JP2021161206A - Resin composition, resin paste, cured product, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device - Google Patents

Abstract

To provide a resin composition excellent in chemical resistance and capable of obtaining a cured product having suppressed warpage; and to provide a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.SOLUTION: A resin composition comprises (A) an epoxy resin and (B) a curing agent, wherein a value Zi (ppm_cm3/mol_K) obtained by dividing an average linear thermal expansion coefficient α of a cured product by a cross-linking density n of the cured product satisfies 10<Zi<100.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. Further, the present invention relates to a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.

Printed wiring boards for semiconductor devices include an insulating layer. A resin composition is used as an insulating material constituting this insulating layer. Patent Document 1 discloses an insulating material containing a thermosetting compound and a curing agent (see claim 1). In such an insulating layer, a conductor made of metal may be formed as a wiring layer.

JP-A-2017-188667

Here, in the step of forming the wiring layer, a chemical (for example, a strong alkaline aqueous solution as a stripping solution for a positive photoresist) is used. Therefore, the cured product of the resin composition is required to have excellent chemical resistance.

On the other hand, when the semiconductor chip is sealed (particularly when one side of the semiconductor chip is sealed), warpage may occur due to the bias of stress. Therefore, it is required to suppress warpage.

However, according to the research results of the inventor, when the content of a component (for example, an inorganic filler) that enhances the mechanical strength of the cured product is increased in the resin composition, it tends to be more difficult to suppress the warp. On the other hand, it was found that when a component that enhances the flexibility of the cured product is added to the resin composition, the chemical resistance tends to be impaired. That is, it is difficult to achieve both excellent chemical resistance and suppression of warpage.

An object of the present invention is a resin composition capable of obtaining a cured product having excellent chemical resistance and suppressed warpage; and a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor. To provide the equipment.

As a result of diligent studies on the resin composition containing (A) epoxy resin and (B) curing agent, the present inventor has determined the average linear thermal expansion coefficient α of the cured product of the resin composition and the cross-linking density n of the cured product. _{Is used as a parameter, and the value Z i} (ppm · cm ³ / mol · K) obtained by dividing the average coefficient of linear thermal expansion α by the cross-linking density n _{satisfies 10 <Z i} <100, thereby solving the above-mentioned problems. This has led to the completion of the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin and (B) a curing agent.
The value Z obtained by dividing the average linear thermal expansion coefficient α (ppm / K) of the cured product obtained by curing the resin composition at 150 ° C. for 60 minutes by the cross-linking density n (mol / cm ^{3) of the cured product.} _i (pm · cm ³ / mol · K) is the following formula:
10 <Z _i <100
A resin composition that meets the requirements.
[2] The resin composition according to [1], further comprising (C) an inorganic filler.
[3] The resin composition according to [2], wherein the content of the component (C) is 80% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[4] The component (B) is an acid anhydride-based curing agent, a maleimide-based curing agent, an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a carbodiimide-based curing agent, a benzoxazine-based curing agent, and an amine-based component. The resin composition according to any one of [1] to [3], which comprises one or more curing agents selected from a curing agent and a cyanate ester-based curing agent.
[5] The resin according to any one of [1] to [4], wherein the content of the component (B) is 0.5% by mass or more when the non-volatile component in the resin composition is 100% by mass. Composition.
[6] The description according to any one of [1] to [5], wherein the component (A) is at least one selected from (A-1) liquid epoxy resin and (A-2) solid epoxy resin. Resin composition.
[7] The resin composition according to [6], wherein the content of the (A-2) solid epoxy resin is 10% by mass or less when the content of the component (A) is 100% by mass.
[8] The mass ratio of the content of the component (A-1) to the content of the component (A-2) ((A-1) :( A-2)) is 1: 0 to 1: 0.1. The resin composition according to [6] or [7], which is within the range.
[9] The resin composition according to any one of [1] to [8], wherein the glass transition temperature Tg (° C.) of the cured product is in the range of 150 to 240 ° C.
[10] The resin composition according to any one of [1] to [9], wherein the average linear thermal expansion coefficient α of the cured product is 21 ppm / K or less.
[11] The storage elastic modulus E of the cured product 'is 1.00 × ¹⁰ 9 Pa, greater than [1] to the resin composition according to any one of [10].
[12] The resin composition according to any one of [1] to [11], wherein the crosslinked density n of the cured product ^{is less than 0.50 mol / cm 3.}
[13] The resin composition according to any one of [1] to [12], wherein the crosslinked density n of the cured product is 0.16 mol / cm ^{3 or more.}
[14] The resin composition according to any one of [1] to [13], which is used for forming an insulating layer.
[15] The resin composition according to any one of [1] to [14], which is used for forming a solder resist layer.
[16] A resin paste formed by containing the resin composition according to any one of [1] to [15].
[17] The resin composition according to any one of [1] to [15] or the cured product of the resin paste according to [16].
[18] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [15].
[19] A printed circuit board comprising the resin composition according to any one of [1] to [15], a cured product of the resin paste according to [16], or an insulating layer formed by the cured product according to [17]. Wiring board.
[20] A semiconductor chip package including the printed wiring board according to [19] and a semiconductor chip mounted on the printed wiring board.
[21] The semiconductor chip and the resin composition according to any one of [1] to [15] for sealing the semiconductor chip, the cured product of the resin paste according to [16], or the cured product according to [17]. Semiconductor chip package including things.
[22] A semiconductor device including the printed wiring board according to [19] or the semiconductor chip package according to [20] or [21].

According to the present invention, a resin composition capable of obtaining a cured product having excellent chemical resistance and suppressed warpage; and a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package and a semiconductor. Equipment can be provided.

Hereinafter, the resin composition, resin paste, cured product, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin and (B) a curing agent, and the average linear thermal expansion of the cured product obtained by curing the resin composition at 150 ° C. for 60 minutes. _{The value Z i} (ppm · cm ³ / mol · K) obtained by dividing the coefficient α by the crosslink density n of the cured product is within the numerical range described later. According to this resin composition, it is possible to obtain a cured product having excellent chemical resistance and suppressed warpage. By using such a resin composition, it is possible to provide a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.

The resin composition of the present invention may further contain any component in combination with the component (A) and the component (B). Examples of the optional component include (C) an inorganic filler, (D) a curing accelerator, and (E) other additives. Hereinafter, each component contained in the resin composition will be described in detail. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

<(A) Epoxy resin>
The resin composition contains (A) epoxy resin. The epoxy resin refers to a resin having one or more epoxy groups in the molecule. When the resin composition contains the epoxy resin (A), a cured product having a crosslinked structure can be obtained.

Examples of the epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Naftor novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type Examples thereof include epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. The epoxy resin may be used alone or in combination of two or more.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in the molecule. When the non-volatile component of the epoxy resin is 100% by mass, 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in the molecule.

The epoxy resin may be (A-1) a liquid epoxy resin or (A-2) a solid epoxy resin. The resin composition may contain a combination of (A-1) a liquid epoxy resin and (A-2) a solid epoxy resin.

((A-1) Liquid epoxy resin)
(A-1) The liquid epoxy resin refers to an epoxy resin that is liquid at a temperature of 20 ° C. The resin composition preferably contains (A-1) a liquid epoxy resin. Here, the liquid epoxy resin is one of the components that tends to lower the glass transition temperature of the cured product of the resin composition, but according to the present invention, even if the resin composition contains such a component. It is possible to obtain a cured product having a sufficiently low average linear thermal expansion coefficient and excellent heat resistance.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in the molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in the molecule is more preferable. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, the cyclohexane type epoxy resin, the cyclohexanedimethanol type epoxy resin, the glycidylamine type epoxy resin, and the epoxy resin having a butadiene structure are preferable, and the bisphenol A type epoxy resin is more preferable.

Specific examples of the liquid epoxy resin include "YX7400" manufactured by Mitsubishi Chemical Co., Ltd .; "HP4032", "HP4032D", "HP-4032-SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd .; "828US" manufactured by Mitsubishi Chemical Co., Ltd. , "JER828EL", "825", "828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" manufactured by Mitsubishi Chemical Co., Ltd. ( Phenol novolac type epoxy resin); Mitsubishi Chemical Co., Ltd. "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) Product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd .; "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "PB-3600" manufactured by Daicel Co., Ltd. (Epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the component (A-1) in the resin composition is determined in the resin composition from the viewpoint of obtaining the effect of containing the component (A-1) (for example, improvement in handleability and improvement in compatibility). When the non-volatile component is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit of the content of the component (A-1) is not particularly limited as long as the effect of the present invention is not excessively impaired, but may be 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less. ..

((A-2) Solid epoxy resin)
The solid epoxy resin refers to a solid epoxy resin at a temperature of 20 ° C. The resin composition may contain only (A-2) solid epoxy resin as the component (A), but from the viewpoint of increasing the crosslink density, it may be combined with (A-1) liquid epoxy resin (A-). 2) It is also preferable to contain a solid epoxy resin. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in the molecule is preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthol type epoxy resin, bisphenol AF type epoxy resin, naphthalene type Epoxy resins and biphenyl type epoxy resins are more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP7200L", "HP-7200", "HP-7200HH" , "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", manufactured by DIC. "HP6000", "HP6000L" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd. ); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayakusha; "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "157S70" (bisphenol A novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ); "YL7760" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin); Mitsubishi Examples thereof include "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Chemical Co., Ltd. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the component (A-2) in the resin composition is the effect of including the component (A-2) (for example, from the viewpoint of lowering the average coefficient of linear thermal expansion, improving heat resistance, or having a good cross-linking density). When the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, in particular. It is preferably 0.2% by mass or more. The upper limit of the content of the component (A-2) is not particularly limited as long as the effect of the present invention is not excessively impaired, but from the viewpoint of appropriately suppressing the crosslink density, 10% by mass or less, 8% by mass or less, and 5% by mass. % Or less, 3% by mass or less, or 1% by mass or less.

When (A-1) liquid epoxy resin and (A-2) solid epoxy resin are used in combination as the component (A), their quantity ratios (liquid epoxy resin: solid epoxy resin) are mass ratios. The range of 1: 0.01 to 1: 0.8 is preferable. By setting the amount ratio of (A-1) liquid epoxy resin and (A-2) solid epoxy resin within such a range, i) appropriate adhesiveness when used in the form of a resin composition molded product can be obtained. There are effects such as ii) improved handleability when used in the form of a molded resin composition, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of obtaining the effects of i) to iii) and appropriately suppressing the crosslink density, the mass ratio of (A-1) liquid epoxy resin and (A-2) solid epoxy resin (liquid epoxy resin: solid epoxy). The resin) is more preferably in the range of 1: 0.01 to 1: 0.5 and further preferably in the range of 1: 0.01 to 1: 0.1 in terms of mass ratio.

The content of the component (A) in the resin composition is preferably 0.5% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of exerting the desired effect of the present invention. It is more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but may be 70% by mass or less, 60% by mass or less, 50% by mass or 35% by mass or less.

The epoxy equivalent of the component (A) is preferably 50 g / eq. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 70 g / eq. ~ 2000 g / eq. , Even more preferably 70 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslink density of the cured product becomes sufficient, and a cured product having excellent strength and heat resistance can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(B) Hardener>
The resin composition contains (B) a curing agent. As the component (B), a component having a function of curing the component (A) can be used. When the resin composition contains (A) an epoxy resin and (B) a curing agent, a cured product having excellent heat resistance can be obtained. The component (B) may be a liquid curing agent at a temperature of 20 ° C. (hereinafter, also referred to as “liquid curing agent”), or a solid curing agent at a temperature of 20 ° C. (hereinafter, “solid curing agent”). It may also be referred to as), or these may be combined. Preferably, component (B) contains a liquid curing agent and, if necessary, a solid curing agent.

Examples of the curing agent (B) include acid anhydride-based curing agents, maleimide-based curing agents, active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, and amines. Examples thereof include a system curing agent and one or more types of curing agents selected from cyanate ester type curing agents. The curing agent may be used alone or in combination of two or more.

Above all, from the viewpoint of enhancing the desired effect of the present invention, the component (B) preferably contains an acid anhydride-based curing agent.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride. Anhydride, Trialkyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Trianhydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like. Commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nihon Rika Co., Ltd., and "OSA" manufactured by Mitsubishi Chemical Corporation. Examples thereof include "YH-306" and "YH-307", "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

Examples of amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, and alicyclic amines. Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. As the amine-based curing agent, a primary amine or a secondary amine is preferable, and a primary amine is more preferable. Specific examples of amine-based curing agents include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, Examples thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine-based curing agent. For example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard AB" manufactured by Nippon Kayaku Co., Ltd. may be used. Examples include "Kayahard AS", "Epicure W" manufactured by Mitsubishi Chemical Corporation, and "DTDA" manufactured by Sumitomo Seika Chemical Co., Ltd.

(Maleimide-based curing agent)
As the maleimide-based curing agent, the (B-2a) molecule may have an alkyl group having 5 or more carbon atoms which may have a substituent and 5 carbon atoms which may have a substituent. Maleimide compounds having at least one of the above-mentioned hydrocarbon chains of alkylene groups (hereinafter, may also be referred to as “aliphatic structure-containing maleimide compound”) can be mentioned. Moreover, as a maleimide-based curing agent, a maleimide-based curing agent other than the components (B-2b) and (B-2a) can be mentioned. The maleimide-based curing agent may be used alone or in combination of two or more. The maleimide-based curing agent preferably contains the component (B-2a), and may further contain the component (B-2b) in combination.

The maleimide-based curing agent is a compound containing at least one maleimide group represented by the following formula in the molecule, and is preferably an aliphatic structure-containing maleimide compound. In the structure shown in the following formula, one of the three bonds of the nitrogen atom that is not bonded to the other atom means a single bond.

The number of maleimide groups per molecule in the maleimide-based curing agent is 1 or more, and from the viewpoint of enhancing the desired effect of the present invention, it is preferably 2 or more, more preferably 3 or more, and the upper limit is The number is not limited, but may be 10 or less, 6 or less, 4 or less, or 3 or less.

The number of carbon atoms of the alkyl group having 5 or more carbon atoms in the aliphatic structure-containing maleimide compound is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Is. The alkyl group may be linear, branched or cyclic, and the linear group is preferable. Examples of such an alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like. The alkyl group having 5 or more carbon atoms may be a substituent of an alkylene group having 5 or more carbon atoms.

The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. The alkylene group may be linear, branched or cyclic, and the linear group is preferable. Here, the cyclic alkylene group is a concept including a case where it is composed of only a cyclic alkylene group and a case where it contains both a linear alkylene group and a cyclic alkylene group. Examples of such an alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group and an octylene-cyclohexylene. Examples thereof include a group having a structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

From the viewpoint of enhancing the desired effect of the present invention, the aliphatic structure-containing maleimide compound may have a substituent in the (B-1a) molecule, an alkyl group having 5 or more carbon atoms, and a substituent. A maleimide compound having at least one hydrocarbon chain of an alkylene group having 5 or more carbon atoms which may have a group, an alkyl group having 5 or more carbon atoms and an alkylene having 5 or more carbon atoms. It is preferably a maleimide compound having both groups.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may be in the form of a chain, but at least a part of the carbon atoms may be bonded to each other to form a ring. The ring structure also includes a spiro ring and a fused ring. Examples of the ring formed by bonding with each other include a cyclohexane ring and the like.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may have no substituent or may have a substituent. Examples of the substituent include a halogen atom, -OH, -OC _1-10 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C 6-10 aryl group, _and-. NH ₂ , -CN, -C (O) O-C _1-10 alkyl group, -COOH, -C (O) H, -NO _{2 and the} like can be mentioned. Here, the term "C _x-y " (x and y are positive integers and satisfy x <y) is described immediately after this term when the number of carbon atoms of the organic group is xy. Indicates that there is. For example, _{the expression "C 1-10} alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms. The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

In the aliphatic structure-containing maleimide compound, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group.

The number of maleimide groups per molecule of the aliphatic structure-containing maleimide compound may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. be. When the aliphatic structure-containing maleimide compound has two or more maleimide groups per molecule, the desired effect of the present invention can be enhanced.

The aliphatic structure-containing maleimide compound is preferably a maleimide compound represented by the following general formula (B1).

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the above-mentioned alkylene group having 5 or more carbon atoms. Examples of the substituent of M include a halogen atom, -OH, -OC _1-10 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-10 alkyl group, and C _6-10 aryl group. , -NH ₂ , -CN, -C (O) OC _1-10 alkyl group, -COOH, -C (O) H, -NO _{2 and the} like. Here, the term "C _x-y " (x and y are positive integers and satisfy x <y) is described immediately after this term when the number of carbon atoms of the organic group is xy. Indicates that there is. For example, _{the expression "C 1-10} alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent. The substituent of M is preferably an alkyl group having 5 or more carbon atoms. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkylene group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C (= O)-, -C (= O) -O-, and -NR ^0- (R ⁰ is a hydrogen atom and carbon. Alkyl group with 1-3 atoms), oxygen atom, sulfur atom, C (= O) NR ⁰ −, divalent group derived from phthalimide, divalent group derived from diimide pyromellitic acid, and two or more of these. Examples thereof include a group consisting of a combination of divalent groups. A group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, and a combination of two or more divalent groups has a carbon atom number. May have 5 or more alkyl groups as substituents.

The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and specifically, is a group represented by the following general formula. In the formula, "*" represents a bond.

The divalent group derived from diimide pyromellitic acid represents a divalent group derived from diimide pyromellitic acid, and specifically, is a group represented by the following general formula. In the formula, "*" represents a bond.

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. .. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group and a hexatria. Examples thereof include a contylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. .. The alkenylene group may be linear, branched or cyclic. Examples of such an alkenylene group include a methylethyleneylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group and the like.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. .. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptinylene group, an octynylene group and the like.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 14 carbon atoms. , An arylene group having 6 to 10 carbon atoms is even more preferable. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group and the like.

The divalent linking group in L, such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, may have a substituent. The substituent is the same as the substituent of M in the general formula (B1), and is preferably an alkyl group having 5 or more carbon atoms.

Examples of the group consisting of a combination of two or more divalent groups in L include an alkylene group, a divalent group derived from phthalimide, and a divalent group consisting of a combination with an oxygen atom; a divalent group derived from phthalimide. , A divalent group consisting of a combination of an oxygen atom, an arylene group and an alkylene group; a divalent group consisting of a combination of an alkylene group and a divalent group derived from diimide pyromellitic acid; and the like. A group composed of a combination of two or more kinds of divalent groups may form a ring such as a fused ring by the combination of each group. Further, the group composed of a combination of two or more kinds of divalent groups may be a repeating unit having 1 to 10 repeating units.

Among them, L in the general formula (B1) includes an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, and 1 to 1 which may have a substituent. A divalent group consisting of 50 alkylene groups, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, or a combination of 2 or more of these groups. It is preferable to have. Among them, L is an alkylene group; an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group having a divalent group structure derived from phthalimide; an alkylene group-a divalent group derived from phthalimide- Oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-divalent group having a divalent group structure derived from phthalimide; divalent group having a divalent group structure derived from alkylene-pyromellitic acid diimide Groups are more preferred.

The aliphatic structure-containing maleimide compound is preferably a maleimide compound represented by the following general formula (B2).

M ¹ represents an alkylene group having 5 or more carbon atoms, which may independently have a substituent. M ¹ is the same as M in the general formula (B1).

A represents an alkylene group having 5 or more carbon atoms which may independently have a substituent or a divalent group having an aromatic ring which may have a substituent. The alkylene group in A may be chain-shaped, branched-chain-shaped, or cyclic, and among them, a cyclic, that is, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferable. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

Examples of the aromatic ring in the divalent group having the aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a diimide ring of pyromellitic acid, an aromatic heterocycle, and the like, and a benzene ring and a phthalimide ring. A ring and a diimide ring of pyromellitic acid are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a substituent are substituted. A divalent group having a diimide ring of pyromellitic acid, which may have a group, is preferable. The divalent group having an aromatic ring includes, for example, a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group. Group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a divalent group derived from diimide pyromellitic acid; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; etc. Can be mentioned. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B1).

The divalent group having an alkylene group and an aromatic ring represented by A may have a substituent. The substituent is the same as the substituent represented by the substituent of M in the general formula (B1).

Specific examples of the group represented by A include the following groups. In the formula, "*" represents a bond.

The maleimide compound represented by the general formula (B2) may be either a maleimide compound represented by the following general formula (B2-1) or a maleimide compound represented by the following general formula (B2-2). preferable.

M ² and M ³ each represent an alkylene group having 5 or more carbon atoms which may have a substituent independently. M ² and M ³ are the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (B1), and a hexatriacontylene group is preferable.

Each of R ³⁰ independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B1). R ³⁰ is preferably a group consisting of a combination of two or more divalent groups or an oxygen atom.

Examples of the group consisting of a combination of two or more divalent groups in R ³⁰ include a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of a group consisting of a combination of two or more divalent groups include the following groups. In the formula, "*" represents a bond.

M ⁴ , M ⁶ and M ⁷ each represent an alkylene group having 5 or more carbon atoms which may independently have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as the alkylene group having 5 or more carbon atoms which may have the substituent represented by M in the general formula (B1), and are hexylene group, heptylene group and octylene. A group, a nonylene group and a decylene group are preferable, and an octylene group is more preferable.

M ⁵ represents a divalent group having an aromatic ring, each of which may independently have a substituent. M ⁵ is the same as a divalent group having an aromatic ring which may have a substituent represented by A in the general formula (B2), and is a divalent group derived from an alkylene group and diimide pyromellitic acid. Group consisting of a combination; a group composed of a combination of a divalent group derived from phthalimide and an alkylene group is preferable, and a group composed of a combination of a divalent group derived from an alkylene group and diimide pyromellitic acid is more preferable.

Specific examples of the group represented by M ^{5 include the following groups.} In the formula, "*" represents a bond.

R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms. R ³¹ and R ³² are the same as the above-mentioned alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group, and more preferably a hexyl group and an octyl group.

u1 and u2 each independently represent an integer of 1 to 15, and an integer of 1 to 10 is preferable.

Specific examples of the aliphatic structure-containing maleimide compound include the following compounds (b1), (b2), (b3) and (b4). However, the aliphatic structure-containing maleimide compound is not limited to these specific examples. In the formulas (b1), (b2), and (b3), n9, n10, and n11 represent integers of 1 to 10.

Specific examples of the aliphatic structure-containing maleimide compound include "BMI-1500" (compound of formula (b1)), "BMI-1700" (compound of formula (b2)), and "BMI-" manufactured by Designer Moleculars. Examples thereof include "3000J" (compound of formula (b3)) and "BMI-689" (compound of formula (b4)). Above all, it is preferable to use a liquid maleimide compound (for example, "BMI-689").

The maleimide group equivalent of the maleimide-based curing agent is preferably 50 g / eq. From the viewpoint of enhancing the desired effect of the present invention. ~ 2000 g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. , More preferably 150 g / eq. ~ 500 g / eq. Is. The maleimide group equivalent is the mass of the maleimide compound containing 1 equivalent of the maleimide group.

The active ester-based curing agent is not particularly limited, but generally contains one molecule of an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having two or more of them are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of active ester-based curing agents include "EXB-9451", "EXB-9460", "EXB-9460S", and "HPC-96000-65T" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "HPC-8000H-65TM", "HPC-8000L-65TM" (manufactured by DIC), "EXB-9416-70BK", "EXB-8100L-65T", "EXB-" as active ester compounds containing a naphthalene structure. 8150-65T ”,“ EXB-8150L-65T ”,“ HPC-8150-60T ”,“ HPC-8150-62T ”,“ HP-B-8151-62T ”(manufactured by DIC), acetylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, and "" as an active ester-based curing agent which is an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as active ester-based curing agents that are benzoylates of phenol novolac. ), Examples of the active ester compound containing a styryl group include "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.).

As the phenol-based curing agent (excluding the active ester compound) and the naphthol-based curing agent (excluding the active ester compound), a phenol-based curing agent having a novolak structure or a cresol novolak structure, or novolak, from the viewpoint of heat resistance and water resistance. A naphthol-based curing agent having a structure is preferable. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Meiwakasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH" manufactured by Nippon Steel & Sumitomo Metal Corporation, "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395", "TD-2090", "LA-7052", "LA-7854", "LA-1356", "LA-3018-50P", "EXB-9500", manufactured by DIC Corporation, Examples thereof include "KA-1160".

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07", "V-09", and "Elastostab H01" manufactured by Nisshinbo Chemical Co., Ltd.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "P-d" manufactured by Shikoku Chemicals Corporation. "FA" can be mentioned. The benzoxazine-based curing agent is a compound having a benzoxazine structure. The benzoxazine structure is a substituted or unsubstituted benzoxazine ring (for example, 1,2-benzoxazine ring, 1,3-benzoxazine ring), or a benzoxazine ring in which a part of the double bond is hydrogenated. (For example, 3,4-dihydro-2H-1,3-benzoxazine ring).

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which a part or all of bisphenol A disianate is triazined to form a trimer) and the like.

The amount ratio of (A) epoxy resin and (B) curing agent is the ratio of [total number of epoxy groups in epoxy resin]: [total number of reactive groups in curing agent], 1: 0.01 to 1: The range of 2 is preferable, 1: 0.05 to 1: 3 is more preferable, and 1: 0.1 to 1: 1.5 is even more preferable. Here, the reactive group of the (B) curing agent is an active ester group, an active hydroxyl group, or the like, and differs depending on the type of the (B) curing agent. The total number of epoxy groups in (A) epoxy resin is the total number of all epoxy resins obtained by dividing the non-volatile content mass of each of (A) epoxy resins by the epoxy equivalent, and (B) curing. The total number of reactive groups of the agent is (B) the value obtained by dividing the non-volatile content mass of each of the curing agents by the reactive group equivalent, and is the total value for all the curing agents. By setting the amount ratio of the epoxy resin (A) to the curing agent (B) within such a range, the desired effect of the present invention can be enhanced.

The content of the component (B) is preferably determined so as to satisfy the range of the amount ratio of the epoxy resin (A) and the curing agent (B) described above. From the viewpoint of enhancing the desired effect of the present invention, the content of the component (B) is 0.5% by mass or more, 1% by mass or more, and 2% by mass when the non-volatile content in the resin composition is 100% by mass. % Or more or 3% by mass or more, 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, or 17% by mass or less.

<(C) Inorganic filler>
The resin composition may contain (C) an inorganic filler. From the viewpoint of reducing the average coefficient of linear thermal expansion of the cured product of the resin composition, it is preferable that the resin composition contains an inorganic filler.

The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotal. Sight, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Examples thereof include bismuth acid, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available silica products include "SO-C2" and "SO-C1" manufactured by Admatex, "UFP-30" and "UFP-40" manufactured by Denka.

The average particle size of the inorganic filler is usually 30 μm or less, and is preferably 25 μm or less, more preferably 20 μm or less, still more preferably 18 μm or less, from the viewpoint of enhancing the desired effect of the present invention. The lower limit of the average particle size may be 1 nm (0.001 μm) or more, 5 nm or more, 10 nm or more, etc., but from the viewpoint of enhancing the desired effect of the present invention, it is preferably 2.0 μm or more, more preferably 3.0 μm. Above, more preferably 5.0 μm or more or more than 10 μm.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like can be used.

The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving embedding property, and is preferably a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, or a mercaptosilane-based material. It is more preferable that the treatment is performed with one or more surface treatment agents such as a coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent, and the treatment is performed with an aminosilane-based silane coupling agent. It is more preferable that it is. The surface treatment agent preferably has a functional group that reacts with another component, for example, a resin, for example, an epoxy group, an amino group or a mercapto group, and more preferably the functional group is bonded to a terminal group. Examples of commercially available surface treatment agents include a silane-based coupling agent "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and a silane-based coupling agent "KBM803" manufactured by Shin-Etsu Chemical Industry Co., Ltd. ( 3-Mercaptopropyltrimethoxysilane), silane-based coupling agent "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., silane-based coupling agent "KBM573" (N-phenyl-) manufactured by Shin-Etsu Chemical Industry Co., Ltd. 3-Aminopropyltrimethoxysilane), Shinetsu Chemical Industry Co., Ltd. silane coupling agent "SZ-31" (hexamethyldisilazane), Shinetsu Chemical Industry Co., Ltd. alkoxysilane compound "KBM103" (phenyltrimethoxysilane), Shinetsu Silane-based coupling agent "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Kagaku Kogyo Co., Ltd., silane-based coupling agent "KBM-7103" (3,3,3-trifluoropropyl) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. Trimethoxysilane) and the like.

The degree of surface treatment with the surface treatment agent is such that the surface treatment is performed with 0.2 parts by mass to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (C) from the viewpoint of improving the embedding property. The surface treatment is preferably 0.2 parts by mass to 4 parts by mass, and the surface treatment is preferably 0.3 parts by mass to 3 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler from the viewpoint or the like to improve the filling property, preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} or more Is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the non-volatile components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The specific surface area of the component (C) is preferably 0.3 m ² / g or more, more preferably 0.5 m ² / g or more, and particularly preferably 0.7 m ² / g or more. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, 50 m ² / g or less, or 40 m ² / g or less. For the specific surface area, nitrogen gas is adsorbed on the sample surface using a BET fully automatic specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. Obtained by doing.

The content of the component (C) is preferably 40% by mass or more when the non-volatile content in the resin composition is 100% by mass from the viewpoint of reducing the average coefficient of linear thermal expansion of the cured product of the resin composition. It is more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, 75% by mass or more, or 80% by mass or more. The upper limit is not particularly limited, but is usually 96% by mass or less, and may be 95% by mass or less or 94% by mass or less. In the present invention, as illustrated in Examples, when the non-volatile component in the resin composition is 100% by mass, even if the content of the component (C) is 80% by mass or more, the chemical resistance is excellent. Moreover, it has been confirmed that a cured product with suppressed warpage was obtained.

<(D) Curing accelerator>
The resin composition may contain (D) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1, Examples thereof include 8-diazabicyclo (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, the imidazole compound "1B2PZ" manufactured by Shikoku Chemicals Corporation, "P200-H50" manufactured by Mitsubishi Chemical Corporation, and "2MA-OK-PW" manufactured by Shikoku Chemicals Corporation. And so on.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

When the resin composition contains the component (D), the content of the component (D) is usually 0.001% by mass or more, preferably 0.01 when the non-volatile content in the resin composition is 100% by mass. It is mass% or more, more preferably 0.02 mass% or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. Thereby, the curing of the resin composition can be surely promoted.

<(E) Arbitrary additive>
In one embodiment, the resin composition may further contain (E) other additives, if desired, such other additives include, for example, siloxane compounds, thermoplastic resins, organic fillings. Examples thereof include organic metal compounds such as materials, organic copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants. The content of the component (E) is arbitrary as long as the intended effect of the present invention is not excessively impaired, but when the non-volatile component in the resin composition is 100% by mass, for example, 0.1% by mass. The above is 0.3% by mass or more or 0.5% by mass or more, and may be, for example, 15% by mass or less, 13% by mass or less, or 10% by mass or less.

(Siloxane compound)
The siloxane compound refers to a compound having a siloxane (Si—O—Si) bond. The siloxane compound preferably contains a reactive functional group. The reactive functional group is, for example, a hydroxyl group. Therefore, the siloxane compound has one or more (preferably two or more) hydroxyl groups and one or more (preferably two or more, particularly preferably two or more) siloxane (Si—O—). It is preferably a compound having a Si) bond (hereinafter, also referred to as “(E-1) component” or “hydroxyl-containing siloxane compound”).

The (E-1) hydroxyl group-containing siloxane compound may be a siloxane compound having a cyclic siloxane skeleton or a siloxane compound having a chain siloxane skeleton, but may be a siloxane compound having a chain siloxane skeleton. preferable.

The number of hydroxyl groups in the (E-1) hydroxyl group-containing siloxane compound is not particularly limited, but may be preferably 10 or less, and more preferably 5 or less in one molecule. (E-1) When the hydroxyl group-containing siloxane compound is a hydroxyl group-containing chain siloxane compound, it has a side chain type having a hydroxyl group in the side chain, a biterminal type having a hydroxyl group at both ends, and a hydroxyl group in both the side chain and the terminal. It may be any of the side chain terminal types having.

The number of silicon atoms forming a siloxane bond in the (E-1) hydroxyl group-containing siloxane compound is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 as the lower limit in one molecule. The number may be 2,000 or less, more preferably 1,000 or less, and particularly preferably 500 or less.

(E-1) As for the silicon atom in the hydroxyl group-containing siloxane compound, all substitutable sites that are not involved in the formation of a siloxane bond are preferably substituted with a monovalent organic group having or not having a hydroxyl group, and the hydroxyl group is preferable. It is more preferable that it is substituted with an arbitrarily substituted monovalent hydrocarbon group having or not having.

The hydroxyl group-containing siloxane compound (E-1) preferably has the formula (1):

Wherein at least two of the 2n + 2 pieces of R ¹ and two R ² are, independently, represents a monovalent hydrocarbon group optionally substituted with one or more hydroxyl groups, and others, independent to, any substitution or a monovalent hydrocarbon group; at least two of or 2n + 2 pieces of R ¹ is independently a monovalent hydrocarbon group optionally substituted with one or more hydroxyl groups shown, others independently represents a monovalent hydrocarbon group optionally substituted, and two R ² are, shows one -O- together and bonded to each other, a cyclic siloxane skeleton Form. n represents an integer of 2 or more. ]
It is a siloxane compound represented by.

The "monovalent hydrocarbon group" may be, for example, an alkyl group, an alkenyl group, an aryl group or a combination thereof, and the combination may be an aryl group, an alkenyl group and / or an aryl group substituted with an alkyl; an aryl group. Group-substituted alkyl groups; aryl group-substituted alkenyl groups and the like can be mentioned, but are not particularly limited.

The "arbitrarily substituted monovalent hydrocarbon group having one or more hydroxyl groups" is a monovalent hydrocarbon group which may have one or more arbitrary substituents, and is at least one. It means a group having a hydroxyl group. The "arbitrarily substituted monovalent hydrocarbon group" means a monovalent hydrocarbon group which may have one or more arbitrary substituents (provided, "optionally having one or more hydroxyl groups". It means that it does not have a hydroxyl group to distinguish it from the "substituted monovalent hydrocarbon group").

"Alkyl (group)" refers to a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl (group)" is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the "alkyl (group)" include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and neopentyl. Examples thereof include a group, a sec-pentyl group, a tert-pentyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group and the like.

"Alkenyl (group)" refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The "alkenyl (group)" is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of the "alkenyl (group)" include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and a 3-. Methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group , 2-Cyclohexenyl group and the like.

"Aryl (group)" refers to a monovalent aromatic hydrocarbon group. The "aryl (group)" is preferably an aryl group having 6 to 10 carbon atoms. Examples of the "aryl (group)" include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

The arbitrary substituent in the "arbitrarily substituted monovalent hydrocarbon group" is not particularly limited, but for example, a halogen atom, a cyano group, a nitro group, an alkyl-oxy group, a mono or di (alkyl). -Amino group, alkyl-carbonyl group, alkyl-oxy-carbonyl group, mono or di (alkyl) -amino-carbonyl group, alkyl-carbonyl-oxy group, mono or di (alkyl-carbonyl) -amino group, alkenyl-oxy Group, mono or di (alkenyl) -amino group, alkenyl-carbonyl group, alkenyl-oxy-carbonyl group, mono or di (alkenyl) -amino-carbonyl group, alkenyl-carbonyl-oxy group, mono or di (alkenyl-carbonyl) )-Amino group, aryl-oxy group, mono or di (aryl) -amino group, aryl-carbonyl group, aryl-oxy-carbonyl group, mono or di (aryl) -amino-carbonyl group, aryl-carbonyl-oxy group , Mono or di (aryl-carbonyl) -amino group, aryl-oxy group, aryl-carbonyl group, aryl-oxy-carbonyl group, aryl-carbonyl-oxy group and the like, or a combination thereof. The number of substituents is preferably 1 to 3.

The "arbitrarily substituted monovalent hydrocarbon group having one or more hydroxyl groups" in the formula (1) is, for example, an alkyl group having one or more hydroxyl groups, an alkenyl group having one or more hydroxyl groups, and one. Aryl groups having the above hydroxyl groups, aryl group-substituted alkyl groups having one or more hydroxyl groups, aryl group-substituted alkenyl groups having one or more hydroxyl groups, and alkyl group-substituted aryl groups having one or more hydroxyl groups, An alkenyl group-substituted aryl group having one or more hydroxyl groups, an aryl group substituted with an aryl group having one or more hydroxyl groups, and the like can be mentioned, and an alkyl group having one or more hydroxyl groups or an alkyl group having one or more hydroxyl groups can be mentioned. It is preferably an aryl group substituted alkyl group. The number of hydroxyl groups in the "arbitrarily substituted monovalent hydrocarbon group having one or more hydroxyl groups" is preferably 1 to 3, particularly preferably 1. The "arbitrarily substituted monovalent hydrocarbon group having one or more hydroxyl groups" is preferably bonded to a different silicon atom. In one embodiment, the hydroxyl group is preferably a phenolic hydroxyl group because it is present on an aryl (group). That is, in one embodiment, the (B-1) hydroxyl group-containing siloxane compound is preferably a phenolic hydroxyl group-containing siloxane compound from the viewpoint of reactivity with the (C) epoxy resin.

The "arbitrarily substituted monovalent hydrocarbon group" in the formula (1) is, for example, an alkyl group, an alkenyl group, an aryl group, an alkyl group substituted with an aryl group, an alkenyl group substituted with an aryl group, or an aryl group substituted with an alkyl group. , An aryl group substituted with an alkenyl group, an aryl group substituted with an aryl group and the like, and an alkyl group is preferable, and a methyl group is particularly preferable.

In formula (1), preferably, ^{at least two of 2n + 2 R 1} and 2 R ² are arbitrarily substituted monovalent hydrocarbon groups having one or more hydroxyl groups independently. In addition, the others are independently substituted monovalent hydrocarbon groups, do not form a cyclic siloxane skeleton, and are chain siloxanes. More preferably, at least two of the 2n + 2 pieces of R ¹ and two R ² are, independently, a monovalent hydrocarbon group having one or more hydroxyl groups, and others, independently, It is a monovalent hydrocarbon group. More preferably, at least two of the 2n + 2 pieces of R ¹ and two R ² are, independently, alkyl group, or an aryl group substituted alkyl group having 1 or more hydroxyl groups having one or more hydroxyl groups And others are independently alkyl groups.

In the formula (1), n represents an integer of 1 or more, preferably an integer of 2 to 2,000, more preferably an integer of 2 to 1,000, and even more preferably an integer of 5 to 500. be.

Examples of commercially available hydroxyl group-containing siloxane compounds include "X-22-160AS", "KF-6001", "KF-6002", "KF-6003", and "KF" manufactured by Shin-Etsu Chemical Co., Ltd. -6012 "," X-22-4039 "," X-22-4015 "(carbinol type hydroxyl group-containing siloxane compound)," KF-2201 "," X-22-1821 "(phenolic) manufactured by Shin-Etsu Chemical Co., Ltd. Hydroxyxane-containing siloxane compound) and the like.

The weight average molecular weight (Mw) of the (E-1) hydroxyl group-containing siloxane compound can be preferably 50,000 or less, more preferably 20,000 or less. The lower limit of the weight average molecular weight (Mw) can be preferably 500 or more, more preferably 1,000 or more. The number average molecular weight (Mn) of the (E-1) hydroxyl group-containing siloxane compound can be preferably 50,000 or less, more preferably 20,000 or less. The lower limit of the number average molecular weight (Mn) can be preferably 500 or more, more preferably 1,000 or more. The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by the gel permeation chromatography (GPC) method (polystyrene conversion).

The hydroxyl value of the (E-1) hydroxyl group-containing siloxane compound is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less, still more preferably 100 mgKOH / g or less, and particularly preferably 80 mgKOH. It can be less than / g. The lower limit of the hydroxyl value can be preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, still more preferably 25 mgKOH / g or more, and particularly preferably 30 mgKOH / g or more. The hydroxyl value indicates the amount of potassium hydroxide (mg per 1 g of the compound) required to neutralize free acetic acid when the hydroxyl group of the compound is acetylated with acetic anhydride.

The hydroxyl group equivalent of the (E-1) hydroxyl group-containing siloxane compound is preferably 10000 g / eq. Hereinafter, more preferably 5000 g / eq. Hereinafter, more preferably 3000 g / eq. Hereinafter, particularly preferably, 2000 g / eq. It can be: The lower limit of the hydroxyl group equivalent is preferably 100 g / eq. As mentioned above, more preferably 200 g / eq. Above, more preferably 500 g / eq. As mentioned above, 700 g / eq. Is particularly preferable. It can be more than that. The hydroxyl group equivalent is the mass (g) of the compound per hydroxyl group equivalent.

The viscosity (25 ° C.) of the (E-1) hydroxyl group-containing siloxane compound is, for example, 3000 mm ² / s or less, preferably 2000 mm ² / s or less, and more preferably 1800 mm ² / s or less. The lower limit of the viscosity (25 ° C.) can be, for example, 10 mm ² / s or more, 30 mm ² / s or more, 50 mm ² / s or more, or 60 mm ² / s or more.

The content of the (E-1) hydroxyl group-containing siloxane compound in the resin composition is 0% by mass or more when the non-volatile component of the resin component in the resin composition is 100% by mass. From the viewpoint of enhancing the effect, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 2% by mass or more. The upper limit of the content of the (E-1) hydroxyl group-containing siloxane compound in the resin composition is not limited as long as the intended effect of the present invention is not excessively impaired, but the non-volatile component of the resin component is 100. When it is set to mass%, it can be, for example, 20% by mass or less, 15% by mass or less, and 10% by mass or less. The resin component refers to a component excluding (C) the inorganic filler from all the components contained in the resin composition.

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyether etherketone resin, and polyester resin. And so on. The thermoplastic resin preferably has a reactive functional group, which allows it to be incorporated into a crosslinked structure composed of the components (A) and (B). The reactive functional group may be one that exhibits reactivity by heating or light irradiation. The content of the thermoplastic resin is arbitrary as long as the intended effect of the present invention is not excessively impaired, but when the non-volatile component in the resin composition is 100% by mass, for example, 0.1% by mass or more. , 0.2% by mass or more or 0.3% by mass or more, and from the viewpoint of increasing the cross-linking density, it may be 5% by mass or less, 3% by mass or less, or 1% by mass or less.

As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles. As the rubber particles, commercially available products may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd. The content of the organic filler is arbitrary as long as the intended effect of the present invention is not excessively impaired, but when the non-volatile component in the resin composition is 100% by mass, for example, 0.1% by mass or more. , 0.3% by mass or more or 0.5% by mass or more, and may be, for example, 10% by mass or less, 7% by mass or less, or 5% by mass or less.

<Characteristics of resin composition>
(Value Z _i )
_{The resin composition of the present invention has a value Z i} (ppm · cm ³ / mol · K) obtained by dividing the average linear thermal expansion coefficient α by the crosslink density n with respect to the cured product obtained by curing at 150 ° C. for 60 minutes. Satisfy 10 <Z _i <100. As a result, as demonstrated in the column of Examples, the resin composition of the present invention can obtain a cured product having excellent chemical resistance and suppressed warpage as compared with Comparative Examples. Preferably, here, Z _i can be acquired according to < _{Acquisition of value Z i> described later.} Z _i is usually more than 10 (ppm · cm ³ / mol · K), preferably 10 (ppm · cm ³ / mol · K) or more, and the desired effect (chemical resistance and chemical resistance) of the present invention. From the viewpoint of enhancing (suppression of warpage), it is preferably 11 (ppm · cm ³ / mol · K) or more, more preferably 12 (ppm · cm ³ / mol · K) or more, and is usually 100 (ppm · cm ^{3) or more.} It is less than / mol · K), preferably 100 (ppm · cm ³ / mol · K) or less, and preferably 90 (ppm · cm ³ / mol · K) from the viewpoint of enhancing the desired effect of the present invention. ) Or less, more preferably 80 (ppm · cm ³ / mol · K) or less. Here, the value Z _i can be adjusted according to, for example, the type and amount of components such as the component (A) and the component (B) contained in the resin composition. The value Z _i is a parameter expressed by the relational expression between the average linear thermal expansion coefficient α and the crosslink density n, and is a parameter related to chemical resistance and suppression of warpage. Therefore, (i) generally average linear thermal expansion. Presence / absence and content of (C) component, which is a component that lowers the coefficient α, (ii) presence / absence and content of a component or site that can reduce the chemical resistance of the cured product formed by the epoxy resin and the curing agent, (Iii) Presence / absence and content of components or sites (for example, components (D) and (F)) that can inhibit the formation of the crosslinked structure formed by the epoxy resin and the curing agent or suppress the increase in the crosslinked density. , And (iv) the presence or absence of a component that can promote the formation of the crosslinked structure (for example, the component (D)) and its content can be grasped as one of the indexes that already reflects the parameters.

(Glass transition temperature Tg)
From the viewpoint of obtaining a cured product having excellent heat resistance, the resin composition of the present invention has a glass transition temperature Tg (° C.) of the cured product obtained by curing at 150 ° C. for 60 minutes within a range of 150 to 240 ° C. Is preferable. The glass transition temperature Tg (° C.) can be obtained in <Measurement of dynamic elastic modulus> described later. The glass transition temperature Tg (° C.) is usually 150 ° C. or higher, and is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of obtaining a cured product having excellent heat resistance. The upper limit of the glass transition temperature Tg (° C.) is usually 240 ° C. or lower, but for example, from the viewpoint of obtaining a cured product having excellent handleability, it may be 235 ° C. or lower, 233 ° C. or lower, or 230 ° C. or lower.

(Average coefficient of linear thermal expansion α)
From the viewpoint of enhancing the desired effect of the present invention, the resin composition of the present invention preferably has a small average linear thermal expansion coefficient α of the cured product obtained by curing at 150 ° C. for 60 minutes. Here, the value of the average coefficient of linear thermal expansion α can be adjusted to be lowered depending on the type and amount of the components (A) and (B) contained in the resin composition, for example. The average coefficient of linear thermal expansion α can be measured according to <Measurement of average coefficient of linear thermal expansion (CTE) α> described later. The average coefficient of linear thermal expansion α of such a cured product is usually less than 23 ppm / K, more preferably 21 ppm / K or less, still more preferably 20 ppm / K or less, and particularly preferably 17 ppm / K or less. Yes, and the lower limit is not limited, but may be, for example, 0 ppm / K or more or 1 ppm / K or more. The average linear thermal expansion coefficient of such a cured product α is, from the viewpoint of the value Z _i satisfies the above range, for example, may be a 3 ppm / K or more, or 4 ppm / K or more.

(Storage modulus E'at a predetermined temperature T (K))
The resin composition of the present invention, per cured product obtained by curing for 60 minutes at 0.99 ° C., the storage modulus E at a given temperature T (K) 'is usually not more than 7.00 × ¹⁰ 9 Pa. The predetermined temperature T (K) is a temperature indicating the sum of the glass transition temperature Tg (° C.) and 353 (K) of the cured product (that is, the glass transition temperature Tg (° C.)). Is a value obtained by adding 273K and adding 80K in order to convert the unit K into a unit K). Here, the value of the storage elastic modulus E'at a predetermined temperature T (K) can be adjusted by, for example, the type and amount of components such as the component (A) and the component (B) contained in the resin composition. From the viewpoint of enhancing the desired effect of the present invention, such a storage elastic modulus E'is preferably ^{less than 6.50 × 10 9} Pa, more preferably 6.00 × 10 ⁹ Pa or less, and is usually 0. It is 0.05 × 10 ⁹ Pa or more, preferably 0.50 × 10 ⁹ Pa or more, more preferably more than 1.00 × 10 ⁹ Pa, and further preferably 1. It is 50 × 10 ⁹ Pa or more. The predetermined temperature T (K) is, for example, in the range of 473K to 673K.

(Crosslink density n)
From the viewpoint of enhancing the desired effect of the present invention, the resin composition of the present invention has a crosslink density n of a cured product obtained by curing at 150 ° C. for 60 minutes, preferably ^{more than 0.15 mol / cm 3} , more preferably. Is 0.16 mol / cm ³ or more. Here, the value of the crosslink density n can be adjusted by, for example, the type and amount of components such as the component (A) and the component (B) contained in the resin composition. The crosslink density n can be obtained by using the measurement result in <Measurement of dynamic elastic modulus> described later. From the viewpoint of enhancing the desired effect of the present invention, such a crosslink density n is preferably ^{less than 0.50 mol / cm 3} , more preferably 0.46 mol / cm ³ or less, still more preferably 0.42 mol / cm ^3. It is as follows. Average linear thermal expansion coefficient α is equal to or less than 21 ppm / K, and the storage elastic modulus E 'is the 1.00 × ¹⁰ 9 Pa greater and crosslink density n is less than 0.50 mol / cm ³ Is preferable.

The resin composition of the present invention can obtain an insulating layer formed of a cured product having excellent chemical resistance and suppressed warpage. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board), and the printed wiring board can be used. It can be more preferably used as a resin composition for forming an interlayer insulating layer (a resin composition for forming an interlayer insulating layer of a printed wiring board). Further, since the resin composition of the present invention provides an insulating layer formed of a cured product having excellent chemical resistance and suppressed warpage, it is also suitable when the printed wiring board is a circuit board with built-in components. Can be used for. Further, since the resin composition of the present invention provides an insulating layer formed of a cured product having excellent chemical resistance and suppressed warpage, a resin composition for forming a solder resist layer (printed wiring). It can be more preferably used as a resin composition for forming a solder resist layer of a plate). Further, since the resin composition of the present invention provides an insulating layer formed of a cured product in which warpage is suppressed, a resin composition for forming a sealing layer for sealing a semiconductor chip for a semiconductor chip package. It can be suitably used as (resin composition for forming a sealing layer of a semiconductor chip package). Further, the resin composition of the present invention can be suitably used as a resin composition for forming a rewiring cambium of a semiconductor chip package (resin composition for forming a rewiring cambium for a semiconductor chip package). can.

The semiconductor chip package including the rewiring cambium is manufactured, for example, through the following steps (1) to (6).
(1) A process of laminating a temporary fixing film on a base material,
(2) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(3) Step of forming a sealing layer on a semiconductor chip,
(4) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off, and (6) A rewiring layer as a conductor layer is formed on the rewiring forming layer. Step of Forming Further, when a semiconductor chip package including a sealing layer is manufactured, a rewiring layer may be further formed on the sealing layer.

<Manufacturing method of resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is mixed with a solvent as necessary and dispersed using a rotary mixer or the like. In one embodiment, the amount of the solvent is preferably small, and when the non-volatile component of the resin composition is 100% by mass, 0.5% by mass or less is more preferable, 0.1% by mass or less is further preferable, and 0% by mass is used. % (Not included) is particularly preferable. In producing the resin composition of the present invention, the selection of the component (A) and component (B), by adjusting the content of the content and the component (B) of the component (A), the above value Z _i Can be kept within the above range. Further, in order to reduce the amount of the solvent, it is preferable to use a liquid component as at least one selected from the component (A) and the component (B).

The resin composition can be obtained as a resin varnish by containing, for example, a solvent. In one embodiment, the amount of the solvent is preferably small, and the amount of the solvent is more preferably 0.5% by mass or less and 0.1% by mass or less when the non-volatile component of the resin composition is 100% by mass. More preferred.

<Physical characteristics and applications of cured resin composition>
(chemical resistance)
The cured product obtained by thermally curing the resin composition of the present invention usually has excellent chemical resistance. The chemical resistance can be evaluated according to the description of <Evaluation of chemical resistance> described later. For example, a cured product having a thickness of 100 μm obtained by thermally curing the resin composition at 150 ° C. for 60 minutes is a strong alkaline aqueous solution (for example, potassium hydroxide aqueous solution, tetramethylammonium hydroxide solution, sodium hydroxide aqueous solution). Or even if it is immersed in an aqueous solution of sodium carbonate), the mass reduction rate before and after that can be 1% by mass or less.

(Suppression of warpage)
When the cured product obtained by thermally curing the resin composition of the present invention is formed on a substrate, the warp of the substrate is usually suppressed. The warp can be evaluated according to the description of <Evaluation of warp> described later. For example, the maximum amount of warpage that can occur on a substrate on which a cured product having a thickness of 300 μm obtained by thermally curing a resin composition at 150 ° C. for 60 minutes can be 2000 μm or less.

(Glass transition temperature Tg)
The cured product obtained by thermosetting the resin composition of the present invention preferably has a glass transition temperature Tg (° C.) in the range of 150 to 240 ° C. from the viewpoint of excellent heat resistance. The more preferable range and the like are as described above for the resin composition.

(Average coefficient of linear thermal expansion α)
The cured product obtained by thermally curing the resin composition of the present invention preferably has a small average linear thermal expansion coefficient α from the viewpoint of enhancing the desired effect of the present invention. The more preferable range and the like are as described above for the resin composition.

(Storage modulus E'at a predetermined temperature T (K))
A cured product obtained by thermally curing the resin composition of the present invention, the storage modulus E at a given temperature T (K) 'is usually not more than 7.00 × 10 9 ^Pa. The preferred range and the like are as described above for the resin composition.

(Crosslink density n)
The cured product obtained by thermosetting the resin composition of the present invention preferably has a crosslink density n of more than ^{0.15 mol / cm 3 from the viewpoint of enhancing the desired effect of the present invention, preferably 0.16 mol / cm /.} More preferably cm ³ or more. More preferable ranges and the like are as described above for the resin composition.

(Value Z _i )
The cured product obtained by thermally curing the resin composition of the present invention has a value Z _i (ppm · cm ³ / mol · K) obtained by dividing the average linear thermal expansion coefficient α by the cross-linking density n of 10 <. It is preferable to satisfy Z _{i <100.} As demonstrated in the column of Examples, such a cured product has excellent chemical resistance and suppression of warpage. The more preferable range and the like are as described above for the resin composition.

The cured product of the resin composition of the present invention has excellent chemical resistance and is suppressed from warping. Therefore, the cured product of the resin composition of the present invention can be suitably used as an insulating layer of a printed wiring board, and can be more preferably used as an interlayer insulating layer of a printed wiring board. Further, since the cured product of the resin composition of the present invention provides an insulating layer having excellent chemical resistance and suppressed warpage, it is also suitably used when the printed wiring board is a circuit board with built-in components. be able to. Further, since the cured product of the resin composition of the present invention provides an insulating layer formed of the cured product having excellent chemical resistance and suppressed warpage, it can be more preferably used as a solder resist layer. can. Further, since the cured product of the resin composition of the present invention provides an insulating layer formed of the cured product in which warpage is suppressed, it is suitably used as a sealing layer for sealing a semiconductor chip for a semiconductor chip package. be able to. Further, the cured product of the resin composition of the present invention can be suitably used as a rewiring forming layer (insulating layer) for forming a rewiring layer of a semiconductor chip package.

[Resin paste]
The resin paste of the present invention contains the above-mentioned resin composition. The resin paste of the present invention usually contains only the above-mentioned resin composition. The viscosity of the resin paste at 25 ° C. is preferably in the range of 20 Pa · s to 1000 Pa · s. The heat loss of the resin paste is preferably 5% or less in order to suppress the generation of voids.

[Resin composition molded article]
The resin composition of the present invention may be made into a resin composition molded product by compression molding or the like. Further, the shape of the resin composition molded product is not limited to the sheet shape, and the resin composition may be processed into any shape. Further, by a method other than compression molding or compression molding, the resin composition of the present invention may be referred to as a powder, granule, or pellet-shaped resin composition molded product (each of which is referred to as a resin powder, a resin granule, or a resin pellet). Good) may be formed.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer containing the resin composition of the present invention provided on the support.

The thickness of the resin composition layer of the resin sheet is usually 150 μm or less, preferably 110 μm or less, and may be 50 μm or less or 40 μm or less from the viewpoint of thinning the printed wiring board. The thickness may be further reduced. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) And other polyesters, polycarbonates (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further contain other layers, if desired. Examples of such other layers include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol and the like. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more. In one embodiment, the smaller the amount of the organic solvent, the more preferable (for example, when the non-volatile component in the resin composition is 100% by mass, 0.5% by mass or less, 0.1% by mass or less, 0.01% by mass). Below), it is particularly preferable not to include it.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet of the present invention provides an insulating layer formed of a cured product having excellent chemical resistance and suppressed warpage. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed wiring board (resin sheet for forming an insulating layer of a printed wiring board), and can be used as an interlayer insulating layer of the printed wiring board. It can be more preferably used as a resin sheet for forming (a resin sheet for an interlayer insulating layer of a printed wiring board). Further, the resin sheet of the present invention can be suitably used as a resin sheet for forming a solder resist layer of a printed wiring board (a resin sheet for forming a solder resist layer of a printed wiring board). Further, since the resin sheet of the present invention provides an insulating layer formed of a cured product in which warpage is suppressed, a resin composition for forming a sealing layer for sealing a semiconductor chip for a semiconductor chip package (a resin composition for forming a sealing layer for sealing a semiconductor chip for a semiconductor chip package). It can be suitably used as a resin sheet for forming a sealing layer of a semiconductor chip package). Further, the resin sheet of the present invention can be suitably used as a resin sheet (resin sheet for forming a rewiring forming layer for a semiconductor chip package) for forming a rewiring forming layer (insulating layer) of a semiconductor chip package. can.

<Printed circuit board>
The printed wiring board of the present invention includes an insulating layer formed by containing a cured product of the resin composition of the present invention. This printed wiring board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).
(1) A step of forming a resin composition layer containing a resin composition on a base material using the resin composition of the present invention.
(2) A step of thermosetting the resin composition layer to form an insulating layer.

In step (1), a base material is prepared. Examples of the base material include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a base material having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on a surface of the second metal layer opposite to the first metal layer. Examples of the base material having such a metal layer include an ultrathin copper foil "Micro Tin" with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.

Further, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be appropriately referred to as a “base material with a wiring layer”. As the conductor material contained in the conductor layer, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Materials containing the above metals can be mentioned. As the conductor material, a single metal may be used, or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel-chrome alloy as an alloy from the viewpoint of versatility, cost, and ease of patterning for forming a conductor layer. , Copper / nickel alloy, copper / titanium alloy; is preferable. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and a nickel-chromium alloy; are more preferable, and a single metal of copper is particularly preferable.

The conductor layer may be patterned, for example, to function as a wiring layer. At this time, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and further. It is preferably 5/5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the printed wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

The conductor layer is, for example, a step of laminating a dry film (photosensitive resist film) on a substrate, exposing and developing the dry film under predetermined conditions using a photomask to form a pattern, and pattern drying. It can be formed by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as an electrolytic plating method using the developed pattern dry film as a plating mask, and a step of peeling off the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolak resin or an acrylic resin can be used. The laminating conditions of the base material and the dry film may be the same as the laminating conditions of the base material and the resin sheet described later. The peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution.

After preparing the base material, a resin composition layer is formed on the base material. When the conductor layer is formed on the surface of the base material, it is preferable that the resin composition layer is formed so that the conductor layer is embedded in the resin composition layer.

The formation of the resin composition layer is performed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by attaching the resin composition layer to the base material by heat-pressing the resin sheet to the base material from the support side. Examples of the member for heat-pressing the resin sheet to the base material (hereinafter, may be referred to as “heat-bonding member”) include a heated metal plate (SUS end plate and the like) or a metal roll (SUS roll and the like). Be done. It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

Lamination of the base material and the resin sheet may be carried out by, for example, a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The heat crimping pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 13 hPa or less.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The laminating and smoothing treatments may be continuously performed using a vacuum laminator.

Further, the resin composition layer can be formed by, for example, a compression molding method. As the molding conditions, the same conditions as the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later may be adopted.

After forming the resin composition layer on the base material, the resin composition layer is heat-cured to form an insulating layer. The thermosetting conditions of the resin composition layer differ depending on the type of resin composition, but the curing temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 220 ° C., more preferably 140 ° C. to 200 ° C.). The curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a printed wiring board having an insulating layer can be manufactured. Further, the method for manufacturing the printed wiring board may further include an arbitrary step.
For example, when a printed wiring board is manufactured using a resin sheet, the method for manufacturing the printed wiring board may include a step of peeling off the support of the resin sheet. The support may be peeled off before the thermosetting of the resin composition layer, or may be peeled off after the thermosetting of the resin composition layer.

The method for manufacturing a printed wiring board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinding machine.

The method for manufacturing a printed wiring board may include, for example, a step of interconnecting conductor layers (3), for example, a step of drilling holes in an insulating layer. As a result, holes such as via holes and through holes can be formed in the insulating layer. Examples of the method for forming the via hole include laser irradiation, etching, and mechanical drilling. The dimensions and shape of the via hole may be appropriately determined according to the design of the printed wiring board. In the step (3), the interlayer connection may be performed by polishing or grinding the insulating layer.

After forming the via hole, it is preferable to perform a step of removing the smear in the via hole. This process is sometimes referred to as the desmear process. For example, when the conductor layer is formed on the insulating layer by a plating step, the via holes may be subjected to a wet desmear treatment. Further, when the conductor layer is formed on the insulating layer by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Further, the insulating layer may be roughened by the desmear step.

Further, the insulating layer may be roughened before the conductor layer is formed on the insulating layer. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As the roughening treatment, either a dry type or a wet type roughening treatment may be performed. Examples of the dry roughening treatment include plasma treatment and the like. Further, as an example of the wet roughening treatment, a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be mentioned in this order.

After forming the via hole, a conductor layer may be formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are made conductive, and the interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, and a vapor deposition method, and the plating method is particularly preferable. In a preferred embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method, a full additive method, or the like to form a conductor layer having a desired wiring pattern. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by the subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Further, the conductor layer may have a single-layer structure, or may have a multi-layer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which the conductor layer is formed on the insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer is formed on the formed plating seed layer corresponding to a desired wiring pattern. After forming an electrolytic plating layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by a treatment such as etching to form a conductor layer having a desired wiring pattern. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

The method for manufacturing a printed wiring board may include a step (4) of removing a base material. By removing the base material, a printed wiring board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when a base material having a peelable metal layer is used.

<Semiconductor chip package>
The semiconductor chip package according to the first embodiment of the present invention includes the above-mentioned printed wiring board and the semiconductor chip mounted on the printed wiring board. This semiconductor chip package can be manufactured by joining a semiconductor chip to a printed wiring board.

As the joining condition between the printed wiring board and the semiconductor chip, any condition can be adopted in which the terminal electrode of the semiconductor chip and the circuit wiring of the printed wiring board can be connected by a conductor. For example, the conditions used in flip-chip mounting of semiconductor chips can be adopted. Further, for example, the semiconductor chip and the printed wiring board may be bonded to each other via an insulating adhesive.

An example of the joining method is a method of crimping a semiconductor chip to a printed wiring board. As the crimping conditions, the crimping temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is usually in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

Further, as another example of the joining method, there is a method of reflowing a semiconductor chip onto a printed wiring board and joining the semiconductor chips. The reflow condition may be in the range of 120 ° C. to 300 ° C.

After joining the semiconductor chip to the printed wiring board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-mentioned resin composition may be used, or the above-mentioned resin sheet may be used.

The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition that seals the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include a fan-out type WLP.

The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of forming a sealing layer on a semiconductor chip,
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
(F) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer, and
(G) A step of forming a solder resist layer on the rewiring layer,
Can be included. Further, the method for manufacturing the above-mentioned semiconductor chip package is as follows.
(H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them may be included.

(Step (A))
The step (A) is a step of laminating a temporary fixing film on the base material. The laminating conditions of the base material and the temporary fixing film can be the same as the laminating conditions of the base material and the resin sheet in the method for manufacturing the printed wiring board.

As the base material, for example, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); FR-4 substrate or the like, the glass fiber is impregnated with epoxy resin or the like. Examples thereof include a heat-cured substrate; a substrate made of a bismaleimide triazine resin such as a BT resin; and the like.

As the temporary fixing film, any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

(Step (B))
The step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using, for example, a device such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor chip packages, and the like. For example, semiconductor chips may be arranged and temporarily fixed in a matrix having a plurality of rows and a plurality of columns.

(Step (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by the cured product of the resin composition described above. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermosetting the resin composition layer to form a sealing layer.

The resin composition layer is preferably formed by a compression molding method. In the compression molding method, a semiconductor chip and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor chip.

The specific operation of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. Further, the resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition is attached to the lower mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are molded, and heat and pressure are applied to the resin composition to perform compression molding.

Further, the specific operation of the compression molding method may be as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. Place the resin composition on the lower mold. Further, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are molded so that the resin composition placed on the lower mold comes into contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions differ depending on the composition of the resin composition, and appropriate conditions can be adopted so that good sealing is achieved. For example, the temperature of the mold at the time of molding is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, particularly preferably 90 ° C. or higher, preferably 200 ° C. or lower, more preferably 170 ° C. or lower, and particularly preferably 150 ° C. It is as follows. The pressure applied during molding is preferably 1 MPa or more, more preferably 2 MPa or more, particularly preferably 3 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 3 minutes or longer, preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Usually, the mold is removed after the formation of the resin composition layer. The mold may be removed before the thermosetting of the resin composition layer or after the thermosetting.

The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, a resin composition layer can be formed on a semiconductor chip by heat-pressing the resin composition layer of the resin sheet and the semiconductor chip. The laminating of the resin sheet and the semiconductor chip can usually be performed by using the semiconductor chip instead of the base material in the same manner as the laminating of the resin sheet and the base material in the method for manufacturing a printed wiring board.

After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermosetting to obtain a sealing layer covering the semiconductor chip. As a result, the semiconductor chip is sealed with the cured product of the resin composition. As the thermosetting condition of the resin composition layer, the same conditions as the thermosetting condition of the resin composition layer in the method for manufacturing a printed wiring board may be adopted. Further, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. As the treatment conditions for this preheat treatment, the same conditions as those for the preheat treatment in the method for manufacturing a printed wiring board may be adopted.

(Step (D))
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming or expanding the temporary fixing film to peel it off. Further, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through a base material to reduce the adhesive force of the temporary fixing film and peeling the film can be mentioned.

In the method of heating, foaming or expanding the temporary fixing film to peel it off, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method for peeling by reducing the adhesive strength of the temporary fixing film by ultraviolet irradiation, irradiation amount of ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

(Step (E))
The step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.

As the material of the rewiring cambium, any material having an insulating property can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as this thermosetting resin.

After forming the rewiring cambium, via holes may be formed in the rewiring cambium in order to interconnect the semiconductor chip and the rewiring layer between layers.

In the method of forming a via hole when the material of the rewiring cambium is a photosensitive resin, the surface of the rewiring cambium is usually irradiated with active energy rays through a mask pattern to illuminate the rewiring cambium of the irradiated portion. Cure. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is brought into close contact with the rewiring cambium and exposed, and a non-contact exposure method in which the mask pattern is exposed using parallel rays without being brought into close contact with the rewiring cambium. Can be mentioned.

After the rewiring cambium is photocured, the rewiring cambium is developed to remove unexposed areas to form via holes. The development may be either wet development or dry development. Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

Examples of the method for forming the via hole when the material of the rewiring cambium is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Above all, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine that uses a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring cambium.

(Step (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing a printed wiring board. Further, the steps (E) and (F) may be repeated, and the rewiring layer and the rewiring forming layer may be alternately stacked (build-up).

(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having an insulating property can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as a thermosetting resin.

Further, in the step (G), a bumping process for forming bumps may be performed, if necessary. The bumping process can be performed by a method such as solder balls or solder plating. Further, the formation of the via hole in the bumping process can be performed in the same manner as in the step (E).

(Step (H))
The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces. The method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device>
The semiconductor device includes a semiconductor chip package. Semiconductor devices include, for example, electrical products (eg computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, etc.). And various semiconductor devices used for aircraft, etc.).

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[Example 1]
<Preparation of resin paste A>
Bisphenol A type epoxy resin as a component (A-1) ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g / eq.) 1.5 parts, naphthalene type epoxy resin as a component (A-1) (A-1) "HP-4032" manufactured by DIC, epoxy equivalent: 144 g / eq.) 1 part, biphenyl type epoxy resin as a component (A-2) ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g / eq.) 0.5 parts, glycidylamine type epoxy resin as component (A-1) ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g / eq.) 5 parts, acid anhydride-based curing agent as component (B) ("MH-700" manufactured by Shin Nihon Rika Co., Ltd., acid anhydride base equivalent: 164 g / eq.) 10 parts, hydroxyl group-containing siloxane compound as component (E-1) (polyether-modified silicone resin manufactured by Shinetsu Chemical Industry Co., Ltd. KF-6012 ”, viscosity (25 ° C.): 1500 mm ² / s) 1 part, 140 parts of inorganic filler A as component (C), and imidazole-based curing accelerator as component (D) (“2MA” manufactured by Shikoku Kasei Co., Ltd. -OK-PW ") 0.1 part was mixed and uniformly dispersed using a mixer.

Here, as the inorganic filler A, spherical silica surface-treated with "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., having a maximum cut diameter of 25 μm was used. .. As a result of measurement, the average particle size of the inorganic filler A was 10 μm, and the specific surface area of the inorganic filler A was 3.6 m ² / g.

As described above, a paste-like resin composition was prepared. Hereinafter, the resin composition prepared in the form of a paste in this way is also collectively referred to as "resin paste A".

<Preparation of cured product B for evaluation>
Using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes), the resin paste A was compression-molded on a 12-inch disk-shaped silicon wafer that had undergone a mold release treatment. As a result, a resin composition molded product having a thickness of 100 μm was formed on the silicon wafer. Then, the resin composition molded product was peeled off from the silicon wafer. The obtained resin composition molded product was heat-cured at 150 ° C. for 60 minutes. As a result, a cured product for evaluation was obtained. Hereinafter, the evaluation cured product thus produced is also collectively referred to as "evaluation cured product B".

<Acquisition and evaluation of various parameters of cured product of resin composition>
Using the resin paste A or the cured product B for evaluation, various parameters were obtained for the cured product of the resin composition, and evaluation was performed according to the evaluation method described later from the viewpoint of chemical resistance and warpage.

[Example 2]
In Example 1, 140 parts of the inorganic filler A as the component (C) was changed to 170 parts of the inorganic filler C as the component (C). Here, as the inorganic filler C, spherical alumina treated with "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and having a maximum cut diameter of 45 μm was used. .. As a result of measurement, the average particle size of the inorganic filler B was 15 μm, and the specific surface area was 0.9 m ² / g.

A resin paste A was prepared in the same manner as in Example 1 except for the above items. Then, the resin paste A is used to obtain a cured product B for evaluation in the same manner as in Example 1, and the resin paste A or the cured product B for evaluation is used to cure the resin composition in the same manner as in Example 1. The thing was used for evaluation.

[Example 3]
In Example 1, 1.5 parts of a bisphenol A type epoxy resin (“jER828EL” manufactured by Mitsubishi Chemical Co., Ltd.) as a component (A-1) and a naphthalene type epoxy resin (“HP” manufactured by DIC Co., Ltd.) as a component (A-1). -4032 ") 1 part, biphenyl type epoxy resin as (A-2) component ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.) 0.5 part and glycidylamine type epoxy resin as (A-1) component (Mitsubishi Chemical) 5 parts of "630" manufactured by Mitsubishi Chemical Co., Ltd., 2.5 parts of bisphenol A type epoxy resin as component (A-1) ("jER828EL" manufactured by Mitsubishi Chemical Co., Ltd.), glycidylamine type epoxy resin as component (A-1) It was changed to 5 parts ("630" manufactured by Mitsubishi Chemical Co., Ltd.) and 0.5 part of epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 418 g / eq.) As a component (A-1). Further, in Example 1, 10 parts of an acid anhydride-based curing agent (manufactured by Shin Nihon Rika Co., Ltd. “MH-700”) as a component (B) and a phenol-based curing agent (manufactured by Meiwa Kasei Co., Ltd.) as a component (B) were used. "MEH-8000H", phenol equivalent: 240) was changed to 5 parts. Further, in Example 1, 140 parts of the inorganic filler A as the component (C) was changed to 110 parts of the inorganic filler A as the component (C). Further, in Example 1, 0.1 part of an imidazole-based curing accelerator (“2MA-OK-PW” manufactured by Shikoku Chemicals Corporation) as a component (D) was used as a component (D), and a curing accelerator (Shikoku Chemicals Corporation) was used as a component (D). Made by the company, "1B2PZ") Changed to 0.1 copies.

A resin paste A was prepared in the same manner as in Example 1 except for the above items. Then, the resin paste A is used to obtain a cured product B for evaluation in the same manner as in Example 1, and the resin paste A or the cured product B for evaluation is used to cure the resin composition in the same manner as in Example 1. The thing was used for evaluation.

[Comparative Example 1]
In Example 1, 1.5 parts of a bisphenol A type epoxy resin (“jER828EL” manufactured by Mitsubishi Chemical Co., Ltd.) as a component (A-1) and a naphthalene type epoxy resin (“HP” manufactured by DIC Co., Ltd.) as a component (A-1). -4032 ") 1 part, biphenyl type epoxy resin as (A-2) component ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.) 0.5 part and glycidylamine type epoxy resin as (A-1) component (Mitsubishi Chemical) 5 parts of "630" manufactured by Mitsubishi Chemical Co., Ltd., 2 parts of bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Co., Ltd.) as component (A-1) and glycidylamine type epoxy resin (Mitsubishi) as component (A-1) Changed to 6 parts ("630") manufactured by Chemical Co., Ltd. Further, in Example 1, one part of the hydroxyl group-containing siloxane compound (polyether-modified silicone resin “KF-6012” manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (E-1) was not used. Further, in Example 1, 140 parts of the inorganic filler A as the component (C) was changed to 200 parts of the inorganic filler B as the component (C). Further, in Example 1, 0.1 part of an imidazole-based curing accelerator (“2MA-OK-PW” manufactured by Shikoku Chemicals Corporation) as a component (D) was used as a component (D), and a curing accelerator (Shikoku Chemicals Corporation) was used as a component (D). Made by the company, "1B2PZ") Changed to 0.1 copies.

Here, as the inorganic filler B, spherical silica surface-treated with "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., having a maximum cut diameter of 45 μm was used. .. As a result of measurement, the average particle size of the inorganic filler B was 15 μm, and the specific surface area of the inorganic filler A was 2.5 m ² / g.

A resin paste A was prepared in the same manner as in Example 1 except for the above items. Then, the resin paste A is used to obtain a cured product B for evaluation in the same manner as in Example 1, and the resin paste A or the cured product B for evaluation is used to cure the resin composition in the same manner as in Example 1. The thing was used for evaluation.

[Comparative Example 2]
In Example 3, 2.5 parts of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "jER828EL") as a component (A-1) and a glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation) as a component (A-1). 5 parts of "jER630") and 0.5 part of epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation) as a component (A-1), and bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) as a component (A-1). "JER828EL") 1 part, glycidylamine type epoxy resin as (A-1) component ("630" manufactured by Mitsubishi Chemical Corporation) 3 parts and epoxy resin as component (A-1) ("YX7400" manufactured by Mitsubishi Chemical Corporation) ) Changed to 4 copies. Further, in Example 3, one part of the hydroxyl group-containing siloxane compound (polyether-modified silicone resin “KF-6012” manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (E-1) was not used. Further, in Example 3, 0.1 part of the curing accelerator (manufactured by Shikoku Chemicals Corporation, “1B2PZ”) as the component (D) and the imidazole-based curing accelerator (manufactured by Shikoku Chemicals Corporation, “1B2PZ”) as the component (D) were used. 2MA-OK-PW ") Changed to 0.1 part.

A resin paste A was prepared in the same manner as in Example 3 except for the above items. Then, the resin paste A is used to obtain a cured product B for evaluation in the same manner as in Example 1, and the resin paste A or the cured product B for evaluation is used to cure the resin composition in the same manner as in Example 1. The thing was used for evaluation.

[Comparative Example 3]
In Example 3, 5 parts of a phenol-based curing agent (“MEH-8000H” manufactured by Meiwa Kasei Co., Ltd.) as a component (B) and an acid anhydride-based curing agent (“MH-8000H” manufactured by Shin Nihon Rika Co., Ltd.) as a component (B) were used. -700 ") Changed to 10 copies. Further, in Example 3, one part of the hydroxyl group-containing siloxane compound (polyether-modified silicone resin “KF-6012” manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (E-1) was not used. Further, in Example 3, 110 parts of the inorganic filler A as the component (C) was changed to 40 parts of the inorganic filler A as the component (C).

A resin paste A was prepared in the same manner as in Example 3 except for the above items. Then, the resin paste A is used to obtain a cured product B for evaluation in the same manner as in Example 1, and the resin paste A or the cured product B for evaluation is used to cure the resin composition in the same manner as in Example 1. The thing was used for evaluation.

[Evaluation method]
Using the cured product of the resin paste A or the cured product B for evaluation obtained in the above-mentioned Examples and Comparative Examples, various parameters are acquired for the cured product of the resin composition, and from the viewpoint of chemical resistance and warpage, It was evaluated by the following method. Table 1 shows the parameters used for the evaluation among the acquired parameters. The evaluation results are shown in Table 1.

<Acquisition of various parameters>
(Measurement of average coefficient of linear thermal expansion (CTE) α)
The cured product B for evaluation was cut into a width of about 5 mm and a length of about 15 mm to obtain a test piece A. The test piece A was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after the test piece A was attached to the thermomechanical analyzer, the coefficient of thermal expansion was measured twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. Then, based on the result of the second measurement, the average coefficient of linear thermal expansion α (ppm / K) in the range of 25 ° C. (298K) to 150 ° C. (423K) was calculated.

(Measurement of dynamic elastic modulus; acquisition of glass transition temperature Tg, storage elastic modulus E'and crosslink density n)
The cured product B for evaluation was cut into a width of 5 mm and a length of 15 mm to obtain a test piece B. This test piece B was subjected to thermomechanical analysis by a tensile weighting method using a viscoelasticity measuring device (“DMA7100” manufactured by Hitachi High-Tech Science Corporation). Specifically, after mounting the test piece E on the thermomechanical analyzer, the storage elastic modulus and the loss elastic modulus were measured under the measurement conditions of a load of 200 mN and a heating rate of 5 ° C./min.

First, the glass transition temperature Tg (° C.) was obtained from the peak top of tan δ (temperature-dependent curve of the ratio of storage elastic modulus and loss elastic modulus) obtained as a measurement result.

Subsequently, a predetermined temperature T (K) was determined. Specifically, the predetermined temperature T (K) was determined by adding 273K and adding 80K in order to convert the acquired glass transition temperature Tg (° C.) into the unit K. In the temperature range near the predetermined temperature T (K), the value of the storage elastic modulus tends not to fluctuate significantly. Therefore, the determined predetermined temperature T (K) is within the range of −5 ° C. to + 5 ° C. It is permissible that an error may occur in. Then, the measured value E 'of the storage elastic modulus at the determined predetermined temperature T (K) (unit: GPa, i.e. ¹⁰ 9 Pa) were obtained.

^{Next, the crosslink density n (mol / cm 3} ) was calculated by substituting the obtained E'(Pa) of the storage elastic modulus into the following equation. Here, the cross-linking density n can be considered as an index indicating the number of cross-linked molecules present per unit volume.
n = E'/ 3RT
(In the above formula, T is a predetermined temperature T (K), E'is a measured value (Pa) of the storage elastic modulus at a predetermined temperature T (K), and R is 8310000 as a gas constant. a ^{(Pa · cm 3 / mol ·} K). Incidentally, 'as / 3, the shear modulus G at a given temperature T (K)' E can be used measure of ⁽¹⁰ 9 Pa).)

(Acquisition of value Z _i)
The value Z _i is defined as a value obtained by dividing the average linear thermal expansion coefficient α (ppm / K) of the cured product by the cross-linking density n (mol / cm ³ _{) of the cured product, and this value Z i} (ppm · cm). ³ / mol · K) was obtained as a parameter of the cured product of the resin composition. By collating and evaluation results of each evaluation to be described later acquired value Z _i, were studied range capable of solving the problems of the present invention.

<Evaluation of warpage>
(Making a silicon wafer with an insulating layer for warpage measurement)
The resin paste A was compression-molded on a 12-inch disk-shaped silicon wafer (thickness 775 μm) using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). As a result, a resin composition molded product having a thickness of 300 μm was formed on the silicon wafer. Then, the resin composition molded article was heat-cured by heating at 150 ° C. for 60 minutes. As a result, a silicon wafer with a resin composition molded product that had been cured (that is, a silicon wafer with an insulating layer) was obtained.
(Measurement of warpage)
With one end of the obtained silicon wafer with an insulating layer pressed against a flat table, the distance between the lower surface of the end of the silicon wafer with an insulating layer and the upper surface of the table in the vertical direction is measured as the amount of warpage, and the maximum warp is measured. The end indicating the amount (μm) was identified.
(evaluation)
The maximum amount of warpage (μm) specified as described above was evaluated according to the following criteria.
"○": When the maximum warp amount is within the range of 0 μm or more and 2000 μm or less, the warp is small and the warp is sufficiently suppressed. “×”: When the maximum warp amount is more than 2000 μm, the warp is large and the warp is sufficiently suppressed. Is not sufficiently suppressed

<Evaluation of chemical resistance>
(Chemical immersion test)
A plurality of test pieces C were obtained by cutting the cured product B for evaluation into squares having a side of 5 cm. Specimen C was immersed in a strong alkaline aqueous solution at 70 ° C. for 1 hour. As the strong alkaline aqueous solution, a 1% by mass potassium hydroxide aqueous solution was used. After that, the test piece C was taken out, washed with distilled water, and dried in an oven at 130 ° C. for 1 hour. As a result, a test piece C'after the chemical immersion test was obtained.

(Measurement of mass before and after chemical immersion test and calculation of mass reduction rate)
The mass of the test piece C was measured, and this was defined as the mass M ₀ before the chemical immersion test. Further, the mass of the test piece C'was measured and used as the mass M ₁ before the chemical immersion test.
Subsequently, the mass reduction rate (%) before and after the chemical immersion test was calculated based on the following formula.
Mass reduction rate (%) = {(M _0- M ₁ ) / M ₀ } x 100
(evaluation)
The mass reduction rate (%) obtained as described above was evaluated according to the following criteria.
"○": When the mass reduction rate (%) is less than 1% by mass, the portion dissolved in the chemical is sufficiently small and the chemical resistance is excellent. "×": The mass reduction rate (%) is 1. When it is mass% or more, there are many parts dissolved in the chemical and the chemical resistance is inferior.

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in Table 1 below. In Table 1 below, the amount of each component represents the non-volatile component conversion amount. Further, the "inorganic filler content ratio" shown in Table 1 indicates the content of the component (C) when the resin component in the resin composition is 100% by mass. Further, α represents the average linear thermal expansion coefficient, T represents a predetermined temperature, E'represents the storage elastic modulus at a predetermined temperature T, n represents the cross-linking density, and Z _i represents the average. It represents a value obtained by dividing the linear thermal expansion coefficient α by the storage elastic modulus E'at a predetermined temperature T, and Tg represents the glass transition temperature.

<Examination>
As can be seen from Table 1, from the comparison between the examples and the comparative examples, in the examples, in the resin composition containing the components (A) and (B), the average linear thermal expansion coefficient α (ppm / K) of the cured product was obtained. ) Is divided by the crosslink density n (mol / cm ³ ) of the cured product, and the value Z _i (ppm · cm ³ / mol · K) is calculated by the following formula:
10 <Z _i <100
It was found that there is a tendency to provide a resin composition which is excellent in chemical resistance and can obtain a cured product in which warpage is suppressed by satisfying the above conditions.

Furthermore, it has been found that it is also possible to provide a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device according to an embodiment.

In addition, in Examples 1 to 3, it has been confirmed that even when the components (C) to (E) are not contained, the results are the same as those in the above Examples, although the degree is different. .. Further, in Examples 1 to 3, the strong alkaline aqueous solution used for the evaluation of chemical resistance may be any of a tetramethylammonium hydroxide solution, a sodium hydroxide aqueous solution and a sodium carbonate aqueous solution instead of the potassium hydroxide aqueous solution. , It has been confirmed that the result is similar to that of the above embodiment.

Claims (22)

A resin composition containing (A) an epoxy resin and (B) a curing agent.
The value Z obtained by dividing the average linear thermal expansion coefficient α (ppm / K) of the cured product obtained by curing the resin composition at 150 ° C. for 60 minutes by the cross-linking density n (mol / cm ^{3) of the cured product.} _i (pm · cm ³ / mol · K) is the following formula:
10 <Z _i <100
Meet,
Resin composition. The resin composition according to claim 1, further comprising (C) an inorganic filler. The resin composition according to claim 2, wherein the content of the component (C) is 80% by mass or more when the non-volatile component in the resin composition is 100% by mass. The component (B) is an acid anhydride-based curing agent, a maleimide-based curing agent, an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a carbodiimide-based curing agent, a benzoxazine-based curing agent, an amine-based curing agent, The resin composition according to any one of claims 1 to 3, which comprises one or more curing agents selected from cyanate ester-based curing agents. The resin composition according to any one of claims 1 to 4, wherein the content of the component (B) is 0.5% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 5, wherein the component (A) is one or more selected from (A-1) liquid epoxy resin and (A-2) solid epoxy resin. .. The resin composition according to claim 6, wherein the content of the solid epoxy resin (A-2) is 10% by mass or less when the content of the component (A) is 100% by mass. The mass ratio of the content of the component (A-1) to the content of the component (A-2) ((A-1) :( A-2)) is within the range of 1: 0 to 1: 0.1. The resin composition according to claim 6 or 7. The resin composition according to any one of claims 1 to 8, wherein the glass transition temperature Tg (° C.) of the cured product is in the range of 150 to 240 ° C. The resin composition according to any one of claims 1 to 9, wherein the cured product has an average linear thermal expansion coefficient α of 21 ppm / K or less. The storage elastic modulus E at a given temperature T (K) of the cured product 'is a 1.00 × ¹⁰ 9 Pa greater, wherein the predetermined temperature T (K) has a glass transition temperature Tg of the cured product The resin composition according to any one of claims 1 to 10, which is a temperature indicating the sum of (° C.) and 353 (K). The resin composition according to any one of claims 1 to 11, wherein the crosslinked density n of the cured product ^{is less than 0.50 mol / cm 3.} The resin composition according to any one of claims 1 to 12, wherein the crosslinked density n of the cured product is 0.16 mol / cm ^{3 or more.} The resin composition according to any one of claims 1 to 13, which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 14, which is used for forming a solder resist layer. A resin paste formed by containing the resin composition according to any one of claims 1 to 15. The cured product of the resin composition according to any one of claims 1 to 15 or the resin paste according to claim 16. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 15. A printed wiring board comprising an insulating layer formed by the resin composition according to any one of claims 1 to 15, the cured product of the resin paste according to claim 16, or the cured product according to claim 17. A semiconductor chip package including the printed wiring board according to claim 19 and a semiconductor chip mounted on the printed wiring board. The semiconductor chip and the resin composition according to any one of claims 1 to 15 or the cured product of the resin paste according to claim 16 or the cured product according to claim 17 for sealing the semiconductor chip. Including semiconductor chip package. A semiconductor device comprising the printed wiring board according to claim 19 or the semiconductor chip package according to claim 20 or 21.