 part by mass and wetting dispersant DISPERBYK-161, BYK Chemie 1.0 parts by mass, manufactured by Japan, 0.5 parts by mass of imidazole-based hardening accelerator (2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)), and fused silica (SC-4053SQ, 200 parts by mass of Admatechs (products) were mixed and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric, and heated and dried at 130 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 45% by mass.

(Comparative Example 1) 10.0 parts by mass of an α-naphthol aralkyl cyanate resin obtained in Synthesis Example 1, a novolac maleimide compound (BMI-2300, manufactured by Yamato Chemical Industries, Ltd., functional Base equivalent: 186 g / eq.) 45.0 parts by mass, bisallyl nadic acid imine (BANI-M, manufactured by Maruzan Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.) 25.0 parts by mass, which is aromatic 5.0 parts by mass of diallyl bisphenol A (DABPA, manufactured by Daiwa Chemical Industry Co., Ltd., hydroxyl equivalent: 154 g / eq.) Of compound (A1), a monofunctional ring of a compound having a monovalent organic group represented by R 7.5 parts by mass of an oxygen compound (product name "ED-509E", manufactured by ADEKA), a biphenylaralkyl epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.) 7.0 parts by mass, silane coupling agent (Z-6040, manufactured by Toray Dow Corning Co., Ltd.) 6.9 parts by mass, moist dispersant (DISPERBYK-111, BYK Chemie Japan Co., Ltd.) 1.0 part by mass, and moist dispersant DISPERBYK -161, 1.0 part by mass of BYK Chemie Japan (stock), 0.5 part by mass of imidazole-based hardening accelerator (2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)), and melting Silicon oxide (SC-4053SQ, Admatechs (shares) Ltd.) 200 parts by mass mixed, diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric, and heated and dried at 130 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 45% by mass.

(Comparative Example 2) 10.0 parts by mass of an α-naphthol aralkyl-type cyanate resin obtained in Synthesis Example 1, a novolac-type maleimide compound (BMI-2300, manufactured by Yamato Chemical Industries, Ltd., functional Group equivalent: 186 g / eq.) 47.0 parts by mass, bisallyl nadic acid imine (BANI-M, manufactured by Maruzan Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.) 36.0 parts by mass, biphenyl aromatic Alkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.) 7.0 parts by mass, silane coupling agent (Z-6040, manufactured by Toray Dow Corning Co., Ltd.) 6.9 parts by mass, 1.0 part by mass of a wet dispersant (DISPERBYK-111, BYK Chemie Japan (stock)) and 1.0 part by mass of a wet dispersant DISPERBYK-161, manufactured by BYK Chemie Japan (stock), imidazole-based hardening accelerator (2 0.5 parts by mass of 4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 parts by mass of fused silica (SC-4053SQ, manufactured by Admatechs Co., Ltd.) were mixed and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric, and heated and dried at 130 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 45% by mass.

[Production of a metal foil-clad laminate] For one piece of the prepreg obtained as described above, a 12 μm-thick electrolytic copper foil (3EC-III, manufactured by Mitsui Metals Mining Co., Ltd.) was placed at a pressure of 30 kgf / cm ² The laminate was formed at a temperature of 220 ° C for 120 minutes to obtain a copper-clad laminate having an insulation layer thickness of 0.1 mm.

[Glass Transition Temperature (Tg)] After obtaining the copper-clad laminate as described above, the copper foils on both sides thereof were removed by etching to obtain a sample. For this sample, a dynamic viscoelasticity measuring device (manufactured by TA Instrument Japan Co., Ltd.) was used in accordance with JIS K7244-3 (JIS C6481) at a start temperature of 50 ° C, an end temperature of 350 ° C, and a heating rate of 10 ° C / min. Conditions determine dynamic viscoelasticity. The maximum value of the loss elastic modulus (E ") obtained at this time is the glass transition temperature. The glass transition temperature is an index of heat resistance. Also, in Table 1, the glass transition temperature is registered in the region below 350 ° C. When there is no glass transition temperature in the area below 350 ° C, "＞ 350 ° C" is registered. The results are shown in Table 1.

[Formability of Printed Circuit Board] After the copper-clad laminated board was obtained as described above, the copper foils on both sides thereof were removed by etching to obtain a sample. The surface of this sample was visually observed, and the presence or absence of porosity was evaluated. When many pores are confirmed, they are regarded as incapable of forming, and they are rated as "C". When there are many pores, but they are few, they are rated as "formable." Rated "A". The results are shown in Table 1.

[Minimum Melt Viscosity of Prepregs] Regarding the minimum melt viscosity of the prepregs obtained in the above examples and comparative examples, a rheometer (manufactured by TA Instrument Japan Co., Ltd.) was used to start the temperature at 80 ° C and end the temperature at 180 Measured under the conditions of ℃, heating rate of 3 ℃ / min, frequency of 10 pts / s, and strain of 0.1%. The lower the minimum melt viscosity, the better the flow characteristics (resin flowability) at the time of manufacturing the laminate, and the better the moldability. The results are shown in Table 1.

[Preservation stability of prepreg] The prepreg obtained as described above was stored in a thermostatic bath and stored at 40 ° C for one week. The change in viscosity before and after this storage was measured using a flow meter. The details were measured using a flow meter (Shimadzu Corporation) under the conditions of a measurement temperature of 120 ° C., a tensile load of 10 kg, a mold hole diameter of 1 mm, and a mold length of 10 mm. The smaller the change in viscosity, the longer the period during which the flow characteristics (resin fluidity) of the laminated board is maintained and the longer the preservation period is, which means that the storage stability of the prepreg is excellent. The results are shown in Table 1.

【Table 1】

This application is based on a Japanese patent application filed on May 26, 2017 (Japanese Patent Application No. 2017-104096), the contents of which are incorporated herein by reference. (Industrial availability)

According to the present invention, a resin composition and the like having excellent formability of a printed circuit board and storage stability of a prepreg can be provided. Therefore, the printed circuit board used in a semiconductor plastic package has industrial applicability.

Claims (16)

A resin composition comprising: an aromatic compound (A) in which a monovalent substituent represented by the following formula (1a) and a monovalent substituent represented by the following formula (1b) are directly bonded to an aromatic ring; Imine compound (B); CH ₂ = CR ^a CH _2- (1a) R ^b O- (1b) In the formula (1a), R ^a represents a hydrogen atom or a monovalent organic group, and in the formula (1b), R ^b Represents a monovalent organic group. For example, the resin composition of claim 1 in the patent application, wherein in the aromatic compound (A), the carbon atom in the aromatic ring bonded to the monovalent substituent represented by the formula (1a) and the aromatic ring The carbon atoms bonded to the monovalent substituent represented by the formula (1b) are adjacent to each other. For example, the resin composition according to item 1 or 2 of the patent application scope, wherein the monovalent substituent represented by the formula (1b) is any of the monovalent substituents represented by the following formulas (2), (3), and (4). One of In formulae (2), (3), and (4), R ¹ represents a linear or branched alkyl or aryl group having 1 or more carbon atoms which may have a substituent. For example, the resin composition of claim 3, wherein R ¹ is a substituent represented by the following formula (5); In formula (5), R ² represents a hydrogen atom or a monovalent organic group. For example, the resin composition of the scope of application for the patent item 1 or 2, wherein the aromatic compound (A) includes a compound represented by the following formula (6); In formula (6), two R ³ each independently represent a hydroxyl group or any of the substituents represented by the following formulae (2), (3), and (4), and at least one of them represents the following formulae (2), (3 ) And (4), each of R ⁴ represents a single bond, an alkylene group, a phenylene group, a phenylene group, or a naphthyl group, and R ⁵ each independently represents a hydrogen atom, an alkyl group, or a phenyl group. , Biphenyl, or naphthyl; In formulae (2), (3), and (4), R ¹ represents a linear or branched alkyl or aryl group having 1 or more carbon atoms which may have a substituent. For example, the resin composition of claim 1 or 2, wherein the maleimide compound (B) is selected from the group consisting of bis (4-maleimidephenyl) methane, 2,2-bisamidine 4 -(4-maleimidoiminophenoxy) -phenylphosphonium propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polycyclobutane oxide- At least one member of the group consisting of bis (4-maleimide iminobenzoate) and a maleimide compound represented by the following formula (7); [化 5] In formula (7), R ⁶ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. For example, the resin composition of item 1 or 2 of the patent application scope further includes at least one selected from the group consisting of epoxy resin, cyanate compound, and nadiimide substituted with alkenyl group. For example, the resin composition in the scope of claims 1 or 2 further includes an inorganic filler (C). For example, the resin composition according to item 8 of the patent application scope, wherein the inorganic filler (C) includes at least one selected from the group consisting of silica, alumina, and boehmite. For example, the resin composition according to item 8 of the patent application range, wherein the content of the inorganic filler (C) is 30 to 500 parts by mass relative to 100 parts by mass of the resin solid content. A prepreg comprising: a substrate; and a resin composition impregnated or coated on the substrate as described in any one of claims 1 to 10 of the scope of patent application. A resin sheet comprising: a support; and the resin composition according to any one of claims 1 to 10 applied to the support. A laminated board is formed by stacking more than one piece of at least one selected from the group consisting of a prepreg such as item 11 of the patent application scope and a resin sheet such as item 12 of the patent application scope, and containing A hardened product of a resin composition included in at least one selected from the group consisting of the prepreg and the resin sheet. A metal foil-clad laminate having at least one member selected from the group consisting of a prepreg as in item 11 of the patent application scope and a resin sheet as in item 12 of the patent application scope, and arranged in a group selected from the group consisting of A prepreg and at least one kind of metal foil in a group consisting of the resin sheet and a resin containing at least one kind selected from the group consisting of the prepreg and the resin sheet A hardened composition. A printed circuit board includes an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer contains the resin composition according to any one of claims 1 to 10. A method for producing a resin composition, comprising the following steps: an aromatic compound (A1) in which a monovalent substituent represented by the following formula (1a) and a phenolic hydroxyl group are directly bonded to an aromatic ring; a meeting; and a phenolic hydroxyl group The reacted compound is reacted to obtain an aromatic compound (A) in which a monovalent substituent represented by the following formula (1a) and a monovalent substituent represented by the following formula (1b) are directly bonded to an aromatic ring; Step of aromatic compound (A) and maleimide compound (B); CH ₂ = CR ^a CH _2- (1a) R ^b O- (1b) In the formula (1a), R ^a represents a hydrogen atom or 1 Valent organic group, in the formula (1b), R ^b represents a monovalent organic group.