CN106973490B

CN106973490B - Use of siloxane compounds for printed wiring boards

Info

Publication number: CN106973490B
Application number: CN201611030566.4A
Authority: CN
Inventors: 小竹智彦; 长井骏介; 桥本慎太郎; 安部慎一郎; 宫武正人; 高根泽伸; 村井曜
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Lishennoco Co ltd; Resonac Holdings Corp
Priority date: 2012-11-28
Filing date: 2013-11-28
Publication date: 2020-07-07
Anticipated expiration: 2033-11-28
Also published as: CN106973490A; CN104812805B; JPWO2014084310A1; KR20150089017A; JP6372071B2; JP6747655B2; TW201434850A; JPWO2014084318A1; TW201428030A; JP2014129520A; TWI614286B; TWI614262B; JP6375951B2; WO2014084318A1; CN107254049A; CN104812805A; KR102166235B1; WO2014084310A1

Abstract

The present invention provides a siloxane compound having a structure represented by the following general formula (1) and the following general formula (2). [ formula 1]

R₁And R₂Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an acetyl group, a hydroxyl group, a sulfonic group, a sulfoalkoxy group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and x and y are each independently an integer of 0 to 4. A is a single bond, or azomethine, ester, amide, azoxy, azo, ethylene or ethynyl. [ chemical formula 2)]

R₃And R₄Each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100.

Description

Use of siloxane compounds for printed wiring boards

The present application is a divisional application of patent applications of inventions having international application numbers PCT/JP2013/082072, application number 201380061809.9 at the stage of entering china, and invention names "silicone compound, modified imide resin, thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package", which are filed by the applicant on application date 2013, 11/28.

Technical Field

The present invention relates to a silicone compound suitable for use in semiconductor packages and printed wiring boards, a modified imide resin using the same, a thermosetting resin composition, a prepreg, a film with resin, a laminate, a multilayer printed wiring board, and a semiconductor package.

Background

With the recent trend toward miniaturization and high performance of electronic devices, the density and integration of wiring in multilayer printed wiring boards have been increasing, and accordingly, there has been an increasing demand for improvement in reliability due to improvement in heat resistance of multilayer printed wiring laminates. In such applications, particularly in semiconductor packages, excellent heat resistance and low thermal expansion are required at the same time. In addition, dielectric characteristics corresponding to the increase in frequency of electric signals are also required.

In this regard, known liquid crystalline polymers such as polyester-based, polyamide-based, polycarbonate-based, polythiol-based, polyether-based, and polyazomethine-based ones are thermosetting resins having excellent low thermal expansion properties, dielectric properties, and heat resistance, but have problems of processability and moldability, and are difficult to handle due to low solubility in organic solvents.

Among these liquid crystalline polymers, since g.f.d' Alelio found polyazomethine as a liquid crystalline oligomer (see non-patent document 1), many cases of resins using polyazomethine have been reported (see patent documents 1 to 7).

Patent document 1 discloses various polyazomethines, and patent documents 2 to 7 disclose polyazomethines having a specific structure. Patent documents 8 and 9 disclose thermosetting polyazomethine resins containing an unsaturated group, and these resins are described to exhibit high heat resistance.

Documents of the prior art

Patent document

Patent document 1 Japanese patent laid-open No. Sho 51-138800

Patent document 2 Japanese laid-open patent publication No. 60-181127

Patent document 3 Japanese laid-open patent publication No. 60-101123

Patent document 4 Japanese patent laid-open No. 2003-073470

Patent document 5 Japanese patent laid-open No. 63-193925

Patent document 6, Japanese patent application laid-open No. H01-069631

Patent document 7 Japanese patent application laid-open No. H01-079233

Patent document 8, Japanese patent application laid-open No. H05-140067

Patent document 9, Japanese patent application laid-open No. 2011-

Non-patent document

Non-patent document 1 Polymer Sci.Tech., Wiley-Interscience, New York, 1969, Vol.10, pp.659-670

Disclosure of Invention

Problems to be solved by the invention

However, the polyazomethines described in patent documents 1 to 7 may be insufficient in heat resistance and moldability when applied to a copper-clad laminate or an interlayer insulating material.

Further, the thermosetting polyazomethine resin described in patent document 8 still has insufficient improvement in heat resistance and toughness, and when these resins are applied to a copper-clad laminate or an interlayer insulating material, heat resistance, reliability, processability, and the like may be insufficient.

Further, the thermosetting polyazomethine resin described in patent document 9 is unsatisfactory in terms of low curing shrinkage and low thermal expansion coefficient.

In view of such a situation, an object of the present invention is to provide a silicone compound, a modified imide resin, a thermosetting resin composition, a prepreg using the same, a film with resin, a laminate, a multilayer printed wiring board, and a semiconductor package, which can realize a thermosetting resin composition that exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications.

Means for solving the problems

The present inventors have made extensive studies to achieve the above-mentioned object, and as a result, have found that the above-mentioned object can be achieved by using a modified siloxane compound having an aromatic azomethine, and have completed the present invention. The present invention is based on this finding.

Namely, the present invention provides the following silicone compound, modified imide resin, thermosetting resin composition, prepreg, resin-attached film, laminate, multilayer printed wiring board, and semiconductor package.

[1] A siloxane compound having a structure represented by the following general formula (1) or the following general formula (2).

[ solution 1]

In the formula, R₁And R₂Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, or an acetyl groupA hydroxyl group, a sulfonic group, a sulfoalkoxy group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, wherein x and y are each independently an integer of 0 to 4. A is a single bond, or an azomethine group, an ester group, an amide group, an azoxy group, an azo group, an ethylene group or an ethynyl group (アセチレン group).

[ solution 2]

In the formula, R₃And R₄Each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100.

[2] The siloxane compound according to [1], which further comprises an aromatic azomethine.

[3] The siloxane compound according to [2], which is obtained by reacting an aromatic amine compound (A) having at least 2 primary amino groups in 1 molecule, an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule, and a siloxane compound (C) having at least 2 amino groups at the molecular terminal.

[4] The siloxane compound according to [2], which is obtained by reacting an aromatic amine compound (A) having at least 2 primary amino groups in 1 molecule with an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule, and then reacting a siloxane compound (C) having at least 2 amino groups at the molecular terminal.

[5] The siloxane compound according to [2], which is obtained by reacting an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule with a siloxane compound (C) having at least 2 amino groups at the molecular terminal and then reacting an aromatic amine compound (A) having at least 2 primary amino groups in 1 molecule.

[6] A modified imide resin which comprises an aromatic azomethine obtained by reacting a siloxane compound according to any one of [1] to [5] with a maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule.

[7] The modified imide resin according to [6], which further has an acidic substituent derived from the acidic substituent of the amine compound (E) represented by the following general formula (3).

[ solution 3]

In the formula, R₅Each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R₆Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.

[8] A thermosetting resin composition comprising the siloxane compound according to any one of [1] to [5] and a maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule.

[9] The thermosetting resin composition according to [8], which further comprises an amine compound (E) having an acidic substituent represented by the following general formula (3).

[ solution 4]

[10] The thermosetting resin composition according to [8] or [9], which further comprises a thermoplastic elastomer (F).

[11] The thermosetting resin composition according to any one of [8] to [10], further comprising at least one thermosetting resin (G) selected from epoxy resins and cyanate resins.

[12] The thermosetting resin composition according to any one of [8] to [11], further comprising an inorganic filler (H).

[13] The thermosetting resin composition according to any one of [8] to [12], further comprising a curing accelerator (I).

[14] A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of [8] to [13 ].

[15] A resin-coated film obtained by forming a layer of the thermosetting resin composition according to any one of [8] to [13] on a support.

[16] A laminated board obtained by laminating and molding the prepregs described in [14 ].

[17] A laminated sheet obtained by laminating and molding the resin-attached film described in [15 ].

[18] A multilayer printed wiring board produced using the laminate sheet as recited in [16] or [17 ].

[19] A semiconductor package, wherein a semiconductor element is mounted on the multilayer printed wiring board as recited in [18 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a siloxane compound, a modified imide resin, a thermosetting resin composition, a prepreg using the same, a film with resin, a laminate, a multilayer printed wiring board, and a semiconductor package, which can realize a thermosetting resin composition that exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and a high elastic modulus when applied to various applications.

In particular, the prepreg obtained by impregnating and coating a substrate with the thermosetting resin composition containing the modified siloxane compound having an aromatic azomethine of the present invention, the film with a resin obtained by coating a support, and the laminate produced by laminating and molding the prepregs of the present invention have particularly low curing shrinkage, low thermal expansion, excellent dielectric properties, and high elastic modulus, and are useful as a multilayer printed wiring board and a semiconductor package.

Detailed Description

The present invention will be described in detail below.

(siloxane Compound)

The siloxane compound of the present invention has a structure represented by the following general formula (1) and the following general formula (2). This structure can be obtained, for example, by reacting a compound having a structure represented by the following general formula (1) with a compound having a structure represented by the following general formula (2).

[ solution 5]

In the formula, R₁And R₂Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an acetyl group, a hydroxyl group, a sulfonic group, a sulfoalkoxy group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and x and y are each independently an integer of 0 to 4. A is a single bond, or azomethine, ester, amide, azoxy, azo, ethylene or ethynyl.

[ solution 6]

In addition, the siloxane compound of the present invention preferably contains an aromatic azomethine.

The aromatic azomethine is a substance in which at least 1 aromatic group is bonded to schiff base (-N ═ CH-).

The silicone compound of the present invention will be described in detail below.

The siloxane compound of the present invention is obtained by reacting an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule (hereinafter sometimes referred to as aromatic amine compound (a)), an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule (hereinafter sometimes referred to as aromatic aldehyde compound (B)), and a siloxane compound (C) having at least 2 amino groups at the molecular terminals (hereinafter sometimes referred to as siloxane compound (C)).

Examples of the aromatic amine compound (A) having at least 2 primary amino groups in 1 molecule of the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1, 4-diaminobenzene, 2, 5-dimethyl-1, 4-diaminobenzene, 4 '-diaminodiphenylmethane, 4' -diamino-3, 3 '-dimethyl-diphenylmethane, 4' -diamino-3, 3 '-diethyl-diphenylmethane, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl ketone, benzidine, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dihydroxybiphenylamine, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, 2-bis (4-aminophenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4 ' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9-bis (4-aminophenyl) fluorene, 4 ' -diaminobenzanilide, bis (4-aminophenyl) terephthalamide, 4-aminophenyl-4 ' -aminobenzoate, 3, 5-diaminobenzylbenzoate, 9-bis (4-aminophenyl) fluorene, 4, 4 ' -diaminoazobenzene, 3 ' -diamino-2, 2 ' -dimethylazoxybenzene, (E) -4, 4 ' -diaminostilbene, (Z) -4, 4 ' -diaminostilbene, 4 ' -diaminostilbene-2, 2 ' -disulfonic acid, 1, 3-bis (4-aminophenoxy) -5- (2-phenylethynyl) benzene, and the like. These may be used alone, or 2 or more of them may be used in combination.

Among them, for example, from the viewpoint of high reactivity during the reaction and realization of higher heat resistance, 4 '-diaminodiphenylmethane, 3' -dimethyl-4, 4 '-diaminobiphenyl, 4' -diamino-3, 3 '-dimethyl-diphenylmethane, 4' -diamino-3, 3 '-diethyl-diphenylmethane, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) propane and the like are more preferable. Further, from the viewpoint of low cost and solubility in a solvent, 4 ' -diaminodiphenylmethane, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 4 ' -diamino-3, 3 ' -diethyl-diphenylmethane, bis (4- (4-aminophenoxy) phenyl) propane are preferable. In addition, 4 '-diamino-3, 3' -diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are particularly preferable from the viewpoint of low thermal expansion properties and dielectric characteristics. Also preferred are p-phenylenediamine, m-phenylenediamine, 3-methyl-1, 4-diaminobenzene, and 2, 5-dimethyl-1, 4-diaminobenzene, which can be molded with high elasticity.

Examples of the aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule of the present invention include terephthalaldehyde, isophthalaldehyde, phthalaldehyde, 2 '-bipyridine-4, 4' -dicarboxaldehyde, and the like. Among them, terephthalaldehyde which can be more easily thermally expanded, has high reactivity during reaction, and is excellent in solvent solubility and commercially available is particularly preferable.

The siloxane compound (C) having at least 2 amino groups at the molecular terminals of the present invention comprises a structure represented by the following general formula (2).

[ solution 7]

In the formula of the general formula (2), n is an integer of 1 to 100, more preferably an integer of 2 to 50.

As the silicone compound (C) having at least 2 amino groups at the molecular terminals, commercially available products can also be used. Examples of commercially available products include "KF-8010" (amino equivalent 430), "X-22-161A" (amino equivalent 800), "X-22-161B" (amino equivalent 1500), "KF-8012" (amino equivalent 2200), "KF-8008" (amino equivalent 5700), "X-22-9409" (amino equivalent 700), "X-22-1660B-3" (amino equivalent 2200) (manufactured BY shin-Etsu chemical Co., Ltd.), "BY-16-853U" (amino equivalent 460), "BY-16-853" (amino equivalent 650), "BY-16-853B" (amino equivalent 2200) (manufactured BY Toyodo Corning Corp., Ltd.). These may be used alone, or 2 or more of them may be used in combination.

Among them, for example, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3 and BY-16-853B are preferable from the viewpoint of high reactivity and low thermal expansion during synthesis, and X-22-161A, X-22-161B is particularly preferable from the viewpoint of excellent compatibility and capability of high elastic modulus.

In the present invention, the reaction for obtaining the siloxane compound includes, for example, the following methods.

Reaction method a: siloxane compound (i) can be obtained by reacting aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule, aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule, and siloxane compound (C) having at least 2 amino groups at the molecular terminal.

Reaction method b: first, an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule and an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule are reacted to obtain an aromatic azomethine compound having at least 1 aldehyde group in 1 molecule. Then, the compound and the siloxane compound (C) having at least 2 amino groups at the molecular terminal are subjected to dehydration condensation reaction in an organic solvent to obtain a modified siloxane compound (ii) having an aromatic azomethine.

Reaction method c: first, an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule and a siloxane compound (C) having at least 2 amino groups at the molecular terminals are reacted with each other to obtain a modified siloxane compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule. Then, the compound is reacted with an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule to obtain a modified siloxane compound (iii) having an aromatic azomethine.

The siloxane compound of the present invention can be obtained by any of the above-mentioned reaction methods a, b and c, and for example, the operation of the reaction method a is particularly simple and effective when the modified siloxane compound of the present invention has insufficient solvent solubility. The reaction method b is characterized in that the molecular weight of the aromatic azomethine in the molecule of the siloxane compound of the present invention can be easily controlled, and is particularly effective for the high elastic modulus of the resin composition containing the compound. Further, the reaction method c is characterized in that the molecular weight of siloxane in the molecule of the siloxane compound of the present invention can be easily controlled, and is effective for reducing the thermal expansion coefficient of the resin composition containing the siloxane compound.

First, the reaction method a will be described in detail. In reaction method a, the siloxane compound (i) of the present invention can be obtained by reacting an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule, an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule, and a siloxane compound (C) having at least 2 amino groups at the molecular terminal.

Here, the amount of the aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule, the aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule, and the siloxane compound (C) having at least 2 amino groups at the molecular terminal is preferably such that the number of primary amino groups of the aromatic amine compound (a) and the siloxane compound (C) [ the amount of the aromatic amine compound (a) used/the primary amino group equivalent of the aromatic amine compound (a) + the amount of the siloxane compound (C) used/the primary amino group equivalent of the siloxane compound (C) ] is 1.0 to 10.0 times the number of aldehyde groups of the aromatic aldehyde compound (B) [ the amount of the aromatic aldehyde compound (B) used/the aldehyde group equivalent of the aromatic aldehyde compound (B) ]. By setting the amount to 1.0 time or more, the solubility in a solvent tends to be reduced. Further, when the amount is 10.0 times or less, the heat resistance of the thermosetting resin containing the modified siloxane compound (i) having an aromatic azomethine tends to be reduced.

An organic solvent may be used in the reaction. The organic solvent used is not particularly limited, but examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, sulfur atom-containing solvents such as dimethylsulfoxide, and ester solvents such as γ -butyrolactone. These may be used in 1 kind or in combination of 2 or more kinds. Among them, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide and γ -butyrolactone are preferable from the viewpoint of solubility. Further, propylene glycol monomethyl ether and toluene are more preferable because they have high volatility and are difficult to remain as residual solvents in the production of prepregs. In addition, since this reaction is a dehydration condensation reaction, water is produced as a by-product. For the purpose of removing the water as a by-product, it is preferable to carry out the reaction while removing the water as a by-product by azeotropy with an aromatic solvent, for example.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass per 100 parts by mass of the total of the aromatic amine compound (a), the aromatic aldehyde compound (B), and the siloxane compound (C) in terms of solid content. If the amount of the organic solvent used is 25 parts by mass or more, the solubility tends to be less than sufficient. Further, if it is 2000 parts by mass or less, the reaction time is suitable.

In this reaction, a reaction catalyst may be used as necessary. The reaction catalyst used is not particularly limited. Examples of the reaction catalyst include an acidic catalyst such as p-toluenesulfonic acid, an amine such as triethylamine, pyridine, or tributylamine, an imidazole such as methylimidazole or phenylimidazole, a phosphorus-based catalyst such as triphenylphosphine, and the like. These may be used in 1 kind or in combination of 2 or more kinds. For the dehydration condensation reaction to proceed efficiently, an acidic catalyst such as p-toluenesulfonic acid is preferable.

The siloxane compound (i) can be obtained by charging the above-mentioned raw materials, organic solvent, and if necessary, reaction catalyst into a reaction vessel, stirring for 0.1 to 10 hours while heating and holding the temperature as necessary, and subjecting the mixture to a dehydration condensation reaction.

The reaction temperature is, for example, preferably 70 to 150 ℃, and the reaction is preferably carried out while removing water as a by-product, and more preferably 100 to 130 ℃. If the temperature is lower than 70 ℃, the reaction rate becomes slow, and if the temperature is 150 ℃ or lower, a solvent with a high boiling point is not necessary in the reaction solvent, and when a prepreg is produced, it is difficult to leave a residual solvent, and a decrease in heat resistance can be suppressed.

The reaction method b will be described in detail below. In the reaction method B, first, an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule and an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule are reacted to obtain an aromatic azomethine compound having at least 1 aldehyde group in 1 molecule. Then, by reacting the compound with a siloxane compound (C) having at least 2 amino groups at the molecular terminal, a modified siloxane compound (ii) having an aromatic azomethine can be obtained.

In the reaction method b, the same organic solvent and, if necessary, the same reaction catalyst as those used in the reaction method a can be used as desired.

First, an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule and an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule are subjected to dehydration condensation reaction in an organic solvent to obtain an aromatic azomethine compound having at least 1 aldehyde group in 1 molecule.

Here, the amounts of the aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule and the aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule are preferably used, for example, in such a range that the number of primary amino groups of the aromatic amine compound (a) [ the amount of the aromatic amine compound (a) used/the primary amino group equivalent of the aromatic amine compound (a) ] is 0.1 to 5.0 times the number of aldehyde groups of the aromatic aldehyde compound (B) [ the amount of the aromatic aldehyde compound (B) used/the aldehyde group equivalent of the aromatic aldehyde compound (B) ]. When the amount is 0.1 times or more, the decrease in the molecular weight of the aromatic azomethine compound obtained by the present reaction tends to be suppressed. Further, by setting the amount to 5.0 times or less, the decrease in solubility in a solvent can be suppressed.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of the resin components of the aromatic amine compound (a) and the aromatic aldehyde compound (B). When the amount of the organic solvent used is 25 parts by mass or more, the solubility tends to be suppressed from being insufficient. Further, if it is 2000 parts by mass or less, the reaction time is suitable.

The above raw materials, organic solvent, and reaction catalyst used as needed are added to a reaction vessel, and the mixture is stirred for 0.1 to 10 hours while being heated and maintained at a temperature as needed to perform a dehydration condensation reaction, whereby an aromatic azomethine compound having at least 1 aldehyde group in 1 molecule can be obtained.

The reaction temperature is, for example, preferably 70 to 150 ℃ and more preferably 100 to 130 ℃. In addition, it is preferable to carry out the reaction while removing water as a by-product. If the temperature is 70 ℃ or higher, the reaction rate tends not to be too slow. When the reaction temperature is 150 ℃ or lower, a solvent having a high boiling point is not required as the reaction solvent, and thus, it is difficult to leave a residual solvent in the production of a prepreg, and a decrease in heat resistance can be suppressed.

Then, the aromatic azomethine compound having at least 1 aldehyde group in 1 molecule obtained by the above reaction and the siloxane compound (C) having at least 2 amino groups at the molecular terminal are subjected to dehydration condensation reaction in an organic solvent to obtain a modified siloxane compound (ii) having an aromatic azomethine.

The amount of the aromatic azomethine compound and the siloxane compound (C) to be used is preferably in the range of, for example, 1.0 to 10.0 times the number of primary amino groups of the siloxane compound (C) [ the amount of the siloxane compound (C) to be used per primary amino group equivalent of the siloxane compound (C) ] as many as the number of aldehyde groups of the aromatic azomethine compound [ the amount of the aromatic azomethine compound to be used per aldehyde group equivalent of the aromatic azomethine compound ]. By setting the amount to 1.0 time or more, the solubility in a solvent tends to be reduced. Further, when the amount is 10.0 times or less, the decrease in the elastic modulus of the thermosetting resin containing the modified siloxane compound (ii) having an aromatic azomethine group tends to be suppressed.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of the resin components of the aromatic azomethine compound having at least 1 aldehyde group in 1 molecule and the siloxane compound (C). When the amount of the organic solvent used is 25 parts by mass or more, the solubility tends to be suppressed from being insufficient. Further, if it is 2000 parts by mass or less, the reaction time is suitable.

The above raw materials, organic solvent and, if necessary, a reaction catalyst are charged into a reaction vessel, and the mixture is stirred for 0.1 to 10 hours while being heated and maintained at a temperature as necessary to carry out a dehydration condensation reaction, whereby a modified siloxane compound (ii) having an aromatic azomethine can be obtained.

The reaction temperature is, for example, preferably 70 to 150 ℃ and more preferably 100 to 130 ℃. In addition, it is preferable to carry out the reaction while removing water as a by-product. If the reaction temperature is 70 ℃ or higher, the reaction rate tends not to be too slow. When the reaction temperature is 150 ℃ or lower, a solvent having a high boiling point is not required as the reaction solvent, and thus, it is difficult to leave a residual solvent in the production of a prepreg, and a decrease in heat resistance can be suppressed.

The reaction method c will be described in detail below. In the reaction method C, first, an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule and a siloxane compound (C) having at least 2 amino groups at the molecular terminal are reacted to obtain a modified siloxane compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule. Then, the compound is reacted with an aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule to obtain a modified siloxane compound (iii) having an aromatic azomethine.

In the reaction method c, the same organic solvent and, if necessary, the same reaction catalyst as used in the reaction methods a and b can be used as desired.

A modified silicone compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule is obtained by subjecting an aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule and a silicone compound (C) having at least 2 amino groups at the molecular terminals to a dehydration condensation reaction in an organic solvent.

Here, the amount of the aromatic aldehyde compound (B) having at least 2 aldehyde groups in 1 molecule and the siloxane compound (C) having at least 2 amino groups at the molecular terminal are preferably used in a range of, for example, 0.1 to 5.0 times the number of primary amino groups of the siloxane compound (C) [ amount of the siloxane compound (C) used/primary amino group equivalent of the siloxane compound (C) ] as the number of aldehyde groups of the aromatic aldehyde compound (B) [ amount of the aromatic aldehyde compound (B) used/aldehyde group equivalent of the aromatic aldehyde compound (B) ]. By setting the amount to 0.1 times or more, the decrease in solubility in a solvent can be suppressed. Further, by setting the ratio to 5.0 or less, the molecular weight of the modified siloxane compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule obtained by the present reaction can be suppressed from decreasing.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of the resin components of the aromatic aldehyde compound (B) and the siloxane compound (C). If the amount of the organic solvent used is 25 parts by mass or more, the solubility is not insufficient, and if it is 2000 parts by mass or less, the reaction time is suitable.

The above raw materials, an organic solvent, and a reaction catalyst used as needed are charged into a reaction vessel, and the mixture is stirred for 0.1 to 10 hours while being heated and maintained at a temperature as needed to perform a dehydration condensation reaction, whereby a modified siloxane compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule can be obtained.

Then, the modified siloxane compound (iii) having an aromatic azomethine can be obtained by subjecting the modified siloxane compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule obtained by the above reaction and the aromatic amine compound (a) having at least 2 primary amino groups in 1 molecule to dehydration condensation reaction in an organic solvent.

Here, the amount of the modified siloxane compound and the aromatic amine compound (a) to be used is preferably in the range of, for example, 1.0 to 10.0 times the number of primary amino groups of the aromatic amine compound (a) [ amount of the aromatic amine compound (a) to be used/primary amino group equivalent of the aromatic amine compound (a) ] as much as the number of aldehyde groups of the modified siloxane compound [ amount of the modified siloxane compound to be used/aldehyde group equivalent of the modified siloxane compound ]. By setting the amount to 1.0 time or more, the thermosetting resin containing the modified siloxane compound (iii) having an aromatic azomethine tends to be inhibited from lowering in low thermal expansion properties. Further, by setting the amount to 10.0 times or less, the solubility in a solvent tends to be reduced.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of the resin components of the modified siloxane compound having at least 1 aldehyde group and an azomethine group (-N ═ CH-) in 1 molecule and the aromatic amine compound (a). When the amount of the organic solvent used is 25 parts by mass or more, the solubility tends to be suppressed from being insufficient. Further, if it is 2000 parts by mass or less, the reaction time is suitable.

The modified siloxane compound (iii) having an aromatic azomethine can be obtained by adding the above-mentioned raw materials, an organic solvent, and a reaction catalyst to be used as needed to a reaction vessel, stirring for 0.1 to 10 hours while heating and holding the temperature as needed, and then subjecting the mixture to a dehydration condensation reaction.

The modified siloxane compound of the present invention obtained by the above-mentioned reaction methods a, b and c can be confirmed by performing IR measurement. By IR measurement, it was confirmed that 1620cm was caused by azomethine group (-N-CH-)^-1In addition, the presence of 3440cm due to primary amino groups was confirmed^-1And 3370cm^-1The peak in the vicinity was confirmed to be a good progress of the reaction, and the desired compound was obtained. The weight average molecular weight (Mw) is, for example, preferably 1000 to 300000, particularly preferably 6000 to 150000. When the weight average molecular weight (Mw) is not less than the lower limit, low curing shrinkage and low thermal expansion are improved, and when it is not more than the upper limit, compatibility and elastic modulus are improved. The weight average molecular weight (Mw) is a value measured by Gel Permeation Chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene. For example, the reaction can be carried out under the following conditions. As measuring devices, automatic taking is usedPrototype (AS-8020 manufactured by Tosoh corporation), column oven (860-C0 manufactured by Nippon spectral Co., Ltd.), RI detector (830-RI manufactured by Nippon spectral Co., Ltd.), UV/VIS detector (870-UV manufactured by Nippon spectral Co., Ltd.), and HPLC pump (880-PU manufactured by Nippon spectral Co., Ltd.).

Further, as the column used, TSKgel SuperHZ2000, 2300 available from Tosoh corporation can be used, and as the measurement conditions, the measurement temperature was 40 ℃, the flow rate was 0.5ml/min, and the measurement was carried out using tetrahydrofuran as a solvent.

(modified imide resin)

The modified imide resin of the present invention is obtained by reacting the amino-modified siloxane compound of the present invention described above with a maleimide compound (C) having at least 2N-substituted maleimide groups in 1 molecule.

The modified imide resin is preferably a resin having an acidic substituent derived from an acidic substituent of the amine compound (D) represented by the following general formula (3). The acidic substituent may be introduced by reacting the amine compound (D). By having such an acidic substituent, good low thermal expansion properties can be obtained.

[ solution 8]

In the formula (3), R₁Each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R₂Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.

Further details of the amine compound (D) will be described later. The "resin having an acidic substituent derived from the amine compound (D)" means the acidic substituent of the amine compound (D) itself and a resin containing the acidic substituent.

The modified imide resin can be produced in the "pre-reaction" in the production of the thermosetting resin composition described later.

(thermosetting resin composition)

The thermosetting resin composition of the present invention comprises the modified siloxane compound of the present invention and a maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule.

Examples of the maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule (hereinafter sometimes referred to as "maleimide compound (D)") include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanebismaleimide, 4-methyl-1, 3-phenylenebismaleimide, m-phenylenebismaleimide, and 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane. These maleimide compounds may be used alone, or 2 or more kinds may be used in combination.

Among them, for example, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, and 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, which have high reactivity and can achieve higher heat resistance, are preferable, bis (4-maleimidophenyl) methane and 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferable from the viewpoint of solubility in a solvent, and bis (4-maleimidophenyl) methane is particularly preferable from the viewpoint of low cost.

In the thermosetting resin composition of the present invention, the amount of the silicone compound used (amount to be blended) is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass, in terms of copper foil adhesiveness and chemical resistance, per 100 parts by mass of the total amount of the resin components, for example.

The amount of the maleimide compound (D) used is preferably 30 to 99 parts by mass, and more preferably 40 to 95 parts by mass, from the viewpoint of low thermal expansion and high elastic modulus, per 100 parts by mass of the total resin components, for example.

The thermosetting resin composition of the present invention is a composition comprising the siloxane compound of the present invention and a maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule, but the above compound may be pre-reacted to be used as a modified imide resin having an aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further improvement of low curing shrinkage and low thermal expansion can be achieved.

The preliminary reaction is preferably carried out in an organic solvent under heat-holding conditions, and the siloxane compound of the present invention and the maleimide compound (D) are reacted to synthesize a modified imide resin.

The reaction temperature when the modified siloxane compound and the maleimide compound (D) are reacted in an organic solvent is, for example, preferably 70 to 150 ℃, more preferably 100 to 130 ℃. The reaction time is, for example, preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

In the preliminary reaction, the amount of the maleimide compound (D) and the siloxane compound of the present invention used is preferably in the range of, for example, 2.0 to 10.0 times the number of maleimide groups of the maleimide compound (D) [ amount of the maleimide compound (D) used/maleimide group equivalent of the maleimide compound (D) ] as large as the number of primary amino groups of the siloxane compound of the present invention [ amount of the siloxane compound of the present invention used/primary amino group equivalent of the siloxane compound of the present invention ]. When the amount is 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Further, by setting the amount to 10.0 times or less, the solubility in an organic solvent and the heat resistance tend to be suppressed from decreasing.

The amount of the maleimide compound (D) used in the preliminary reaction is preferably 50 to 3000 parts by mass, and more preferably 100 to 1500 parts by mass, for example, per 100 parts by mass of the resin component of the siloxane compound of the present invention, while maintaining the above-mentioned relationship. When the amount is 50 parts by mass or more, the decrease in heat resistance tends to be suppressed. Further, the low thermal expansion property can be kept good by setting 3000 parts by mass or less.

Examples of the organic solvent used in the preliminary reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as ethyl acetate and γ -butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and sulfur atom-containing solvents such as dimethylsulfoxide. These may be used in 1 kind or in combination of 2 or more kinds.

Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ -butyrolactone are preferable from the viewpoint of, for example, solubility, and cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable from the viewpoint of low toxicity, high volatility, and difficulty in remaining as a residual solvent.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of the resin components of the siloxane compound and the maleimide compound (D) of the present invention. If the amount of the organic solvent used is 25 parts by mass or more, the solubility is not insufficient, and if it is 2000 parts by mass or less, the reaction time is appropriate.

In addition, a reaction catalyst may be optionally used in the preliminary reaction. The reaction catalyst is not particularly limited, but examples thereof include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide and potassium amide. These may be used in 1 kind or in combination of 2 or more kinds.

The amount of the modified imide resin having an aromatic azomethine obtained by the above pre-reaction is preferably 50 to 100 parts by mass, and more preferably 60 to 100 parts by mass, based on 100 parts by mass of the total resin components, for example. By setting the amount of the modified imide resin having an aromatic azomethine to 50 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

The modified imide resin having an aromatic azomethine obtained by pre-reacting a thermosetting resin composition comprising the siloxane compound of the present invention and a maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule with the above compound can have good thermal curing reactivity even when used alone, but a curing agent and a radical initiator may be used in combination as required. By using a curing agent and a radical initiator, heat resistance, adhesiveness, and mechanical strength can be improved.

Examples of the curing agent used in combination include aromatic amines such as dicyandiamide, 4 '-diaminodiphenylmethane, 4' -diamino-3, 3 '-diethyl-diphenylmethane, 4' -diaminodiphenylsulfone, phenylenediamine and xylylenediamine, aliphatic amines such as hexamethylenediamine and 2, 5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine.

The radical initiator is not particularly limited, and for example, an organic peroxide such as an acyl peroxide, a hydroperoxide, a ketone peroxide, an organic peroxide having a t-butyl group, or a peroxide having a cumyl group can be used. These may be used alone, or 2 or more of them may be used in combination. Among them, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.

The thermosetting resin composition of the present invention may contain an amine compound (E) having an acidic substituent represented by the following general formula (3).

[ solution 9]

In the formula (3), R₅Each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R₆Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x and y areAnd 5.

Examples of the amine compound (E) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3, 5-dihydroxyaniline, 3, 5-dicarboxylaniline and the like. Among them, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3, 5-dihydroxyaniline are preferable from the viewpoint of solubility and yield of synthesis, and m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance.

The amount of the amine compound (E) having an acidic substituent is preferably 0.5 to 30 parts by mass, and more preferably 1 to 20 parts by mass, in view of low thermal expansibility, per 100 parts by mass of the total amount of the resin components, for example.

The thermosetting resin composition of the present invention may contain the modified siloxane compound of the present invention, a maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule, and an amine compound (E) having an acidic substituent, and the compounds may be pre-reacted to be used as a modified imide resin having an acidic substituent and an aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further improvement of low curing shrinkage and low thermal expansion can be achieved.

The preliminary reaction is preferably carried out in an organic solvent under heat-holding conditions, and the siloxane compound of the present invention, the maleimide compound (D), and the amine compound having an acidic substituent (E) are reacted with each other to synthesize a modified imide resin having an acidic substituent.

The reaction temperature in the reaction of the siloxane compound of the present invention, the maleimide compound (D), and the amine compound (E) having an acidic substituent in an organic solvent is, for example, preferably 70 to 150 ℃, and more preferably 100 to 130 ℃. The reaction time is, for example, preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

In the preliminary reaction, the amount of the maleimide compound (D), the silicone compound of the present invention and the amine compound (E) having an acidic substituent is preferably in a range of, for example, 2.0 to 10.0 times the number of maleimide groups of the maleimide compound (D) [ amount of the maleimide compound (D) used/maleimide group equivalent of the maleimide compound (D) ] as the number of primary amino groups of the silicone compound of the present invention and the amine compound (E) having an acidic substituent [ amount of the silicone compound of the present invention used/primary amino group equivalent of the silicone compound of the present invention + amount of the amine compound (E) having an acidic substituent used/primary amino group equivalent of the amine compound (E) having an acidic substituent ]. When the amount is 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Further, by setting the amount to 10.0 times or less, the solubility in an organic solvent and the heat resistance can be suppressed from being lowered.

The amount of the maleimide compound (D) used in the preliminary reaction is preferably 50 to 3000 parts by mass, and more preferably 100 to 1500 parts by mass, for example, per 100 parts by mass of the resin component of the siloxane compound of the present invention, while maintaining the above-mentioned relationship. By making the amount of the organic solvent to be 50 parts by mass or more, the decrease in heat resistance can be suppressed. Further, the low thermal expansion property can be kept good by setting 3000 parts by mass or less.

The amount of the amine compound (E) having an acidic substituent to be used in the preliminary reaction is, for example, preferably 1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, based on 100 parts by mass of the resin component of the siloxane compound of the present invention. By setting the amount to 1 part by mass or more, the decrease in heat resistance can be suppressed, and by setting the amount to 1000 parts by mass or less, the low thermal expansion property can be kept good.

The organic solvent used in the preliminary reaction is not particularly limited, but examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as ethyl acetate and γ -butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and sulfur atom-containing solvents such as dimethylsulfoxide. These may be used in 1 kind or in combination of 2 or more kinds.

Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ -butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable from the viewpoint of low toxicity, high volatility, and difficulty in remaining as a residual solvent.

The amount of the organic solvent to be used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of the resin components of the siloxane compound, the maleimide compound (D), and the amine compound (E) having an acidic substituent. If the amount of the organic solvent used is 25 parts by mass or more, the solubility tends to be less than sufficient. Further, if it is 2000 parts by mass or less, the reaction time is suitable.

In the preliminary reaction, a reaction catalyst may be optionally used. The reaction catalyst is not particularly limited, but examples thereof include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide and potassium amide. These may be used in 1 kind or in combination of 2 or more kinds.

The amount of the modified imide resin having an acidic substituent and an aromatic azomethine obtained by the above pre-reaction is preferably 50 to 100 parts by mass, and more preferably 60 to 100 parts by mass, based on 100 parts by mass of the total of the resin components, for example. By setting the blending amount of the modified imide resin having an acidic substituent and an aromatic azomethine to 50 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

The thermosetting resin composition comprising the modified siloxane compound having an aromatic azomethine of the present invention, the maleimide compound (D) having at least 2N-substituted maleimide groups in 1 molecule, the amine compound (E) having an acidic substituent, and the above compound are pre-reacted, and the resulting modified imide resin having an acidic substituent and an aromatic azomethine has good thermal curing reactivity even when used alone, but a curing agent and a radical initiator may be used in combination as needed. By using a curing agent and a radical initiator, heat resistance, adhesiveness, and mechanical strength can be improved.

Examples of the radical initiator include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. These may be used alone, or 2 or more of them may be used in combination. Among them, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.

Further, the thermosetting resin composition of the present invention may contain a thermoplastic elastomer (F).

Examples of the thermoplastic elastomer (F) include styrene-based elastomers, olefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and derivatives thereof. These compositions contain a hard segment component and a soft segment component, and generally the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These may be used alone in 1 kind, or in a mixture of 2 or more kinds.

As these elastomers, elastomers having reactive functional groups at molecular terminals or in molecular chains can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanate group, an acryloyl group, a methacryloyl group, and a vinyl group. By having these reactive functional groups at the molecular terminals or in the molecular chains, the compatibility with the resin is improved, and the internal stress generated during curing of the thermosetting resin composition of the present invention can be more effectively reduced. As a result thereof, warpage of the substrate can be significantly reduced.

Among these elastomers, for example, styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, and silicone-based elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene-based elastomers and olefin-based elastomers are particularly preferable from the viewpoint of dielectric characteristics.

The reactive functional groups contained at the molecular terminals or in the molecular chains of these elastomers are preferably epoxy groups, hydroxyl groups, carboxyl groups, amino groups, and amide groups, for example, from the viewpoint of adhesion to the metal foil, and particularly preferably epoxy groups, hydroxyl groups, and amino groups, from the viewpoint of heat resistance and insulation reliability.

The amount of the thermoplastic elastomer (F) component used is preferably 0.1 to 50 parts by mass, for example, per 100 parts by mass of the total of the resin components, and more preferably 2 to 30 parts by mass, in view of good compatibility with the resin and effective expression of low curing shrinkage, low thermal expansion and excellent dielectric properties of the cured product.

The thermosetting resin composition of the present invention may contain at least one thermosetting resin (G) selected from epoxy resins and cyanate resins.

Examples of the epoxy resin include bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, bisphenol F novolac type epoxy resins, stilbene type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenol methane type epoxy resins, biphenyl type epoxy resins, xylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracenes, and phosphorus-containing epoxy resins obtained by introducing a phosphorus compound into these epoxy resins. These may be used alone, or 2 or more of them may be used in combination. Among them, for example, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.

Examples of the cyanate ester resin include bisphenol type cyanate ester resins such as phenol type cyanate ester resin, bisphenol a type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethylbisphenol F type cyanate ester resin, and prepolymers obtained by partially triazinating these resins. These may be used alone, or 2 or more of them may be used in combination. Among them, for example, from the viewpoint of heat resistance and flame retardancy, a phenol type cyanate ester resin is preferable.

In these thermosetting resins (G), a curing agent may be used as needed. Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac, amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone, and acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, and maleic anhydride copolymers. These may be used alone in 1 kind, or in a mixture of 2 or more kinds.

The amount of the thermosetting resin (G) used is preferably 1 to 50 parts by mass, and more preferably 3 to 30 parts by mass, from the viewpoint of heat resistance and chemical resistance, for example, per 100 parts by mass of the total amount of the resin components.

The thermosetting resin composition of the present invention may contain an inorganic filler (H). Examples of the inorganic filler include glass powders such as silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E glass, T glass, and D glass, and hollow glass beads. These may be used alone, or 2 or more of them may be used in combination.

Among these inorganic fillers, silica is particularly preferable from the viewpoint of, for example, dielectric characteristics, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica having a high water content produced by a wet process and dry process silica containing little bound water produced by a dry process. The dry-process silica may be crushed silica, fumed silica, fused spherical silica, or the like, depending on the production method. Among them, fused spherical silica is preferable from the viewpoint of low thermal expansion and high fluidity when filled in a resin.

When fused spherical silica is used as the inorganic filler, the average particle diameter is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm, for example. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity at the time of high-density filling into a resin can be kept good, and by setting the average particle diameter to 10 μm or less, the mixing probability of coarse particles can be reduced, and the occurrence of defects due to the coarse particles can be suppressed. Here, the average particle diameter means a particle diameter at a point corresponding to 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained by assuming that the total volume of the particles is 100%, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.

The content of the inorganic filler is, for example, preferably 20 to 500 parts by mass, and more preferably 50 to 350 parts by mass, based on 100 parts by mass of the total of the resin components. By setting the content of the inorganic filler to 20 to 500 parts by mass with respect to 100 parts by mass of the total of the resin components, the moldability and low thermal expansion of the resin composition can be kept good.

When an inorganic filler is added to the resin composition, the inorganic filler is preferably subjected to a pretreatment with a silane-based or titanate-based coupling agent, or a surface treatment agent such as a silicone oligomer, or a bulk blending treatment.

The thermosetting resin composition of the present invention may contain a curing accelerator (I). Examples of the curing accelerator include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt (II) bisacetoacetonate, and cobalt (III) triacetylacetonate, organic phosphorus compounds such as imidazoles and derivatives thereof, phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone in 1 kind, or in a mixture of 2 or more kinds.

Among them, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable, for example, from the viewpoint of accelerating effect and storage stability.

The content of the curing accelerator is, for example, preferably 0.01 to 3.0 parts by mass, and more preferably 0.05 to 1.5 parts by mass, per 100 parts by mass of the total of the resin components. The content of the curing accelerator is 0.01 to 3.0 parts by mass relative to 100 parts by mass of the total of the resin components, so that the accelerating effect and the storage stability can be kept good.

In the present invention, known thermoplastic resins, organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, adhesion promoters, and the like can be used as desired within a range not prejudicial to the object. These may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of the thermoplastic resin include polyphenylene ether resins, phenoxy resins, polycarbonate resins, polyester resins, polyamide resins, polyimide resins, xylene resins, petroleum resins, and silicone resins.

Examples of the organic filler include resin fillers containing polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, and the like; and a resin filler having a core-shell structure including a rubber-like core layer made of an acrylate-based resin, a methacrylate-based resin, a conjugated diene-based resin, or the like, and a glass-like shell layer made of an acrylate-based resin, a methacrylate-based resin, an aromatic vinyl-based resin, a vinyl cyanide-based resin, or the like.

Examples of the flame retardant include halogen-containing flame retardants containing bromine or chlorine, triphenyl phosphate, tricresyl phosphate, tris (dichlorophenyl) phosphate, phosphate ester compounds, phosphorus flame retardants such as red phosphorus, nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.

In addition, examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, examples of the antioxidant include hindered phenol-based or histamine-based antioxidants, examples of the photopolymerization initiator include benzophenone-based, benzil ketal-based, and thioxanthone-based photopolymerization initiators, examples of the fluorescent brightener include stilbene derivative fluorescent brighteners, and examples of the adhesion promoter include urea compounds such as urea silanes, and coupling agents such as silane-based, titanate-based, and aluminate-based.

The thermosetting resin composition containing a siloxane compound of the present invention is used for a prepreg, and therefore, it is preferable that the thermosetting resin composition is finally prepared in a state of a varnish in which each component is dissolved or dispersed in an organic solvent.

Examples of the organic solvent used in this case include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and sulfur atom-containing solvents such as dimethylsulfoxide. These may be used alone in 1 kind, or in a mixture of 2 or more kinds.

Among them, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.

The resin component in the varnish to be finally obtained is, for example, preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the total varnish. By setting the content of the resin component in the varnish to 40 to 90 mass%, the coatability can be maintained good, and a prepreg having an appropriate amount of the resin component can be obtained.

Here, the "resin component" in the present specification means a siloxane compound, a modified imide resin (including a modified imide resin having an acidic substituent derived from the acidic substituent of the amine compound (D) represented by the general formula (3), a maleimide compound (C), an amine compound (D) having an acidic substituent, a thermoplastic elastomer (E), a thermosetting resin (F), and a reaction product thereof. The "thermosetting resin composition" refers to a composition containing an inorganic filler, a curing accelerator, and the like in the resin component.

(prepreg)

The prepreg of the present invention is obtained by impregnating a substrate with the thermosetting resin composition of the present invention. The prepreg of the present invention will be described in detail below.

The prepreg of the present invention can be produced by impregnating the thermosetting resin composition of the present invention into a base material and semi-curing (b-staging) the composition by heating or the like. The method for impregnating the thermosetting resin composition of the present invention into a substrate is not particularly limited, but examples thereof include a method of immersing the substrate in a resin varnish, a method of coating with various coaters, a spray coating method by spraying, and the like. Among them, a method of impregnating the base material in the resin varnish is preferable. This can improve the impregnation of the resin composition into the base material.

As the substrate of the present invention, for example, known materials used for various laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. In other applications, for example, if the substrate is a fiber-reinforced substrate, carbon fibers or the like may be used.

These base materials have shapes of, for example, woven fabric, nonwoven fabric, roving, chopped strand mat and surfacing mat, and the material and shape may be selected according to the intended use and performance of the molded product, and 2 or more materials and shapes may be used alone or in combination as necessary. The thickness of the substrate can be, for example, about 0.03 to 0.5mm, and is preferably a substrate surface-treated with a silane coupling agent or the like or a substrate mechanically subjected to a fiber-opening treatment in view of heat resistance, moisture resistance and workability.

The prepreg of the present invention can be obtained, for example, by impregnating or coating a substrate with a thermosetting resin composition so that the amount of the thermosetting resin composition attached to the substrate is 20 to 90 mass% based on the content of the thermosetting resin composition in the dried prepreg, and then drying the impregnated substrate by heating at a temperature of usually 100 to 200 ℃ for 1 to 30 minutes to semi-cure (b-stage) the prepreg.

(film with resin)

The resin-attached film of the present invention is a film obtained by forming a layer of the thermosetting resin composition of the present invention on a support. The method for forming a layer of the thermosetting resin composition obtained in the present invention on a support is not particularly limited, but for example, the thermosetting resin composition obtained in the present invention may be applied to a support in a varnish state using various coaters, and then dried by heating, hot air blowing, or the like to form a resin composition layer. The film with resin of the present invention can be produced by performing semi-curing (b-staging) by heating or the like in this manner. The semi-cured state is preferably a state in which the adhesion between the resin composition layer of the resin-coated film and the circuit board can be ensured when the resin-coated film and the circuit board are laminated and cured, and the embedding property (fluidity) into the circuit board can be ensured.

The coating machine used when the thermosetting resin composition of the present invention is coated on the support is not particularly limited, but for example, a die coater, comma coater, bar coater, kiss coater, roll coater, or the like can be used. They may be appropriately selected according to the thickness of the resin composition layer. As a drying method, heating, hot air blowing, or the like can be used.

The thermosetting resin composition is dried under the drying conditions after being applied to the support, for example, so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent, but the varnish containing 30 to 60 mass% of the organic solvent is dried at 50 to 150 ℃ for about 3 to 10 minutes to form a resin composition layer. The drying conditions are preferably set appropriately in advance by simple experiments.

The thickness of the resin composition layer formed on the support is generally equal to or greater than the thickness of the conductor layer included in the circuit board. The thickness of the conductor layer is preferably 5 to 70 μm, for example, and more preferably 5 to 50 μm, and still more preferably 5 to 30 μm, in order to realize the reduction in thickness and size of the multilayer printed wiring board.

Examples of the support in the resin-attached film include films made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter, sometimes simply referred to as "PET"), polyesters such as polyethylene naphthalate, polycarbonates, polyimides, and the like, and metal foils such as release paper, copper foil, and aluminum foil. The support and the protective film described later may be subjected to a mold release treatment in addition to the matting treatment and the corona treatment.

The thickness of the support is, for example, preferably 10 to 150 μm, more preferably 25 to 50 μm. A protective film may be further laminated on the surface of the resin composition layer on which the support is not provided, the protective film being in conformity with the support. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, foreign matter can be prevented from entering.

The film with the resin may be wound into a roll and stored.

(laminated plate)

The laminate of the present invention is obtained by laminating and molding the above-described resin-attached film. For example, the resin-attached film can be produced by laminating a resin-attached film on one or both surfaces of a circuit board, a prepreg, a base material, or the like using a vacuum laminator, and curing the resin by heating as necessary. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. The circuit board referred to herein is a board having a circuit pattern formed on one or both surfaces of the board as described above. In addition, in a printed wiring board in which a plurality of conductor layers and insulating layers are alternately laminated, a printed wiring board in which a circuit pattern is formed on one surface or both surfaces of the outermost layer of the printed wiring board is also included in the circuit board described herein. Furthermore, the surface of the conductor layer may be roughened in advance by blackening treatment or the like.

In the above lamination, in the case where the resin-attached film has a protective film, after the protective film is removed, the resin-attached film and the circuit board are preheated as necessary, and the resin-attached film is pressed and heated and pressed against the circuit board. In the insulating film with a support of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is suitably used. The lamination conditions are, for example, preferably 70 to 140 ℃ in pressure bonding temperature (lamination temperature), 0.1 to 1.1MPa in pressure bonding pressure, and preferably 20mmHg (26.7hPa) or less in air pressure. The lamination method may be a batch method or a continuous method using a roll.

After the resin-containing film is laminated on the circuit board, the film is cooled to around room temperature, and then peeled off with the support peeled off, and thermally cured, whereby an insulating resin layer can be formed on the circuit board. The conditions for heat curing may be appropriately selected depending on the kind, content, and the like of the resin component in the resin composition, but are preferably selected within a range of from 20 minutes to 180 minutes at 150 to 220 ℃, and more preferably from 30 to 120 minutes at 160 to 200 ℃.

In the case where the support is not peeled before curing after the insulating resin layer is formed, peeling is performed at this time. Then, as necessary, a via hole (via hole) or a through hole (via hole) is formed in an insulating layer formed on the circuit substrate. The hole can be drilled by a known method such as a drill, a laser, or plasma, or by a combination of these methods as needed, but the most common method is to drill holes by a laser such as a carbon dioxide laser or a YAG laser.

Then, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin composition layer is roughened with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, or the like), dichromate, ozone, hydrogen peroxide/sulfuric acid, or nitric acid, to form irregular anchors (anchors). As the oxidizing agent, a sodium hydroxide aqueous solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Then, a conductor layer is formed by a method combining electroless plating and electroplating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed by electroless plating alone. As a method of forming a pattern thereafter, for example, a known subtractive method (subtractive), a Semi-Additive method (Semi-Additive), or the like can be used.

The laminate sheet of the present invention is obtained by laminating the prepregs of the present invention described above. The prepreg of the present invention can be produced by laminating 1 to 20 sheets of the prepreg, for example, and laminating the prepreg to have a structure in which a metal foil of copper, aluminum, or the like is disposed on one surface or both surfaces thereof.

The forming conditions for producing the laminated sheet include, for example, a method of forming the laminated sheet and the multilayer sheet for an electrical insulating material, for example, a multi-stage press, a multi-stage vacuum press, a continuous forming, an autoclave forming machine, etc., at a temperature of 100 to 250 ℃, a pressure of 0.2 to 10MPa, and a heating time of 0.1 to 5 hours. The prepreg of the present invention may be combined with an inner layer wiring board and laminated to form a laminate.

(multilayer printed Wiring Board)

The multilayer printed wiring board of the present invention is manufactured using the laminate. For example, the conductor layer of the laminate plate of the present invention may be subjected to wiring by a general etching method to obtain a circuit board. Thereafter, a plurality of laminated plates subjected to wiring processing using the above prepreg are laminated and subjected to heating press processing to be made into a multilayer at a time. Thereafter, a multilayer printed wiring board can be manufactured by forming a through hole or a blind via by drilling or laser processing, and forming an interlayer wiring by plating or a conductive paste.

(semiconductor Package)

The semiconductor package of the present invention is formed by mounting a semiconductor element on the multilayer printed wiring board. The semiconductor package of the present invention is manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the printed wiring board.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The resin sheets obtained in examples and comparative examples were measured and evaluated for cure shrinkage by the following methods, and the copper-clad laminate was measured and evaluated for glass transition temperature, thermal expansion coefficient, copper foil adhesiveness, copper-containing solder heat resistance, flexural modulus, and dielectric properties by the following methods.

(1) Measurement of curing shrinkage of resin sheet

A5 mm square resin plate (thickness: 1mm) was prepared, and thermomechanical analysis was performed by a compression method using a TMA tester (Q400, manufactured by TA Instrument Co.). After the resin plate was mounted on the apparatus in the Z direction, the load was set to 5g, the temperature increase rate was set to 45 ℃/min, and the temperature distribution was measured using a temperature distribution of 20 ℃ (holding for 5 min) to 260 ℃ (holding for 2 min) to 20 ℃ (holding for 5 min). The curing shrinkage of the resin sheet was evaluated from the initial size of the resin sheet, and the amount of change in size at 20 ℃ before and after the start of temperature rise.

Specifically, the curing shrinkage of the resin plate was calculated using the following formula.

Curing shrinkage (%) { (dimension (mm) at 20 ℃ before start of temperature increase-dimension (mm) at 20 ℃ after temperature increase))/dimension (mm) at 20 ℃ before start of temperature increase) } × 100

(2) Determination of glass transition temperature (Tg)

A 5mm square evaluation substrate from which the copper foil was removed was produced by immersing the copper-clad laminate in a copper etching solution, and thermomechanical analysis was performed by a compression method using a TMA tester (Q400, manufactured by TA Instrument). After the evaluation substrate was mounted on the apparatus in the Z direction, the substrate was continuously measured 2 times under the measurement conditions of a load of 5g and a temperature rise rate of 10 ℃/min. The Tg indicated by the intersection of the tangent lines of the difference in thermal expansion curves in the second measurement was obtained, and the heat resistance was evaluated.

(3) Measurement of thermal expansion Rate

A 5mm square evaluation substrate from which the copper foil was removed was produced by immersing the copper-clad laminate in a copper etching solution, and thermomechanical analysis was performed by a compression method using a TMA tester (Q400, manufactured by TA Instrument). After the evaluation substrate was mounted on the apparatus in the Z direction, the substrate was continuously measured 2 times under the measurement conditions of a load of 5g and a temperature rise rate of 10 ℃/min. The average thermal expansion coefficient of 30 ℃ to 100 ℃ in the second measurement was calculated and used as the value of the thermal expansion coefficient.

(4) Evaluation of copper foil adhesiveness (copper foil peeling Strength)

The copper-clad laminate was immersed in a copper etching solution to form a copper foil having a width of 3mm, and an evaluation substrate was prepared, and the adhesiveness (peel strength) of the copper foil was measured using a tensile tester.

(5) Evaluation of Heat resistance of copper-containing solder

A25 mm square evaluation substrate was prepared from the copper-clad laminate, and the heat resistance of the copper-containing solder was evaluated by observing the appearance of the evaluation substrate floating in a solder bath at 288 ℃ for 120 minutes.

(6) Modulus of elasticity in bending

A25 mm × 50mm evaluation substrate from which copper foil was removed was prepared by immersing a copper-clad laminate in a copper etching solution, and the evaluation substrate was measured at a crosshead speed of 1mm/min and a span of 20mm using 5 tons of Tensilon manufactured by Orientech corporation.

(7) Dielectric Properties (dielectric constant and dielectric loss tangent)

A100 mm × 2mm evaluation substrate from which copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and the dielectric constant and dielectric loss tangent at a frequency of 1GHz were measured using a cavity resonator machine (manufactured by Kanto electronics applications Co., Ltd.).

Production example 1: production of siloxane Compound (i-1)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 3, 3 '-dimethyl-4, 4' -diaminobiphenyl: 0.27g, terephthalaldehyde: 0.33g, X-22-161B: 199.4g, propylene glycol monomethyl ether: 300.0g, reacted at 115 ℃ for 4 hours, then heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, to obtain a solution containing the modified siloxane compound (i-1) having an aromatic azomethine (Mw: 30000, resin component: 90 mass%).

Production example 2: production of siloxane Compound (i-2)

To a 2 liter reaction vessel having a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 4, 4' -diaminobenzanilide: 0.27g, terephthalaldehyde: 0.31g, X-22-161B: 199.4g, propylene glycol monomethyl ether: 300.0g was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, thereby obtaining a solution containing the modified siloxane compound (i-2) having an aromatic azomethine (Mw: 31000, resin component: 90 mass%).

Production example 3: production of siloxane Compound (i-3)

To a 2 liter reaction vessel having a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 4-aminophenyl-4' -aminobenzoate: 0.27g, terephthalaldehyde: 0.31g, X-22-161B: 199.4g, propylene glycol monomethyl ether: 300.0g was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, thereby obtaining a solution containing the modified siloxane compound (i-3) having an aromatic azomethine (Mw: 31000, resin component: 90 mass%).

Production example 4: production of siloxane Compound (i-4)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 4, 4' -diaminoazobenzene: 0.27g, terephthalaldehyde: 0.31g, X-22-161B: 199.4g, propylene glycol monomethyl ether: 300.0g, reacted at 115 ℃ for 4 hours, then heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, to obtain a solution containing the modified siloxane compound (i-4) having an aromatic azomethine (Mw: 30000, resin component: 90 mass%).

Production example 5: production of siloxane Compound (i-5)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with reflux condenser, capable of heating and cooling, was added 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane: 0.18g, terephthalaldehyde: 0.19g, KF-8012: 199.6g, propylene glycol monomethyl ether: 300.0g, reacted at 115 ℃ for 4 hours, then heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, to obtain a solution containing the modified siloxane compound (i-5) having an aromatic azomethine (Mw: 50000, resin component: 90 mass%).

Production example 6: production of siloxane Compound (ii-1)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with reflux condenser, capable of heating and cooling, was added 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane: 12.9g, terephthalaldehyde: 17.1g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aromatic azomethine compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, X-22-161B: 325.5g, propylene glycol monomethyl ether: 513.3g of a reaction mixture was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ and dehydrated by concentration under normal pressure to obtain a solution (Mw: 30000, resin component: 90 mass%) containing the modified siloxane compound (ii-1) having an aromatic azomethine.

Production example 7: production of siloxane Compound (ii-2)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 2, 5-dimethyl-1, 4-diaminobenzene: 8.7g, terephthalaldehyde: 21.3g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aromatic azomethine compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, X-22-161B: 413.8g, propylene glycol monomethyl ether: 645.7g, reacted at 115 ℃ for 4 hours, heated to 130 ℃ and dehydrated by concentration under normal pressure to obtain a solution containing the modified siloxane compound (ii-2) having an aromatic azomethine (Mw: 25000 resin component: 90 mass%).

Production example 8: production of siloxane Compound (ii-3)

To a 2 liter reaction vessel having a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 4, 4' -diaminobenzanilide: 12.1g, terephthalaldehyde: 17.9g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aromatic azomethine compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, X-22-161B: 342.1g, propylene glycol monomethyl ether: 538.1g of the reaction solution was reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to condense and dehydrate the reaction solution under normal pressure to obtain a solution containing the modified siloxane compound (ii-3) having an aromatic azomethine (Mw: 31000, resin component: 90 mass%).

Production example 9: production of siloxane Compound (ii-4)

To a 2 liter reaction vessel having a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 4-aminophenyl-4' -aminobenzoate: 12.2g, terephthalaldehyde: 17.9g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aromatic azomethine compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, X-22-161B: 341.6g, propylene glycol monomethyl ether: 537.3g, reacted at 115 ℃ for 4 hours, then heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, to obtain a solution containing the modified siloxane compound (ii-4) having an aromatic azomethine (Mw: 31000, resin component: 90 mass%).

Production example 10: production of siloxane Compound (ii-5)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser, capable of heating and cooling, was added 4, 4' -diaminoazobenzene: 11.6g, terephthalaldehyde: 18.4g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aromatic azomethine compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, X-22-161B: 352.1g, propylene glycol monomethyl ether: 553.1g, reacted at 115 ℃ for 4 hours, heated to 130 ℃ and dehydrated by concentration under normal pressure to obtain a solution (Mw: 30000, resin component: 90 mass%) containing the modified siloxane compound (ii-5) having an aromatic azomethine.

Production example 11: production of siloxane Compound (iii-1)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser tube, capable of heating and cooling, was added terephthalaldehyde: 5.2g, X-22-161A: 24.8g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aldehyde and azo methyl base modified siloxane compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, bis (4- (4-aminophenoxy) phenyl) propane: 13.0g, propylene glycol monomethyl ether: 44.4g of a solution (Mw: 40000, resin component: 90 mass%) containing the modified siloxane compound (iii-1) having an aromatic azomethine was obtained by reacting at 115 ℃ for 4 hours, heating to 130 ℃ and dehydrating by concentration under normal pressure.

Production example 12: production of siloxane Compound (iii-2)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser tube, capable of heating and cooling, was added terephthalaldehyde: 3.0g, X-22-161B: 27.0g, propylene glycol monomethyl ether: 45.0g of the reaction mixture was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ to condense and dehydrate the reaction mixture under normal pressure to obtain a solution (60 mass%) containing a modified siloxane compound having an aldehyde group and an azomethine group.

Then, to the above reaction solution, 3 '-diethyl-4, 4' -diaminodiphenylmethane: 4.6g, propylene glycol monomethyl ether: 31.9g of a reaction mixture was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ and dehydrated by concentration under normal pressure to obtain a solution containing the modified siloxane compound (iii-2) having an aromatic azomethine (Mw: 70000, resin component: 90 mass%).

Production example 13: production of siloxane Compound (iii-3)

To a 2 liter capacity reaction vessel equipped with a thermometer, a stirring device, a moisture meter with a reflux condenser tube, capable of heating and cooling, was added terephthalaldehyde: 3.0g, X-22-161B: 27.0g, propylene glycol monomethyl ether: 45.0g, in 115 degrees C reaction for 4 hours, heated to 130 degrees C and by atmospheric pressure concentration dehydration, containing aldehyde and azo methyl base modified siloxane compounds solution (resin components: 60 mass%).

Then, to the above reaction solution, 4' -diaminobenzanilide: 4.1g, propylene glycol monomethyl ether: 31.2g of the reaction mixture was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, thereby obtaining a solution (Mw: 69000, resin component: 90 mass%) containing the modified siloxane compound (iii-3) having an aromatic azomethine.

Production example 14: production of siloxane Compound (iii-4)

Then, to the above reaction solution, 4-aminophenyl-4' -aminobenzoate was added: 4.5g, propylene glycol monomethyl ether: 31.2g of the reaction mixture was reacted at 115 ℃ for 4 hours, and then the reaction mixture was heated to 130 ℃ and concentrated under normal pressure to dehydrate the reaction mixture, thereby obtaining a solution (Mw: 69000, resin component: 90 mass%) containing the modified siloxane compound (iii-4) having an aromatic azomethine.

Production example 15: production of siloxane Compound (iii-5)

Then, to the above reaction solution, 4' -diaminoazobenzene: 3.9g, propylene glycol monomethyl ether: 30.8g of a solution containing the modified siloxane compound (iii-5) having an aromatic azomethine was obtained by reacting at 115 ℃ for 4 hours, then heating to 130 ℃ and dehydrating by concentration under normal pressure (Mw: 68000, resin component: 90 mass%).

Production example 16: production of modified imide resin (j-1) having aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (i-1) having an aromatic azomethine: 62.4g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.9g, propylene glycol monomethyl ether: 443.8g, reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to concentrate the reaction mixture under normal pressure to obtain a solution (resin component: 60 mass%) containing the modified imide resin (j-1) having aromatic azomethine.

Production example 17: production of modified imide resin (j-2) having aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (i-2) having an aromatic azomethine: 62.5g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.8g, propylene glycol monomethyl ether: 443.8g, reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to concentrate the reaction mixture under normal pressure to obtain a solution (resin component: 60 mass%) containing the modified imide resin (j-2) having aromatic azomethine.

Production example 18: production of modified imide resin (j-3) having aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (ii-1) having an aromatic azomethine: 62.5g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.7g, propylene glycol monomethyl ether: 443.8g, reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to concentrate the reaction mixture under normal pressure to obtain a solution (resin component: 60 mass%) containing the modified imide resin (j-3) having aromatic azomethine.

Production example 19: production of modified imide resin (j-4) having aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (ii-3) having an aromatic azomethine: 62.3g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.9g, propylene glycol monomethyl ether: 443.8g, reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to concentrate the reaction mixture under normal pressure to obtain a solution (resin component: 60 mass%) containing the modified imide resin (j-4) having aromatic azomethine.

Production example 20: production of modified imide resin (j-5) having aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution containing the modified siloxane compound (iii-2) having an aromatic azomethine (resin component: 90 mass%): 62.5g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.8g, propylene glycol monomethyl ether: 443.8g, reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to concentrate the reaction mixture under normal pressure to obtain a solution (resin component: 60 mass%) containing the modified imide resin (j-5) having aromatic azomethine.

Production example 21: production of modified imide resin (j-6) having aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution containing the modified siloxane compound (iii-3) having an aromatic azomethine (resin component: 90 mass%): 61.7g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 244.4g, propylene glycol monomethyl ether: 443.8g, reacted at 115 ℃ for 4 hours, and then heated to 130 ℃ to concentrate the reaction mixture under normal pressure to obtain a solution (resin component: 60 mass%) containing the modified imide resin (j-6) having aromatic azomethine.

Production example 22: production of modified imide resin (k-1) having acidic substituent and aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (i-1) having an aromatic azomethine: 62.5g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238.1g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.8g was reacted at 115 ℃ for 4 hours, and then the reaction solution was concentrated at 130 ℃ under normal pressure to obtain a solution (resin component: 60 mass%) containing a modified imide resin (k-1) having an acidic substituent and an aromatic azomethine.

Production example 23: production of modified imide resin (k-2) having acid substituent and aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (i-2) having an aromatic azomethine: 62.6g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238.0g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.7g was reacted at 115 ℃ for 4 hours, and then the reaction solution was concentrated at 130 ℃ under normal pressure to obtain a solution (resin component: 60 mass%) containing a modified imide resin (k-2) having an acidic substituent and an aromatic azomethine.

Production example 24: production of modified imide resin (k-3) having acid substituent and aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (ii-1) having an aromatic azomethine: 62.5g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238.0g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.8g was reacted at 115 ℃ for 4 hours, and then the reaction solution was concentrated at 130 ℃ under normal pressure to obtain a solution (resin component: 60 mass%) containing a modified imide resin (k-3) having an acidic substituent and an aromatic azomethine.

Production example 25: production of modified imide resin (k-4) having acidic substituent and aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution (resin component: 90 mass%) containing the modified siloxane compound (ii-3) having an aromatic azomethine: 62.3g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238.2g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.8g was reacted at 115 ℃ for 4 hours, and then the reaction solution was concentrated at 130 ℃ under normal pressure to obtain a solution (resin component: 60 mass%) containing a modified imide resin (k-4) having an acidic substituent and an aromatic azomethine.

Production example 26: production of modified imide resin (k-5) having acidic substituent and aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution containing the modified siloxane compound (iii-2) having an aromatic azomethine (resin component: 90 mass%): 62.6g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238.0g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.7g was reacted at 115 ℃ for 4 hours, and then the reaction solution was concentrated at 130 ℃ under normal pressure to obtain a solution (resin component: 60 mass%) containing a modified imide resin (k-5) having an acidic substituent and an aromatic azomethine.

Production example 27: production of modified imide resin (k-6) having acid substituent and aromatic azomethine

To a reaction vessel having a capacity of 2 liters which can be heated and cooled and equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, was added a solution containing the modified siloxane compound (iii-3) having an aromatic azomethine (resin component: 90 mass%): 61.8g, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238.6g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.8g was reacted at 115 ℃ for 4 hours, and then the reaction solution was concentrated at 130 ℃ under normal pressure to obtain a solution (resin component: 60 mass%) containing a modified imide resin (k-6) having an acidic substituent and an aromatic azomethine.

Examples 1 to 39 and comparative examples 1 to 12

Using the solutions containing the modified siloxane compounds having an aromatic azomethine (I-1 to I-5, ii-1 to ii-5, iii-1 to iii-5) obtained in production examples 1 to 15, the solutions containing the modified imide resins having an aromatic azomethine (j-1 to j-6) obtained in production examples 16 to 21, the solutions containing the modified imide resins having an acidic substituent and an aromatic azomethine obtained in production examples 22 to 27, the aromatic amine compounds (a), the aromatic aldehyde compounds (B), the siloxane compounds (C), the maleimide compounds (D), the amine compounds (E) having an acidic substituent, the thermoplastic elastomer (F), the thermosetting resin (G), the inorganic filler (H), the curing accelerator (I), and methyl ethyl ketone as a diluting solvent, varnishes having a resin component of 65 mass% were obtained by mixing the components in the mixing ratios (parts by mass) shown in tables 1 to 9.

Then, the varnish was applied to a 16 μm polyethylene terephthalate film by a film coater (PI-1210, manufactured by Tester industries, Ltd.) so that the dried resin thickness became 35 μm, and the film was dried by heating at 160 ℃ for 10 minutes to obtain a resin powder of a semi-cured product. The support is not particularly limited, and a general-purpose material can be used, and a coating method is not particularly limited, so long as it is applied by using a general bench coater.

This resin powder was put into a template of a teflon (registered trademark) sheet, and a glossy surface of an electrolytic copper foil of 12 μm was arranged in the upper and lower sides, and after punching at a pressure of 2.0MPa and a temperature of 240 ℃ for 60 minutes, the electrolytic copper foil was removed to obtain a resin plate.

Further, the varnish was impregnated and coated on an E glass cloth having a thickness of 0.1mm, and dried by heating at 160 ℃ for 10 minutes to obtain a prepreg having a resin content of 48 mass%.

The prepreg was laminated into 4 sheets, and 12 μm electrolytic copper foils were placed in the upper and lower positions, and pressed at a pressure of 3.0MPa and a temperature of 240 ℃ for 60 minutes to obtain a copper-clad laminate.

The measurement and evaluation results of the obtained resin board and copper-clad laminate are shown in tables 1 to 9.

Aromatic amine Compound (A)

KAYAHARD A-A: 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane [ product name of Nippon Kagaku K.K. ]

4, 4' -Diaminobenzanilide (trade name, product of Tokyo Kasei Co., Ltd.)

4-aminophenyl-4' -aminobenzoate [ product name of Vinza, manufactured by sunshine pharmaceutical Co., Ltd ]

Aromatic aldehyde Compound (B)

TPAL: terephthalaldehyde (trade name, product of Toray Fine chemical Co., Ltd.)

Siloxane compound (C)

X-22-161B: both terminal amino-modified siloxane [ trade name manufactured by shin-Etsu chemical Co., Ltd ]

Maleimide compound (D)

BMI: bis (4-maleimidophenyl) methane [ KI-Compound Co., Ltd., trade name ]

BMI-4000: 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane [ product name of Dahe Kasei Kogyo Co., Ltd ]

Amine Compound (E) having acidic substituent

P-aminophenol (trade name, product of Kanto chemical Co., Ltd.)

Thermoplastic elastomer (F)

Tuftec H1043: hydrogenated styrene-butadiene copolymer resin [ product name of Asahi Kasei Chemicals Co., Ltd ]

Epofriend CT-310: epoxy-modified styrene-butadiene copolymer resin [ product name of Daicel corporation ]

Thermosetting resin (G)

PT-30: phenol type cyanate ester resin [ product name of Lonza Japan K.K. ]

NC-7000L α -Naphthol/cresol novolac type epoxy resin (trade name, manufactured by Nippon Kabushiki Kaisha)

Inorganic filler (H)

SC 2050-KNK: fused silica [ trade name of Admatox K.K. ]

Zinc molybdate (trade name, product of Sherwin-Williams corporation: KEMGARD 1100)

Curing accelerator (I)

Zinc naphthenate (II) 8% Petroleum solvent oil solution (trade name, product of Tokyo Kasei Kogyo Co., Ltd.)

G-8009L: isocyanate-masked imidazole [ product name of first Industrial pharmaceutical Co., Ltd ]

TPP-MK: tetraphenylphosphonium tetra-p-tolylborate [ trade name, made by Beixinghua chemical industry Co., Ltd ]

The amounts (parts by mass) of the solutions containing the siloxane compounds (i-1) to (iii-5), the solutions containing the modified imide resins (j-1) to (j-6) having an aromatic azomethine, and the solutions containing the modified imide resins (k-1) to (k-6) having an acidic substituent and an aromatic azomethine in tables 1 to 4 are shown below as values in terms of the solid content of the resin component.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

As is clear from tables 1 to 9, in the examples of the present invention, the resin sheet was small in cure shrinkage and excellent in low cure shrinkage, and the thermal expansion coefficient, copper foil adhesiveness, elastic modulus, and dielectric characteristics were also excellent in the characteristics of the laminate.

On the other hand, the resin sheet of the comparative example has a large cure shrinkage rate, and the thermal expansion coefficient, copper foil adhesiveness, elastic modulus, and dielectric characteristics are inferior to those of the examples in terms of the characteristics of the laminate.

Industrial applicability

The prepreg obtained by impregnating or applying the thermosetting resin composition containing a siloxane compound of the present invention to a substrate, the resin-carrying film obtained by applying the composition to a support, and the laminate produced by laminating the prepreg have particularly low curing shrinkage, particularly low thermal expansion, copper foil adhesiveness, high elastic modulus, and particularly excellent dielectric properties, and are useful as highly integrated multilayer printed wiring boards for semiconductor packages or electronic devices.

Claims

1. Use of a silicone compound comprising a structure represented by the following general formula (1), and a structure derived from a silicone compound having at least 2 amino groups at a molecular terminal as a structure represented by the following general formula (2), for a printed wiring board;

in the formula, R₁And R₂Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an acetyl group, a hydroxyl group, a sulfonic group, a sulfoalkoxy group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and x and y are each independently an integer of 0 to 4; a is a single bond or an azomethine group, an azoxy group, an azo group, an ethylene group or an ethynyl group;

2. Use of the silicone compound according to claim 1 for a printed wiring board, wherein the silicone compound comprising the structure shown in the general formula (1) and a structure derived from a silicone compound having at least 2 amino groups at a molecular terminal as the structure shown in the general formula (2) further contains an aromatic azomethine.