JP2021042340A - Resin composition - Google Patents

Abstract

To provide a resin composition which can obtain a cured product which can reduce tackiness even when an inorganic filler is blended in a small amount and has excellent flexibility and excellent insulation reliability.SOLUTION: The resin composition contains (A) an epoxy resin, (B) an inorganic filler and (C) a polyimide resin, in which the component (A) contains (A-1) a siloxane skeleton-containing epoxy resin, and a content of the component (B) is 40 mass% or less when a non-volatile component in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing a polyimide resin. Furthermore, the present invention relates to a cured product, a resin sheet, a multilayer flexible substrate, and a semiconductor device obtained by using the resin composition.

In recent years, there has been an increasing demand for semiconductor components that are thinner, lighter, and have a higher mounting density. In order to meet this demand, attention is being paid to using a flexible substrate as a substrate substrate used for a semiconductor component. The flexible substrate can be thinner and lighter than the rigid substrate. Further, since the flexible substrate is flexible and deformable, it can be bent and mounted.

Generally, it is necessary to blend a flexible resin such as a polyimide resin into the insulating material of the flexible substrate. However, when the polyimide resin is blended, the tackiness (adhesiveness) may increase and the handleability may be inferior. .. Although it is possible to suppress the tackiness by blending the inorganic filler (Patent Document 1), it becomes difficult to achieve both flexibility and flexibility when the blending ratio of the inorganic filler is high.

Japanese Unexamined Patent Publication No. 2014-95047

An object of the present invention is a resin composition capable of obtaining a cured product having excellent flexibility and excellent insulation reliability while suppressing low tackiness despite the low content of the inorganic filler. Etc. are to be provided.

As a result of diligent studies to achieve the object of the present invention, the present inventors have obtained a resin composition containing (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin, which is (A). By using a resin composition containing (A-1) a siloxane skeleton-containing epoxy resin as a component, (B) the tackiness can be kept low even if the content of the inorganic filler is as low as 40% by mass or less. It has been found that a cured product having excellent flexibility and excellent insulation reliability can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin.
The component (A) contains (A-1) a siloxane skeleton-containing epoxy resin.
A resin composition in which the content of the component (B) is 40% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[2] The resin composition according to the above [1], wherein the component (A-1) is a cyclic siloxane skeleton-containing epoxy resin.
[3] The component (A-1) is the formula (A1) :.

[In the formula, R ¹ independently represents an epoxyalkyl group; R ² is an independently substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or substituted or unsubstituted. Indicates an aryl group; R ³ and R ⁴ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R ³ and R respectively. ⁴ together indicate one —O— and bind to each other to form a cyclic siloxane skeleton; s represents an integer greater than or equal to 1. ], The resin composition according to the above [1] or [2].
[4] The resin composition according to any one of the above [1] to [3], wherein the molecular weight of the component (A-1) is 800 or less.
[5] The epoxy equivalent of the component (A-1) is 150 g / eq. ~ 250 g / eq. The resin composition according to any one of the above [1] to [4].
[6] The above-mentioned [1] to [5], wherein the content of the component (A-1) is 5% by mass or more when the non-volatile component in the resin composition is 100% by mass. Resin composition.
[7] The above-mentioned [1] to [6], wherein the content of the component (A-1) is 10% by mass or less when the non-volatile component in the resin composition is 100% by mass. Resin composition.
[8] The resin composition according to any one of [1] to [7] above, wherein the average particle size of the component (B) is 1 μm or less.
[9] The resin composition according to any one of the above [1] to [8], wherein the component (B) is silica.
[10] The resin composition according to any one of [1] to [9] above, wherein the weight average molecular weight of the component (C) is 1,000 or more and 100,000 or less.
[11] The resin composition according to any one of [1] to [10] above, wherein the content of the component (C) is 20% by mass or more when the non-volatile component in the resin composition is 100% by mass. Stuff.
[12] The resin composition according to any one of [1] to [11] above, wherein the content of the component (C) is 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. Stuff.
[13] The resin composition according to any one of the above [1] to [12], which further contains (D) a curing agent.
[14] The resin composition according to the above [13], wherein the component (D) contains an active ester-based curing agent.
[15] The resin composition according to any one of the above [1] to [14], which is used for forming an insulating layer of a multilayer flexible substrate.
[16] A cured product of the resin composition according to any one of the above [1] to [15].
[17] A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of the above [1] to [15].
[18] A multilayer flexible substrate including an insulating layer formed by curing the resin composition according to any one of the above [1] to [15].
[19] A semiconductor device including the multilayer flexible substrate according to the above [18].

According to the resin composition of the present invention, it is possible to obtain a cured product having excellent flexibility and excellent insulation reliability while being able to suppress the tackiness to a low level despite the low content of the inorganic filler. it can.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

<Resin composition>
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin, and the component (A) contains (A-1) a siloxane skeleton. It contains an epoxy resin, and the content of the component (B) is 40% by mass or less. By using such a resin composition, it is possible to obtain a cured product having excellent flexibility and excellent insulation reliability while being able to suppress the tackiness to a low level even though the inorganic filler is low in composition. Can be done.

The resin composition of the present invention may further contain any component in addition to (A) epoxy resin, (B) inorganic filler, and (C) polyimide resin. Optional components include, for example, (D) curing agent, (E) curing accelerator, (F) other additives, and (G) organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin. (A) Epoxy resin means a curable resin having an epoxy group. The (A) epoxy resin also includes a modified epoxy resin.

The content of the epoxy resin (A) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass. It is mass% or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the content of the epoxy resin (A) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 70% by mass or less, more preferably 70% by mass or less. Is 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

<(A-1) siloxane skeleton-containing epoxy resin>
The (A) epoxy resin includes (A-1) a siloxane skeleton-containing epoxy resin. (A-1) The siloxane skeleton-containing epoxy resin refers to a compound having two or more epoxy groups and having a siloxane (Si—O—Si) bond.

The (A-1) siloxane skeleton-containing epoxy resin may be a cyclic siloxane skeleton-containing epoxy resin or a chain siloxane skeleton-containing epoxy resin, but a cyclic siloxane skeleton-containing epoxy resin is preferable.

The number of silicon atoms forming a siloxane bond in the (A-1) siloxane skeleton-containing epoxy resin is not particularly limited, but may be preferably 3 or more, preferably 10 or less, and more preferably 8 in one molecule. It can be less than or equal to, more preferably 6 or less, even more preferably 5 or less. Especially preferably, the number is four.

The number of epoxy groups in the (A-1) siloxane skeleton-containing epoxy resin is not particularly limited, but may be preferably 3 or more, preferably 10 or less, more preferably 8 or less, and further preferably 8 or less in one molecule. Can be 6 or less, and even more preferably 5 or less. Especially preferably, the number is four.

(A-1) All the substitutable sites of the silicon atom in the siloxane skeleton-containing epoxy resin are substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, or an aryl group having or not having an epoxy group. Is preferable. The hydrocarbon group may have a substituent other than the epoxy group.

The epoxy resin containing the siloxane skeleton (A-1) is preferably of the formula (A1):

[In the formula, R ¹ independently represents an epoxyalkyl group; R ² is an independently substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or substituted or unsubstituted. Indicates an aryl group; R ³ and R ⁴ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R ³ and R respectively. ⁴ together indicate one —O— and bind to each other to form a cyclic siloxane skeleton; s represents an integer greater than or equal to 1. ] Is a compound represented by.

"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. Examples of the "alkyl (group)" include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, sec-. Examples thereof include a pentyl group, a tert-pentyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a 2-cyclohexylmethyl group, a 2-cyclopentylethyl group and a 2-cyclohexylethyl group.

The "epoxyalkyl group" refers to a group in which two hydrogen atoms bonded to different carbon atoms of an alkyl group are replaced with one oxygen atom to form an oxacyclopropane (ethylene oxide) ring. The "epoxyalkyl group" is preferably an epoxyalkyl group having 2 to 10 carbon atoms. Examples of the "epoxyalkyl group" include linear epoxyalkyl groups such as 2,3-epylpropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group and 5,6-epoxyhexyl group; , 3-epyloxy-2-methylpropyl group, 3,4-epyl-3-methylbutyl group and other branched chain epoxyalkyl groups; 2,3-epoxycyclopentyl group, 3,4-epoxycyclopentyl group, 2,3- Cyclic epoxyalkyl groups such as epoxycyclohexyl group and 3,4-epylcyclohexyl group; 2,3-epyloxycyclopentylmethyl group, 3,4-epylcyclopentylmethyl group, 2,3-epylcyclohexylmethyl group, 3,4-epyl Cyclohexylmethyl group, 2- (2,3-epylcyclopentyl) ethyl group, 2- (3,4-epylcyclopentyl) ethyl group, 2- (2,3-epylcyclohexyl) ethyl group, 2- (3,4-) Epoxycyclohexyl) ethyl group, 3- (2,3-epoxycyclopentyl) propyl group, 3- (3,4-epoxycyclopentyl) propyl group, 3- (2,3-epoxycyclohexyl) propyl group, 3- (3) 4- (4-epylcyclohexyl) propyl group, 4- (2,3-epoxycyclopentyl) butyl group, 4- (3,4-epoxycyclopentyl) butyl group, 4- (2,3-epoxycyclohexyl) butyl group, 4- ( Examples thereof include a linear alkyl group having a cyclic epoxyalkyl group such as 3,4-epylcyclohexyl) butyl group at the end.

"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. 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.

The alkyl group in the "substituted or unsubstituted alkyl group" and the substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but for example, a halogen atom, a cyano group, or a nitro. Group, alkyl-oxy group, alkyl-carbonyl group, alkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-oxy group, alkenyl-carbonyl group, alkenyl-oxy-carbonyl group, alkenyl-carbonyl-oxy group, Examples thereof include an aryl group, an aryl-oxy group, an aryl-carbonyl group, an aryl-oxy-carbonyl group, an aryl-carbonyl-oxy group and the like, or a combination thereof. The number of substituents is preferably 1 to 3, and more preferably 1.

"Aryl (group)" refers to a monovalent aromatic hydrocarbon group. The "aryl (group)" is preferably an aryl group having 6 to 14 carbon atoms. Examples of the "aryl (group)" include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, but for example, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkyl-oxy group, an alkyl-carbonyl group. , Alkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl group, alkenyl-oxy group, alkenyl-carbonyl group, alkenyl-oxy-carbonyl group, alkenyl-carbonyl-oxy group, aryl group, aryl-alkyl group, Examples thereof include an aryl-alkenyl group, an aryl-oxy group, an aryl-carbonyl group, an aryl-oxy-carbonyl group, an aryl-carbonyl-oxy group and the like, or a combination thereof. The number of substituents is preferably 1 to 3, and more preferably 1.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and the like.

In the formula (A1), R ¹ independently represents an epoxyalkyl group, preferably a linear alkyl group having a cyclic epoxyalkyl group at the end, and more preferably a methyl group having a cyclic epoxyalkyl group. Alternatively, it is an ethyl group having a cyclic epoxyalkyl group at the end, and particularly preferably a 2- (3,4-epoxycyclohexyl) ethyl group.

In formula (A1), R ² independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and preferably a substituted or unsubstituted alkyl. It is a group, more preferably an (unsubstituted) alkyl group, still more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and particularly preferably a methyl group.

In formula (A1), R ³ and R ⁴ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, respectively, or R ³ and R ⁴ together show one -O- bonded to each other to form a cyclic siloxane skeleton. R ³ and R ⁴ preferably combine together to represent a single —O— and bind to each other to form a cyclic siloxane backbone.

In the formula (A1), s represents an integer of 1 or more, and is preferably an integer of 2 or more. s is preferably an integer of 9 or less, more preferably an integer of 7 or less, still more preferably an integer of 5 or less, and even more preferably an integer of 4 or less. Particularly preferably, s is 3.

Specific examples of the (A-1) siloxane skeleton-containing epoxy resin include 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -1,1,3,5,5-pentamethyltri. Chain siloxane skeleton-containing epoxy resin such as siloxane; 2,4,6,8-tetrakis (4- (3,4-epoxycyclopentyl) butyl) -2,4,6,8-tetramethylcyclotetrasiloxane, 2, 4,6,8-Tetraxane (3- (3,4-epoxycyclopentyl) propyl) -2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-Tetraxane (2- (3,3) 4-epoxycyclohexyl) ethyl) -2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentakis (2- (3,4-epoxycyclohexyl) ethyl) -2,4 , 6,8,10-Pentamethylcyclopentasiloxane and other cyclic siloxane skeleton-containing epoxy resins, among which 2,4,6,8-tetrakis (2- (3,4-epoxycyclohexyl) ethyl) -2 , 4,6,8-Tetramethylcyclotetrasiloxane is particularly preferred.

As a commercially available product of the (A-1) siloxane skeleton-containing epoxy resin, for example, "KR-470" manufactured by Shin-Etsu Chemical Co., Ltd. (main component: 2,4,6,8-tetrakis (2- (3,4-epoxy)) (Cyclohexyl) ethyl) -2,4,6,8-tetramethylcyclotetrasiloxane), "X-40-2667" (main component: 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) ) -1,1,3,5,5-pentamethyltrisiloxane) and the like.

The molecular weight of the (A-1) siloxane skeleton-containing epoxy resin is preferably 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less, and particularly preferably 800 or less. The lower limit may be, for example, 200 or more, 400 or more, 600 or more, and the like.

The epoxy equivalent of the (A-1) siloxane skeleton-containing epoxy resin is preferably 1,000 g / eq. Hereinafter, more preferably 500 g / eq. Hereinafter, more preferably, 300 g / eq. Hereinafter, particularly preferably 250 g / eq. It is as follows. The lower limit is preferably 50 g / eq. As mentioned above, more preferably 100 g / eq. Above, more preferably 130 g / eq. As mentioned above, particularly preferably 150 g / eq. That is all.

The viscosity (25 ° C.) of the (A-1) siloxane skeleton-containing epoxy resin is preferably 100 mPa · s to 10,000 mPa · s, and more preferably 1,000 mPa · s to 5,000 mPa · s.

The content of the (A-1) siloxane skeleton-containing epoxy resin in the resin composition is not particularly limited, but is preferably 1% by mass or more when the non-volatile component in the resin composition is 100% by mass. , More preferably 3% by mass or more, further preferably 4% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of the (A-1) siloxane skeleton-containing epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass. % Or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

<Any epoxy resin other than component (A-1)>
The (A) epoxy resin may further contain any other epoxy resin in addition to the (A-1) siloxane skeleton-containing epoxy resin.

Examples of the optional epoxy resin other than the component (A-1) 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, and dicyclopentadiene. Type epoxy resin, trisphenol type epoxy resin, naphthol 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 epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, glycidylcyclohexane type epoxy resin and the like. Any epoxy resin may be used alone or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as an arbitrary epoxy resin other than the component (A-1). The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 50% by mass or more, based on 100% by mass of the non-volatile component of any epoxy resin other than the component (A-1). It is 60% by mass or more, particularly preferably 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ). The resin composition of the present invention may contain only a liquid epoxy resin as an arbitrary epoxy resin other than the component (A-1), or may contain only a solid epoxy resin, but the liquid epoxy resin. And a solid epoxy resin are preferably contained in combination.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

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. An alicyclic epoxy resin having an alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycylol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol A type epoxy resin and bisphenol F type) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (Epoxy resin mixture); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd .; "ZX1658", "ZX1658GS" (cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. And so on. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more 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, and tetraphenylethane type epoxy resin are 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 "HP-7200", "HP-7200HH", "HP" -7200H "(dicyclopentadiene type epoxy resin); DIC's" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "( 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", "NC3000FH", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd .; "ESN485" (naphthol type epoxy resin); "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nittetsu Chemical &Materials; "YX4000H", "YX4000", "YX4000HK", "YL7890" manufactured by Mitsubishi Chemical Co., Ltd. (Bixylenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracen type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX7700" (xylene structure) manufactured by Mitsubishi Chemical Co., Ltd. (Containing novolak type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas 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" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as an arbitrary epoxy resin other than the component (A-1), their mass ratios (liquid epoxy resin: solid epoxy resin) are 100: 1 to 1: The range of 100 is preferable, the range of 10: 1 to 1:40 is more preferable, and the range of 1: 1 to 1:20 is even more preferable.

The epoxy equivalent of any epoxy resin other than the component (A-1) is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 60 g / eq. ~ 2,000 g / eq. , More preferably 70 g / eq. ~ 1,000 g / eq. , Even more preferably 80 g / eq. ~ 500 g / eq. Is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of any epoxy resin other than the component (A-1) is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

When the resin composition contains an arbitrary epoxy resin other than the component (A-1), the content of the arbitrary epoxy resin other than the component (A-1) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of any epoxy resin other than the component (A-1) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferable. It is 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

When the resin composition contains an arbitrary epoxy resin other than the component (A-1), the content of the (A-1) siloxane skeleton-containing epoxy resin in the (A) epoxy resin is not particularly limited. When the total amount of the epoxy resin (A) is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of the (A-1) siloxane skeleton-containing epoxy resin in the (A) epoxy resin is not particularly limited, but is preferably 50 when the total amount of the (A) epoxy resin is 100% by mass. It is mass% or less, more preferably 40 mass% or less, still more preferably 30 mass% or less, and particularly preferably 25 mass% or less.

<(B) Inorganic filler>
The resin composition of the present invention contains (B) an inorganic filler. (B) The inorganic filler is contained in the resin composition in the form of particles.

(B) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (B) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (B) As the inorganic filler, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

(B) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatex Co., Ltd. , "YA010C"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ", "SO-C4", "SO-C2" manufactured by Admatex. , "SO-C1"; "UFP-30", "DAW-03", "FB-105FD", etc. manufactured by Denka Corporation.

The average particle size of the inorganic filler (B) is not particularly limited, but is preferably 40 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 3 μm or less, and particularly preferably 1 μm or less. Is. (B) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, still more preferably 0. .1 μm or more, even more preferably 0.2 μm or more, particularly preferably 0.3 μm or more. (B) 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, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method. The average particle size was calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The specific surface area of the inorganic filler (B) is not particularly limited, but is preferably 0.1 m ² / g or more, more preferably 0.5 m ² / g or more, still more preferably 1 m ² / g or more. Particularly preferably, it is 5 m ² / g or more. (B) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 50 m ² / g or less, more preferably 30 m ² / g or less, still more preferably 20 m ² / g or less, and particularly preferably. Is 15 m ² / g or less. For the specific surface area of the inorganic filler, nitrogen gas is adsorbed on the sample surface using a 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. It can be obtained by.

The inorganic filler (B) is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, (B) the moisture resistance and dispersibility of the inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N Amino-based silane coupling agents such as −phenyl-8-aminooctyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; tris- (trimethoxysilylpropyl) isocyanurate, etc. Isocyanurate-based silane coupling agent; ureido-based silane coupling agent such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. An isocyanate-based silane coupling agent such as 3-isocyanoxide propyltriethoxysilane; an acid anhydride-based silane coupling agent such as 3-trimethoxysilylpropyl succinate; a silane coupling agent such as; methyltrimethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimeth Examples thereof include non-silane coupling-alkoxysilane compounds such as xysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Of these, an amino silane coupling agent is preferable. The surface treatment agent may be used alone or in combination of two or more at any ratio.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; "KBM-303", "KBM-402", and "KBM-402". KBM-403 "," KBE-402 "," KBE-403 "(epoxy-based silane coupling agent);" KBM-1403 "(styryl-based silane coupling agent);" KBM-502 "," KBM-503 " , "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-" 903 ”,“ KBE-903 ”,“ KBE-9103P ”,“ KBM-573 ”,“ KBM-575 ”(amino silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X" -12-967C "(acid anhydride-based silane coupling agent);" KBM-13 "," KBM-22 "," KBM-103 "," KBE-13 "," KBE-22 "," KBE-103 " , "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( Non-silane coupling-alkoxysilane compound) and the like.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, and is surface-treated with 0.2% by mass to 3% by mass. It is more preferable that the surface is treated with 0.3% by mass to 2% 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 of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity at the melt viscosity or sheet form a resin composition, preferably from 1.0 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} The following is more preferable.

(B) The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment 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 solid content, 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 content of the (B) inorganic filler in the resin composition is 40% by mass or less, preferably 38% by mass or less, and more preferably 36% by mass, when the non-volatile component in the resin composition is 100% by mass. % Or less, more preferably 34% by mass or less, and particularly preferably 32% by mass or less. The lower limit of the content of the (B) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or more. It is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more.

<(C) Polyimide resin>
The resin composition of the present invention contains (C) a polyimide resin. (C) The polyimide resin is a resin having an imide bond in the repeating unit. The (C) polyimide resin is generally obtained by (1) a resin obtained by an imidization reaction of a diamine compound and a tetracarboxylic dianhydride, or (2) an imidization reaction of a diisocyanate compound and a tetracarboxylic dianhydride. May include resin. The (C) polyimide resin also includes a modified polyimide resin such as a siloxane-modified polyimide resin.

The polyimide resin (C) is not particularly limited, but for example, the formula (C1):

[In the formula, X ¹ represents a tetravalent group obtained by removing two -CO-O-CO- from tetracarboxylic acid dianhydride, for example, from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. It can be an organic group consisting of two or more selected skeleton atoms (eg, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50). X ² _{represents a divalent group obtained by removing two -NH 2} from a diamine compound, or a divalent group obtained by removing two -NCOs from a diisocyanate compound, and represents, for example, a carbon atom, an oxygen atom, and a nitrogen atom. , And an organic group consisting of two or more (eg, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) skeleton atoms selected from sulfur atoms. n represents an integer of 2 or more. ] Can be included. ^{The organic groups of X 1} and X ² in the formula (C1) are not particularly limited as long as they are within the range of a chemically stable structure, and have a structure appropriately selected by those skilled in the art. For example, a known polyimide resin. It can be the structure of. When the polyimide resin (C) contains a structure represented by the formula (C1), the structure represented by the formula (C1) is preferably contained in an amount of 60% by mass or more, more preferably 80% by mass or more, and 90% by mass. It is more preferably contained in an amount of% or more, and particularly preferably 95% by mass or more.

The diamine compound for preparing the (C) polyimide resin is not particularly limited, and examples thereof include an aliphatic diamine compound and an aromatic diamine compound.

Examples of the aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , 1,10-Diaminodecane and other linear aliphatic diamine compounds; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched chain aliphatic diamine compounds such as diaminopentane; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexyl) An alicyclic diamine compound such as amine); a dimer acid type diamine (hereinafter, also referred to as “dimer diamine”) and the like can be mentioned.

The dimer acid type diamine means a diamine compound obtained by substituting two terminal carboxy groups (-COOH) of dimer acid with an aminomethyl group (-CH _2- NH ₂ ) or an amino group (-NH _2). To do. Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial production process is almost the same in the industry. It is standardized. As the dimer acid, a dimer acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid, which are particularly inexpensive and easily available, can be easily obtained. Further, the dimer acid may contain an arbitrary amount of monomeric acid, trimer acid, other polymerized fatty acids and the like depending on the production method, the degree of purification and the like. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in the present specification, hydrogenated substances whose degree of unsaturation has been reduced by further hydrogenation reaction are also included in dimer acid. Commercially available products of the dimer acid type diamine are available, and examples thereof include "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" manufactured by Croda Japan, and "Versamine 551" and "Versamine 552" manufactured by Cognis Japan. ..

Examples of the aromatic diamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, and 3,5-diaminobiphenyl. , 2,4,5,6-Tetrafluoro-1,3-phenylenediamine and other phenylenediamine compounds; 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diamino Naphthalenediamine compounds such as naphthalene; 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3' -Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-aminophenyl4-aminobenzoate, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) propane, 4,4'-(hexafluoroisopropyrine) diamineline, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, α, α-bis [4- (4-aminophenoxy) phenyl ] -1,3-Diisopropylbenzene, α, α-bis [4- (4-aminophenoxy) phenyl] -1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene) dianiline, 2,2-bis (3-Methyl-4-aminophenyl) propane, 2,2-bis (3-methyl-4-aminophenyl) benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-Diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis (3-methyl-4-aminophenyl) fluorene, 5- (4-aminophenoxy) -3- Examples thereof include diaminelin compounds such as [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan and 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate.

As the diamine compound, a commercially available one may be used, or a compound synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

The diisocyanate compound for preparing the (C) polyimide resin is not particularly limited, and examples thereof include an aliphatic diisocyanate compound, an aromatic diisocyanate compound, and isocyanato-based polyurethanes at both ends.

Examples of the aliphatic diisocyanate compound include linear aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, and dodecamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanis, 2,4. Branched chain aliphatic diisocyanate compounds such as 4-trimethylhexamethylene diisocyanate and 2,2-dimethylpentamethylene diisocyanate; isophoron diisocyanis (IPDI), 1,4-cyclohexamethylene diisocyanate (CHDI), 4-methyl-1,3 -Cyclohexamethylene isocyanate, 2-methyl-1,3-cyclohexamethylene isocyanate, 2-methyl-1,4-cyclohexamethylene isocyanate, dicyclohexamethylene-4,4'-diisocyanis, 1,3-bis (isosianatomethyl) cyclohexane An alicyclic diisocyanate compound such as 3,3a, 4,5,6,7,7a-hexahydro-4,7-methanoindan-1,8-irylene diisocyanate; dimeric acid type diisocyanate and the like.

The dimeric acid type diisocyanate means a diisocyanate compound obtained by substituting _{the amino group (-NH 2} ) of the dimer acid type diamine described above with an isocyanato group (-NCO).

Examples of the aromatic diisocyanate compound include phenylenediocyanates such as 1,4-phenylenediocyanate, 1,3-phenylenediocyanate, tolylen-2,6-diisocyanate, tolylen-2,4-diisocyanate and tolylen-3,5-diisocyanate. Compounds; 1,3-naphthalenediyl diisocyanate, 1,6-naphthalenediyl diisocyanate, 1,7-naphthalenediyl diisocyanate, 1,8-naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate, 2,7-naphthalenedyl diisocyanate, etc. Naphthalene diisocyanate compounds; examples thereof include bisisocyanatobenzene compounds such as 4,4'-diphenylmethane diisocyanate and 4,4'-diphenyl ether diisocyanate.

The both-terminal isocyanato-based polyurethane can be obtained by subjecting an aliphatic diisocyanate compound and / or an aromatic diisocyanate compound as described above to a urethanization reaction between both terminal hydroxy group polymers. Examples of the both-terminal hydroxy group polymer include both-terminal hydroxy group polyolefins such as both-terminal hydroxy group polybutadiene, both-terminal hydroxy group hydride polybutadiene, both-terminal hydroxy group polyisoprene, and both-terminal hydroxy group hydride polyisoprene; both-terminal hydroxy groups. It may be a double-ended hydroxy group polyether such as a base polyethylene glycol, a double-ended hydroxy group polypropylene glycol, a double-ended hydroxy group polytetramethylene glycol, or the like.

The number average molecular weight of both terminal hydroxy group polymers is not particularly limited, but is preferably 500 or more, more preferably 1,000 or more, still more preferably 2,000 or more. The upper limit of the number average molecular weight of both terminal hydroxy group polymers is not particularly limited, but is preferably 10,000 or less, more preferably 8,000 or less. The number average molecular weight here is a value measured by a gel permeation chromatography (GPC) method (in terms of polystyrene).

The bi-terminal isocyanato group polyurethane is described, for example, in the formula (C2) :.

[In the formula, X ^2a independently represents a divalent group obtained by removing two -NCOs from an aliphatic diisocyanate compound or an aromatic diisocyanate compound, for example, a carbon atom, an oxygen atom, a nitrogen atom, and It can be an organic group consisting of 2 to 50 skeleton atoms selected from sulfur atoms. Each of X ^2b independently represents a divalent group obtained by removing two -OH from both terminal hydroxy group polymers, and for example, two or more selected from a carbon atom and an oxygen atom (for example, 2 to 1). It can be an organic group consisting of 000, 2 to 500) skeleton atoms. m represents an integer of 1 to 10. ] Is an isocyanato group polyurethane at both ends.

As the diisocyanate compound, a commercially available one may be used, or a compound synthesized by a known method or a method similar thereto may be used. The diisocyanate compound may be used alone or in combination of two or more.

The tetracarboxylic dianhydride for preparing the (C) polyimide resin is not particularly limited, and examples thereof include an aliphatic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride. ..

Specific examples of the aliphatic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexane-1,2,3,4-. Tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'- Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (1,2-ethylene-4,4'-bis ( Cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-bis) Dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride and the like can be mentioned.

Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydrides such as pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride; 1,4,5. , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc. Naphthalenetetracarboxylic dianhydride; 2,3,6,7-anthranetetracarboxylic dianhydride Anthracenetetracarboxylic dianhydrides such as substances; 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfotetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride , 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-diphenylethertetra Carcarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfonate dianhydride, methylene-4,4 '-Diphthalic acid dianhydride, 1,1-ethinilidene-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4, 4'-diphthalic dianhydride, 1,3-trimethylethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene -4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis (2,3-dicarboxy) Diphthal such as phenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4'-(4,4'-isopropydiandiphenoxy) bisphthalic acid dianhydride, etc. Examples include acid dianhydride and the like.

As the tetracarboxylic dianhydride, a commercially available one may be used, or one synthesized by a known method or a method similar thereto may be used. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

The content of the structure derived from the aromatic tetracarboxylic dianhydride with respect to the total structure derived from the tetracarboxylic dianhydride constituting the (C) polyimide resin is preferably 10 mol% or more, preferably 30 mol%. More preferably, it is more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, and even more preferably 100 mol%. Is particularly preferable.

The weight average molecular weight of the polyimide resin (C) is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and particularly preferably 7,000 or more. Is. The upper limit of the weight average molecular weight of the (C) polyimide resin is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50. It is 000 or less.

The number average molecular weight of the polyimide resin (C) is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and particularly preferably 7,000 or more. Is. The upper limit of the number average molecular weight of the (C) polyimide resin is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50. It is 000 or less.

The content of the (C) polyimide resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or more, more preferably 10. It is mass% or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of the (C) polyimide resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 50% by mass or less. Is 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less.

<(D) Hardener>
The resin composition of the present invention may further contain (D) a curing agent. The curing agent (D) has a function of curing the epoxy resin (A).

The curing agent (D) is not particularly limited, but for example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system curing agent. The curing agent may be used alone or in combination of two or more. The curing agent (D) preferably contains a curing agent selected from a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent, and particularly preferably contains an active ester-based curing agent.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" manufactured by Nittetsu Chemical & Materials Co., Ltd. , "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", manufactured by DIC Corporation, Examples thereof include "TD2090" and "TD-2090-60M".

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, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trihydride 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. Examples of commercially available acid anhydride-based curing agents include "HNA-100" and "MH-700" manufactured by New Japan Chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is 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-dicyclopentalene-phenylene.

Commercially available active ester-based curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "" HPC-8000-65T ”,“ HPC-8000H-65TM ”,“ EXB-8000L ”,“ EXB-8000L-65M ”,“ EXB-8000L-65TM ”(manufactured by DIC); "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC); as an active ester-based curing agent which is an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical); "YLH1026" (manufactured by Mitsubishi Chemical), "YLH1030" (manufactured by Mitsubishi Chemical), "YLH1048" (manufactured by Mitsubishi Chemical) as active ester-based curing agents that are benzoylates of phenol novolac. Made); etc.

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 .; "P-d" manufactured by Shikoku Kasei Kogyo Co., Ltd. Examples include "FA".

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A disicanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of the trimers are trizinized) and the like can be mentioned.

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

When the resin composition contains (D) a curing agent, the amount ratio of (A) epoxy resin to (D) curing agent is [(A) number of epoxy groups in the epoxy resin]: [(D) number of reactive groups in the curing agent. ], It is preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and even more preferably 1: 0.4 to 1: 1.4. Here, the reactive group of the (D) curing agent is, for example, an aromatic hydroxyl group in the case of a phenol-based curing agent and a naphthol-based curing agent, and an active ester group in the case of an active ester-based curing agent, depending on the type of the curing agent. different.

(D) The reaction group equivalent of the curing agent is preferably 50 g / eq. ~ 3,000 g / eq. , More preferably 100 g / eq. ~ 1,000 g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , Particularly preferably 100 g / eq. ~ 300 g / eq. Is. The reaction group equivalent is the mass of the curing agent per reaction group equivalent.

When the (D) curing agent contains an active ester-based curing agent, the content thereof is not particularly limited, but when the total amount of the (D) curing agent is 100% by mass, it is preferably 10% by mass. As mentioned above, it is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more.

When the resin composition contains the (D) curing agent, the content of the (D) curing agent in the resin composition is not particularly limited, but the non-volatile component in the resin composition is 100% by mass. In this case, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of the curing agent (D) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, more preferably. Is 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 8% by mass or less.

<(E) Curing accelerator>
The resin composition of the present invention may contain (E) a curing accelerator as an optional component. The (E) curing accelerator has a function of accelerating the curing of the (A) epoxy resin.

The (E) curing accelerator is not particularly limited, but for example, a phosphorus-based curing accelerator, a urea-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and the like. Examples include metal-based curing accelerators. Among them, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an imidazole-based curing accelerator is particularly preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromeritate, and tetrabutylphosphonium hydro. An aliphatic phosphonium salt such as genhexahydrophthalate, tetrabutylphosphonium cresol novolac trimerate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, Butytriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-triltriphenylphosphonium tetra-p-trilborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrap-trilborate, triphenylethylphosphonium Triphenylphosphine, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiosianate, tetraphenylphosphonium thiosianate, butyltriphenylphosphonium Arophenylphosphine salts such as thiosphineate; aromatic phosphine / borane complex such as triphenylphosphine / triphenylborane; aromatic phosphine / quinone addition reactants such as triphenylphosphine / p-benzoquinone addition reaction; tributylphosphine, tri Aliphatic phosphines such as -tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, tricyclohexylphosphine; dibutylphenylphosphine , Di-tert-butylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclophenylphosphine, triphenylphosphine, tri-o-triphenylphosphine, tri-m-trilphosphine, tri-p-trilphosphine, Tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-isopropylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (4-tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris ( 2,5-Diphenylphosphine, tris (2,6-dimethylphenyl) phosphine, tris (3,5-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-- Diphenyl-4-ethoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl-2 -Pyridylphosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphino) Examples include aromatic phosphine such as acetylene and 2,2'-bis (diphenylphosphine) diphenyl ether.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-. Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) ) -1,1-Dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (2-methylphenyl) -1,1-dimethylurea, 3- (4- (4- Methylphenyl) -1,1-dimethylurea, 3- (3,4-dimethylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea, 3- (4-) Methoxyphenyl) -1,1-dimethylurea, 3- (4-nitrophenyl) -1,1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl] -1,1-dimethylurea, 3- [4- (4-Chlorophenoxy) phenyl] -1,1-dimethylurea, 3- [3- (trifluoromethyl) phenyl] -1,1-dimethylurea, N, N- (1,4-phenylene) Aromatic dimethylurea such as bis (N', N'-dimethylurea), N, N- (4-methyl-1,3-phenylene) bis (N', N'-dimethylurea) [toluenebis dimethylurea] And so on.

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 is 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-Imidazole compounds such as phenylimidazolin and adducts of imidazole compounds and epoxy resins can be mentioned.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. 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-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex 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 (E) a curing accelerator, the content of the (E) curing accelerator in the resin composition is not particularly limited, but 100% by mass of the non-volatile component in the resin composition. , It is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit of the content of the (E) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less. It is preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

<(F) Other additives>
The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include organic fillers such as rubber particles, polyamide fine particles, and silicone particles; phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, and poly. Thermoplastic resins such as ether ether ketone resins and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon Colorants such as black; Antipolymerization agents such as hydroquinone, catechol, pyrogallol, phenothiazine; Leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; Thickeners such as Benton and montmorillonite; Silicone-based defoaming agents, acrylic Defoaming agents for defoaming agents, fluorine-based defoaming agents, vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesive improvers such as ureasilane; Triazole-based adhesion-imparting agents, Adhesion-imparting agents such as tetrazole-based adhesion-imparting agents and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent whitening agents such as stillben derivatives; fluorine-based Surfactants such as surfactants and silicone-based surfactants; phosphorus-based flame retardants (eg phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (eg melamine sulfate), halogen-based flame retardants. Examples thereof include flame-retardant agents such as fuel agents and inorganic flame-retardant agents (for example, antimony trioxide). As the additive, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. (F) The content of other additives can be appropriately set by those skilled in the art.

<(G) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component. As the (G) organic solvent, known ones can be appropriately used, and the type thereof is not particularly limited. Examples of the organic solvent (G) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-. Ester solvents such as butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate Ester alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethylsulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other fats Group hydrocarbon-based solvent; Examples thereof include aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. As the organic solvent (G), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

<Manufacturing method of resin composition>
The resin composition of the present invention is, for example, in an arbitrary reaction vessel, (A) epoxy resin, (B) inorganic filler, (C) polyimide resin (preliminized), and if necessary (D). Curing agent, (E) curing accelerator as needed, (F) other additives as needed, and (G) organic solvent as needed, in any order and / or part or all at the same time. In addition, it can be produced by mixing. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end. Further, stirring or shaking may be performed in the process of adding and mixing each component. Further, the resin composition may be stirred at the time of additional mixing or thereafter using a stirring device such as a mixer to uniformly disperse the resin composition.

<Characteristics of resin composition>
Since the resin composition of the present invention contains (A) epoxy resin, (B) inorganic filler, and (C) polyimide resin, and the component (A) contains (A-1) siloxane skeleton-containing epoxy resin, ( B) Even if the content of the inorganic filler is as low as 40% by mass or less, the tackiness can be suppressed to a low level, and a cured product having excellent flexibility and excellent insulation reliability can be obtained.

Since the cured product of the resin composition of the present invention is excellent in flexibility, for example, as in Test Example 1 described below, a layered cured product of a resin composition having a thickness of 40 μm, a width of 15 mm, and a length of 110 mm can be used. When a MIT fold resistance test is performed with a load of 2.5 N, a bending angle of 90 degrees, a bending speed of 175 times / minute, and a bending radius of 1.0 mm in accordance with JIS C-5016, the number of times of folding is preferable. Can be 3,000 times or more, more preferably 5,000 times or more, still more preferably 7,000 times or more, and particularly preferably 8,000 times or more.

Since the cured product of the resin composition of the present invention has excellent insulation reliability, for example, the insulation resistance value of the insulating layer of the evaluation substrate measured by the method of Test Example 3 described below is preferably 1.00 ×. 10 ⁷ Omega or more, more preferably 1.00 × 10 ⁸ Ω or more, more preferably 1.00 × 10 ⁹ Ω or more, and particularly preferably be a 1.00 × ^{10 10 Ω} or more.

Since the resin composition of the present invention can suppress the tackiness to a low level, for example, as in Test Example 2 described below, the diameter of the glass probe used is 5 mm, the load is 1 kgf / cm ² , and the contact speed is 0.5 mm /. The tack force measured under the conditions of seconds, tensile speed 0.5 mm / sec, holding time 10 seconds, and temperature 80 ° C. is preferably 1.8 N or less, more preferably 1.6 N or less, still more preferably 1.4 N or less. Especially preferably, it is 1.2 N or less.

<Use of resin composition>
The resin composition of the present invention can be widely used in insulating materials such as printed wiring boards and multilayer flexible substrates, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component filling resins and the like. The printed wiring board, the multilayer flexible substrate, and the like can be manufactured by using, for example, a sheet-like laminated material such as a resin sheet or a prepreg.

<Resin sheet>
The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 70 μm or less. 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 leaf 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"). ) Etc., polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyethersulfide (PES), polyether. 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 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, a resin varnish prepared by dissolving the resin composition as it is or by dissolving the resin composition in an organic solvent, for example, 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 allowing it to be produced.

Examples of the organic solvent that can be used when coating on the support include those similar to those mentioned in the description of the organic solvent as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

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. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the temperature is 50 ° C to 150 ° C for 3 minutes to 10 to 10. The resin composition layer can be formed by drying for a minute.

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.

<Laminated sheet>
The laminated sheet is a sheet produced by laminating and curing a plurality of resin composition layers. The laminated sheet contains a plurality of insulating layers as a cured product of the resin composition layer. Usually, the number of resin composition layers laminated to produce a laminated sheet corresponds to the number of insulating layers contained in the laminated sheet. The specific number of insulating layers per laminated sheet is usually 2 or more, preferably 3 or more, particularly preferably 5 or more, preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less. ..

The laminated sheet can be a sheet that is used by being bent so that one side thereof faces each other. The minimum bending radius for bending the laminated sheet is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, preferably 5 mm or less, and more. It is preferably 4 mm or less, and particularly preferably 3 mm or less.

Holes may be formed in each insulating layer included in the laminated sheet. This hole can function as a via hole or a through hole in the multilayer flexible substrate.

The laminated sheet may further contain any element in addition to the insulating layer. For example, the laminated sheet may include a conductor layer as an optional element. The conductor layer is usually partially formed on the surface of the insulating layer or between the insulating layers. This conductor layer typically functions as wiring in a multilayer flexible substrate.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor material may be a single metal or an alloy. Examples of the alloy include alloys of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of conductor layer formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloy, copper -Alloys such as nickel alloys and copper / titanium alloys; are preferable. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal; and nickel-chromium alloy; are more preferable, and copper single metal is further preferable.

The conductor layer may have a single-layer structure, or may have a single-metal layer made of different types of metals or alloys, or a multi-layer structure including two or more alloy layers. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The conductor layer may be patterned to function as wiring.

The thickness of the conductor layer depends on the design of the multilayer flexible substrate, 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 thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, preferably 2,000 μm or less, more preferably 1,000 μm or less, and particularly preferably 500 μm or less.

<Manufacturing method of laminated sheet>
The laminated sheet can be produced by a manufacturing method including (a) a step of preparing a resin sheet and (b) a step of laminating and curing a plurality of resin composition layers using the resin sheet. The order of laminating and curing the resin composition layer is arbitrary as long as a desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after all the plurality of resin composition layers are laminated, the laminated plurality of resin composition layers may be cured at once. Further, for example, each time another resin composition layer is laminated on one resin composition layer, the laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiments described below, for the sake of distinction, the resin composition layers are appropriately numbered such as "first resin composition layer" and "second resin composition layer", and further, they are indicated. The insulating layer obtained by curing the resin composition layer of No. 1 is also numbered like "first insulating layer" and "second insulating layer" in the same manner as the resin composition layer.

In one preferred embodiment, step (b) is
(II) A step of curing the first resin composition layer to form a first insulating layer,
(VI) A step of laminating a second resin composition layer on the first insulating layer, and
(VII) A step of curing the second resin composition layer to form a second insulating layer,
including. Further, in step (b), if necessary,
(I) A step of laminating the first resin composition layer on the sheet support base material,
(III) The process of drilling holes in the first insulating layer,
(IV) Step of roughening the first insulating layer,
(V) It may include an arbitrary step such as a step of forming a conductor layer on the first insulating layer. Hereinafter, each step will be described.

The step (I) is a step of laminating the first resin composition layer on the sheet support base material before the step (II). The sheet support base material is a peelable member, and for example, a plate-shaped, sheet-shaped, or film-shaped member is used.

Lamination of the sheet support base material and the first resin composition layer may be carried out by 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., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and 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 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

When a resin sheet is used, the lamination of the sheet support base material and the first resin composition layer is performed, for example, by pressing the resin sheet from the support side and using the first resin composition layer of the resin sheet as the sheet support base material. This can be done by heat crimping. Examples of the member for heat-pressing the resin sheet to the sheet support base material (hereinafter, also referred to as “heat-bonding member”) include, for example, a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). And so on. Rather than pressing the heat-bonded member directly onto the resin sheet, it is preferable to press the member through an elastic material such as heat-resistant rubber so that the first resin composition layer sufficiently follows the surface irregularities of the sheet-supporting base material.

After laminating, the first resin composition layer may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, with a heat-bonding member. For example, when a resin sheet is used, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet from the support side with a heat-bonding member. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The laminating and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

Step (II) is a step of curing the first resin composition layer to form the first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions adopted when forming the insulating layer of the printed wiring board can be arbitrarily applied. The first resin composition layer can be cured by, for example, thermosetting.

Generally, the specific thermosetting conditions differ depending on the type of resin composition. For example, the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., and even more preferably 170 ° C. to 210 ° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and even more preferably 20 minutes to 100 minutes.

Before the first resin composition layer is thermosetting, the first resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the first resin composition layer, the first resin is at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). The composition layer may be preheated for 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, even more preferably 15 to 100 minutes).

Step (III) is a step of drilling a hole in the first insulating layer. By this step (III), holes such as via holes and through holes can be formed in the first insulating layer. Drilling may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition. The size and shape of the hole may be appropriately set according to the design of the multilayer flexible substrate.

Step (IV) is a step of roughening the first insulating layer. Usually, smear removal is also performed in this step (IV). Therefore, the roughening treatment is sometimes called a desmear treatment. Examples of the roughening treatment include a method in which a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order.

The swelling liquid is not particularly limited, and examples thereof include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid can be performed, for example, by immersing the cured product in the swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which a permanganate solution is dissolved in a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing Solution Security P" manufactured by Atotech Japan. .. The roughening treatment with an oxidizing agent can be performed by immersing the cured product in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes.

An acidic aqueous solution is used as the neutralizing solution. Examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the cured product in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the cured product in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes.

The arithmetic mean roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less. The lower limit is not particularly limited, but may be 30 nm or more, 40 nm or more, and 50 nm or more.

The step (V) is a step of forming a conductor layer on the first insulating layer, if necessary. 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. Preferable examples include a method of plating the surface of the first insulating layer by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Above all, the semi-additive method is preferable from the viewpoint of ease of production.

Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown. First, a plating seed layer is formed on the surface of the first insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal 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.

The first insulating layer is obtained in the step (II), and the step (III), the step (IV), and the step (V) are performed as necessary, and then the step (VI) is performed. The step (VI) is a step of laminating the second resin composition layer on the first insulating layer. The lamination of the first insulating layer and the second resin composition layer can be performed by the same method as the lamination of the sheet support base material and the first resin composition layer in the step (I).

However, when the first resin composition layer is formed using the resin sheet, the support of the resin sheet is removed before the step (VI). The removal of the support may be performed between the steps (I) and the step (II), between the steps (II) and the step (III), and between the steps (III) and the step (IV). ), Or between step (IV) and step (V).

After the step (VI), the step (VII) is performed. The step (VII) is a step of curing the second resin composition layer to form a second insulating layer. The curing of the second resin composition layer can be performed in the same manner as the curing of the first resin composition layer in the step (II). Thereby, a laminated sheet including a plurality of insulating layers such as a first insulating layer and a second insulating layer can be obtained.

Further, in the method according to the above-described embodiment, if necessary, (VIII) a step of drilling a hole in the second insulating layer, (IX) a step of roughening the second insulating layer, and (X) a second insulating layer. A step of forming a conductor layer on the layer may be performed. The drilling of the second insulating layer in the step (VIII) can be performed in the same manner as the drilling of the first insulating layer in the step (III). Further, the roughening treatment of the second insulating layer in the step (IX) can be performed by the same method as the roughening treatment of the first insulating layer in the step (IV). Further, the formation of the conductor layer on the second insulating layer in the step (X) can be performed in the same manner as the formation of the conductor layer on the first insulating layer in the step (V).

In the above-described embodiment, an embodiment in which a laminated sheet is produced by laminating and curing two resin composition layers, that is, a first resin composition layer and a second resin composition layer, has been described, but a resin composition having three or more layers has been described. A laminated sheet may be manufactured by laminating and curing a material layer. For example, in the method according to the above-described embodiment, the resin composition layer is laminated and cured by steps (VI) to (VII), and if necessary, holes are drilled in the insulating layer by steps (VIII) to (X). , The roughening treatment of the insulating layer and the formation of the conductor layer on the insulating layer may be repeatedly carried out to produce a laminated sheet. As a result, a laminated sheet containing three or more insulating layers can be obtained.

Furthermore, the method according to the above-described embodiment may include any step other than the above-mentioned steps. For example, when the step (I) is performed, the step of removing the sheet supporting base material may be performed.

<Multilayer flexible substrate>
The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only a laminated sheet, or may include an arbitrary member in combination with the laminated sheet. Examples of the optional member include an electronic component, a coverlay film, and the like.

The multilayer flexible substrate can be manufactured by a manufacturing method including the above-mentioned method for manufacturing a laminated sheet. Therefore, the multilayer flexible substrate can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet and (b) a step of laminating and curing a plurality of resin composition layers using the resin sheet.

The method for manufacturing a multilayer flexible substrate may further include an arbitrary step in combination with the above steps. For example, a method for manufacturing a multilayer flexible substrate including electronic components may include a step of joining electronic components to a laminated sheet. As the joining condition between the laminated sheet and the electronic component, any condition can be adopted in which the terminal electrode of the electronic component and the conductor layer as wiring provided on the laminated sheet can be connected by a conductor. Further, for example, a method for manufacturing a multilayer flexible substrate including a coverlay film may include a step of laminating a laminated sheet and a coverlay film.

The multilayer flexible substrate can be usually used by being bent so that one surface of the laminated sheet included in the multilayer flexible substrate faces each other. For example, a multilayer flexible substrate is housed in a housing of a semiconductor device in a state of being bent to reduce its size. Further, for example, a multilayer flexible substrate is provided in a movable portion of a semiconductor device having a bendable movable portion.

<Semiconductor device>
The semiconductor device includes the multilayer flexible substrate described above. The semiconductor device includes, for example, a multilayer flexible substrate and a semiconductor chip mounted on the multilayer flexible substrate. In many semiconductor devices, the multilayer flexible substrate can be housed in the housing of the semiconductor device by bending so that one surface of the laminated sheet included in the multilayer flexible substrate faces each other.

Examples of semiconductor devices include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.). Be done.

The semiconductor device includes, for example, a step of preparing a multilayer flexible substrate, a step of bending the multilayer flexible substrate so that one surface of the laminated sheet faces each other, and a step of storing the bent multilayer flexible substrate in a housing. It can be manufactured by a manufacturing method including.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "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 (25 ° C., 1 atm) unless otherwise specified.

<Synthesis Example 1: Synthesis of Polyimide Resin 1>
G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5,047 (GPC method), hydroxyl group equivalent = 1,798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) in a reaction vessel. ) 50 g, 23.5 g of Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added with further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product is cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol are added to the reaction product. 40.4 g of acetate (manufactured by Daicel Co., Ltd.) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm ^{-1 was confirmed from FTIR.} The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered with a 100-mesh filter cloth to obtain a polyimide resin 1 having an imide skeleton, a urethane skeleton, and a butadiene skeleton.
Viscosity: 7.5 Pa · s (25 ° C, E-type viscometer)
Acid value: 16.9 mg KOH / g
Solid content: 50% by mass
Number average molecular weight: 13,723
Glass transition temperature: -10 ° C
Content of polybutadiene structural part: 50 / (50 + 4.8 + 8.96) x 100 = 78.4% by mass

<Synthesis Example 2: Synthesis of Polyimide Resin 2>
9.13 g (30 mmol) of 4-aminobenzoate 5-amino-1,1'-biphenyl-2-yl, 4,4'-(4,) in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. 4'-Isopropyridene diphenoxy) Bisphthalic acid dianhydride 15.61 g (30 mmol), N-methyl-2-pyrrolidone 94.64 g, pyridine 0.47 g (6 mmol), toluene 10 g were added, and under a nitrogen atmosphere. A polyimide solution containing the polyimide resin 2 (nonvolatile content: 20% by mass) was obtained by performing an imidization reaction at 180 ° C. for 4 hours while peeping toluene out of the system. No precipitation of the synthesized polyimide resin 2 was observed in the polyimide solution. The weight average molecular weight of the polyimide resin 2 was 45,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3>
Aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4') in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. -Isopropyridenediphenoxy) bisphthalic dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged, and the solution was heated to 60 ° C. Next, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bis (aminomethyl) cyclohexane were added dropwise, and then an imidization reaction was carried out at 140 ° C. for 1 hour. As a result, a polyimide solution containing the polyimide resin 3 (nonvolatile content: 30% by mass) was obtained. The weight average molecular weight of the polyimide resin 3 was 25,000.

<Synthesis Example 4: Synthesis of Polyimide Resin 4>
A 500 mL separable flask equipped with a moisture metering receiver connected to a reflux condenser, a nitrogen introduction pipe, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) 29.6 g of phenyl] -1,1,3-trimethylindan was added, and the mixture was stirred at 45 ° C. for 2 hours under a nitrogen stream to carry out the reaction. Next, the temperature of this reaction solution was raised and the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. It was confirmed that a predetermined amount of water had accumulated in the water content metering receiver and that no outflow of water was observed. After confirmation, the temperature of the reaction solution was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Then, it was cooled to obtain a polyimide solution (nonvolatile content 20% by mass) containing a polyimide resin 4 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 4 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin 4 was 12,000.

<Example 1: Preparation of resin composition 1>
Bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent about 185g / eq.) 5 parts, Naphthalene type epoxy resin (Nippon Steel & Sumitomo Metal Corporation "ESN475V", epoxy equivalent about 332g / eq.), 5 parts, Bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent about 238 g / eq.) 10 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent about 135 g / eq.), And 40 parts of the epoxy resin 1 (50% by mass of the non-volatile component) obtained in Synthesis Example 1 was heated and dissolved in 10 parts of cyclohexanone while stirring. After cooling to room temperature, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl equivalent of about 151 g / eq., 2-methoxypropanol solution having a non-volatile content of 50%), Active ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution with active group equivalent of about 220 g / eq., 65% by mass of non-volatile component), spherical silica ("SC2500SQ" manufactured by Admatex, average) Particle size 0.5 μm, specific surface area 11.2 m ² / g, 100 parts of silica surface treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 25 6 parts of siloxane skeleton-containing epoxy resin (manufactured by Shinetsu Chemical Industry Co., Ltd., "KR470", epoxy equivalent about 200 g / eq.) And 0.2 part of amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) are mixed. Then, after uniformly dispersing with a high-speed rotary mixer, the resin composition 1 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKICHNO).

<Example 2: Preparation of resin composition 2>
Examples except that 100 parts of the polyimide resin 2 (20% by mass of the non-volatile component) obtained in Synthesis Example 2 was used instead of using 40 parts of the polyimide resin 1 (50% by mass of the non-volatile component) obtained in Synthesis Example 1. The same operation as in 1 was carried out to prepare the resin composition 2.

<Example 3: Preparation of resin composition 3>
Except that 66.7 parts of the polyimide resin 3 (30% by mass of the non-volatile component) obtained in Synthesis Example 3 was used instead of using 40 parts of the polyimide resin 1 (50% by mass of the non-volatile component) obtained in Synthesis Example 1. The same operation as in Example 1 was carried out to prepare the resin composition 3.

<Example 4: Preparation of resin composition 4>
Examples except that 100 parts of the polyimide resin 4 (20% by mass of the non-volatile component) obtained in Synthesis Example 4 was used instead of using 40 parts of the polyimide resin 1 (50% by mass of the non-volatile component) obtained in Synthesis Example 1. The same operation as in 1 was carried out to prepare the resin composition 4.

<Comparative Example 1: Preparation of Resin Composition 5>
The resin composition 5 was prepared by performing the same operation as in Example 1 except that 6 parts of a siloxane skeleton-containing epoxy resin (manufactured by Shin-Etsu Chemical Co., Ltd., “KR470”, epoxy equivalent: about 200 g / eq.) Was not used. did.

<Comparative Example 2: Preparation of Resin Composition 6>
Implementation except that 66 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass) was used instead of 40 parts of the polyimide resin 1 (50% by mass of non-volatile component) obtained in Synthesis Example 1. The same operation as in Example 1 was carried out to prepare the resin composition 6.

<Test Example 1: Evaluation of flexibility (MIT folding resistance)>
The thickness of the resin composition layer after drying is 40 μm on the release-treated surface of the PET film (thickness 38 μm) in which the resin compositions of each Example and Comparative Example are treated with an alkyd-based mold release agent. , Was uniformly applied with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet 1.

The obtained resin sheet 1 is laminated on a polyimide film (Ube Industries, Ltd., Upirex S) using a batch type vacuum pressurizing laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.) to protect it. A resin sheet with a film was obtained. The laminate was depressurized for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimped at 120 ° C. for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, the resin composition was cured under curing conditions of 190 ° C. for 90 minutes, and the polyimide film was peeled off to obtain a cured product sample.

The obtained cured product sample was cut into test pieces having a width of 15 mm and a length of 110 mm, and a MIT tester (MIT-DA), a MIT folding fatigue tester manufactured by Toyo Seiki Seisakusho Co., Ltd., was used. According to JIS C-5016, the number of folding resistances until the cured product was broken was measured under the measurement conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute. The measurement was performed on 5 samples, and the average value of the top 3 points was calculated. When the number of times of folding was less than 8,000, it was evaluated as "x", and when it was 8,000 or more, it was evaluated as "○".

<Test Example 2: Evaluation of tackiness (adhesiveness)>
The protective film was peeled off from the resin sheet with the protective film obtained in Test Example 1, and the resin composition layer was subjected to a probe tack tester (manufactured by Tester Sangyo Co., Ltd., "TE-6002") with a glass probe having a diameter of 5 mm. The tack force at a load of 1 kgf / cm ² , a contact speed of 0.5 mm / sec, a tensile speed of 0.5 mm / sec, a holding time of 10 seconds, and a temperature of 80 ° C. was measured. When the tack force exceeded 1.6 N, it was evaluated as “x”, and when it was 1.6 N or less, it was evaluated as “◯”.

<Test Example 3: Evaluation of insulation reliability>
(1) Base treatment of inner layer circuit board Glass cloth base material epoxy resin double-sided copper-clad laminate having circuit conductors (copper) formed with a wiring pattern of L / S = 10 μm / 10 μm on both sides as an inner layer circuit board ( A copper foil thickness of 3 μm, a substrate thickness of 0.15 mm, and Mitsubishi Gas Chemical Company's “HL832NSF LCA” (255 × 340 mm size) were prepared. Both sides of the inner layer circuit board were treated with an organic film on the copper surface with "FlatBOND-FT" manufactured by MEC.

(2) Laminating of resin sheet The protective film is peeled off from the resin sheet with the protective film obtained in Test Example 1, and a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) is used. , The resin composition layer was laminated on both sides of the inner layer circuit board so as to be in contact with the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of Resin Composition Layer The inner layer circuit board on which the resin sheet is laminated is heat-cured for 30 minutes after being placed in an oven at 100 ° C. and then transferred to an oven at 180 ° C. for 30 minutes to provide an insulating layer. Was formed, and the release PET was peeled off.

(4) Roughing treatment The inner layer circuit board on which the insulating layer was formed was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.
Wet desmear treatment:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP" , Aqueous solution of potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", aqueous sulfuric acid solution) After soaking at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes. This was designated as "roughened substrate A".

(5) Conductor layer formation (5-1) Electroless plating In order to form a conductor layer on the surface of the roughened substrate A that has been roughened, a plating step including the following steps 1 to 6 (manufactured by Atotech Japan Co., Ltd.) The conductor layer was formed by performing a copper plating step) using the chemical solution of.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer and charge adjustment)
The surface of the roughened substrate A was washed with a cleaning cleaner security 902 (trade name) at 60 ° C. for 5 minutes.
2. Soft etching (cleaning inside the via hole)
The surface of the roughened substrate A was treated with an aqueous solution of sodium sulfate-acidic peroxodisulfate at 30 ° C. for 1 minute.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
The surface of the roughened substrate A was prepared by Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Add activator (give Pd to the surface of the insulating layer)
The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (Reduction of Pd applied to the insulating layer)
The surface of the roughened substrate A was subjected to Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
6. Electroless copper plating (Cu is deposited on the surface of the insulating layer (Pd surface))
A mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name). The surface of A was treated at 35 ° C. for 20 minutes to form an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electrolytic plating Next, an electrolytic copper plating step was performed under the condition that the via hole was filled with copper using a chemical solution manufactured by Atotech Japan. After that, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm conducted to the lower layer conductor and a circular conductor pattern having a diameter of 10 mm not connected to the lower layer conductor were used to cover the surface of the insulating layer with a diameter of 10 μm. A conductor layer having a land and a conductor pattern in thickness was formed. Next, the annealing treatment was performed at 200 ° C. for 90 minutes. This substrate was designated as "evaluation substrate A".

(6) Evaluation of Insulation Reliability of Insulation Layer The circular conductor side with a diameter of 10 mm of the evaluation substrate A is used as a + electrode, and the lattice circuit conductor (copper) side of the inner layer circuit board connected to the land with a diameter of 1 mm is used as a-electrode. Using an advanced accelerated life tester (ETAC "PM422"), the insulation resistance value when 100 hours have passed under the conditions of 110 ° C., 85% relative humidity, and 20V DC voltage application is measured by an electrochemical migration tester (Electrochemical migration tester). It was measured with "ECM-100" manufactured by J-RAS). This measurement is performed 6 times, and if the resistance value of all 6 test pieces is 1.00 × 10 ⁸ Ω or more, it is “○”, and if even one ^{is less than 1.00 × 10 8} Ω, it is “×”. The evaluation results and insulation resistance values are shown in the table below. The insulation resistance values shown in Table 1 below are the minimum insulation resistance values of the six test pieces.

Table 1 below shows the amounts of non-volatile components used in the resin compositions of Examples and Comparative Examples, the measurement results of Test Examples, the evaluation results, and the like.

A resin composition containing (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin, wherein the component (A) contains (A-1) a siloxane skeleton-containing epoxy resin. By using (B), a cured product having excellent flexibility and excellent insulation reliability can be suppressed in tackiness even if the content of the inorganic filler is as low as 40% by mass or less. It turns out that you can get it.

Claims (19)

A resin composition containing (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin.
The component (A) contains (A-1) a siloxane skeleton-containing epoxy resin.
A resin composition in which the content of the component (B) is 40% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (A-1) is a cyclic siloxane skeleton-containing epoxy resin. The component (A-1) is the formula (A1) :.

[In the formula, R ¹ independently represents an epoxyalkyl group; R ² is an independently substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or substituted or unsubstituted. Indicates an aryl group; R ³ and R ⁴ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R ³ and R respectively. ⁴ together indicate one —O— and bind to each other to form a cyclic siloxane skeleton; s represents an integer greater than or equal to 1. ], The resin composition according to claim 1 or 2. The resin composition according to any one of claims 1 to 3, wherein the molecular weight of the component (A-1) is 800 or less. The epoxy equivalent of the component (A-1) is 150 g / eq. ~ 250 g / eq. The resin composition according to any one of claims 1 to 4. The resin composition according to any one of claims 1 to 5, wherein the content of the component (A-1) is 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 6, wherein the content of the component (A-1) is 10% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 7, wherein the average particle size of the component (B) is 1 μm or less. The resin composition according to any one of claims 1 to 8, wherein the component (B) is silica. The resin composition according to any one of claims 1 to 9, wherein the weight average molecular weight of the component (C) is 1,000 or more and 100,000 or less. The resin composition according to any one of claims 1 to 10, wherein the content of the component (C) is 20% 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 11, wherein the content of the component (C) is 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 12, further comprising (D) a curing agent. The resin composition according to claim 13, wherein the component (D) contains an active ester-based curing agent. The resin composition according to any one of claims 1 to 14, which is used for forming an insulating layer of a multilayer flexible substrate. The cured product of the resin composition according to any one of claims 1 to 15. A resin sheet comprising a support and a resin composition layer formed on the resin composition according to any one of claims 1 to 15. A multilayer flexible substrate including an insulating layer formed by curing the resin composition according to any one of claims 1 to 15. A semiconductor device comprising the multilayer flexible substrate according to claim 18.