JP2020147731A - Resin composition - Google Patents

Abstract

To provide a resin composition that makes it possible to obtain a cured product having excellent elasticity as well as excellent alkali resistance.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) an inorganic filler, the (B) component containing (B-1) an active ester curing agent.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing an epoxy resin, a curing agent, a compound having a rotaxane structure, and an inorganic filler.

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 multilayer flexible substrate as a substrate substrate used for semiconductor components. The multilayer flexible substrate can be thinner and lighter than the rigid substrate. Further, since the multilayer flexible substrate is flexible and deformable, it can be bent and mounted.

In particular, recently, there has been a demand for a multilayer flexible substrate having stability after stretching and stress relaxation in addition to flexibility applicable to elastic devices and the like. As the flexible material, for example, polyethylene resin, urethane resin, silicone resin and the like are known, but polyethylene resin has poor resilience after stretching, and urethane resin and silicone resin have poor stress relaxation property. On the other hand, the epoxy resin is generally inferior in flexibility, but by containing rotaxanes, the flexibility can be improved, and a material having excellent flexibility, resilience and stress relaxation properties can be obtained. It is known that it can be done (Patent Document 1).

Special Table 2016-534164

However, when manufacturing a multilayer flexible substrate, generally, before forming a conductor layer, a strong alkaline swelling liquid, an oxidizing agent, or the like is used to roughen the insulating layer made of a cured resin product. However, since the cured epoxy resin containing rotaxans tends to have low alkali resistance, an insulating layer that can sufficiently withstand the roughening treatment cannot be obtained.

Therefore, an object of the present invention is to provide a resin composition capable of obtaining a cured product having not only excellent elasticity but also excellent alkali resistance.

As a result of diligent studies to solve the above problems, the present inventor has added (B-1) active ester in addition to (A) epoxy resin, (C) compound having a rotaxane structure, and (D) inorganic filler. We have found that by using a resin composition containing a system curing agent, a cured product having not only excellent elasticity but also excellent alkali resistance can be obtained, and the present invention has been completed.
That is, the present invention includes the following.

[1] Containing (A) epoxy resin, (B) curing agent, (C) compound having a rotaxane structure, and (D) inorganic filler, component (B) is (B-1) active ester-based curing agent. Resin composition containing.
[2] The resin composition according to the above [1], wherein the component (C) is polyrotaxane.
[3] The above-mentioned [1] or [2], wherein the content of the component (C) is 0.1% by mass or more and 10% by mass or less when the non-volatile component of the resin composition is 100% by mass. Resin composition.
[4] The resin composition according to any one of the above [1] to [3], wherein the component (C) is in the form of particles.
[5] The resin composition according to the above [4], wherein the average particle size of the component (C) is 100 nm or more and 20,000 nm or less.
[6] The resin composition according to any one of the above [1] to [5], wherein the component (C) contains a cyclic molecule containing cyclodextrins.
[7] The resin composition according to any one of the above [1] to [6], wherein the component (C) contains a shaft molecule containing a polyethylene glycol chain.
[8] The resin composition according to any one of [1] to [7] above, wherein the weight average molecular weight of the shaft molecule in the component (C) is 3,000 or more and 100,000 or less.
[9] The amount of cyclic molecules included in the component (C) is 10% or more and 90% or less, where 100% is the maximum amount of cyclic molecules included in one axis molecule. [1] The resin composition according to any one of [8].
[10] The resin composition according to any one of [1] to [9] above, wherein the content of the component (D) is 50% by mass or more when the non-volatile component of the resin composition is 100% by mass. ..
[11] The resin composition according to any one of [1] to [10] above, wherein the component (B) further contains (B-2) an isocyanate-based curing agent.
[12] A cured product of the resin composition according to any one of the above [1] to [11].
[13] 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 [11].
[14] An insulating layer formed by curing the resin composition according to any one of [1] to [11] above, and a conductive polymer layer containing a conductive polymer formed on the insulating layer. Including laminated sheets.
[15] The laminated sheet according to the above [14], further comprising a metal layer made of a metal formed on a conductive polymer layer.
[16] A multilayer flexible substrate including the laminated sheet according to the above [14] or [15].
[17] A semiconductor device including the multilayer flexible substrate according to the above [16].

According to the resin composition of the present invention, a cured product having excellent elasticity and alkali resistance can be obtained.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can 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 contains (B-1) an active ester-based curing agent in addition to (A) an epoxy resin, (C) a compound having a rotaxane structure, and (D) an inorganic filler (B) a curing agent. Contains. By using such a resin composition, a cured product having excellent elasticity and alkali resistance can be obtained.

Further, the resin composition of the present invention further contains an arbitrary component in addition to (A) epoxy resin, (B) curing agent, (C) compound having a rotaxane structure, and (D) inorganic filler. May be good. Optional components include, for example, (E) curing accelerators, (F) other additives, and (G) organic solvents.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin.

Examples of the epoxy resin (A) include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type. Epoxy resin, 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 butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include a dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. Of these, glycidylamine type epoxy resin, alicyclic epoxy resin, naphthylene ether type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin (A) preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition includes a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “solid epoxy resin”). It is preferable to include them in combination. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable. As the solid epoxy resin, a solid epoxy resin having three 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. Alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, aliphatic epoxy resin, and epoxy resin having a butadiene structure are preferable, and aliphatic epoxy resin and bisphenol A type epoxy resin. , Bisphenol F type epoxy resin is more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) , "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "CEL2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumitomo Metal Corporation. Type epoxy resin), Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin), DIC's "EXA-850CRP" (bisphenol A type epoxy resin), Mitsubishi Chemical's "YED-216D" (fat) Group epoxy resin), "EP-3950S", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "ELM-100H" (glycidylamine type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd. and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000L ", manufactured by DIC. "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Yakusha; "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (Naftor novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd .; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YL7800" (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. .. 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 the component (A), their quantity ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.01 to 1:20 in terms of mass ratio. The range is preferred, the range of 1: 0.01 to 1:15 is more preferred, and the range of 1: 0.01 to 1:10 is even more preferred. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) moderate adhesiveness is provided, ii) sufficient flexibility is obtained, handleability is improved, and iii. ) Effects such as being able to obtain a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the component (A) is preferably 50 g / eq. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslink density of the cured product of the resin sheet becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

The content of the epoxy resin (A) in the resin composition is not particularly limited, but from the viewpoint of obtaining a cured product showing better mechanical strength and insulation reliability, the non-volatile component in the resin composition is used. When it is 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of the epoxy resin (A) is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less. Particularly preferably, it is 30% by mass or less.

<(B) Hardener>
The resin composition of the present invention contains (B) a curing agent. The (B) curing agent has a function of curing the (A) epoxy resin.

The content of the curing agent (B) in the resin composition is not particularly limited, but the non-volatile component in the resin composition is set to 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. In this case, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more. (B) The upper limit of the content of the curing agent is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. Especially preferably, it is 25% by mass or less.

<(B-1) Active ester-based curing agent>
In the resin composition of the present invention, the (B) curing agent contains (B-1) an active ester-based curing agent. The component (B-1) may be used alone or in combination of two or more.

Examples of the (B-1) active ester-based curing agent include a curing agent having one or more active ester groups in one molecule. Among them, as the (B-1) active ester-based curing agent, one molecule of an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is used. Compounds having two or more of them are preferable. The active ester-based curing agent (B-1) 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, trihydroxybenzophenone, 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.

(B-1) Preferred specific examples of the active ester-based curing agent include 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 phenol. Examples include active ester compounds containing novolak benzoylates. 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 structure composed of phenylene-dicyclopentylene-phenylene.

(B-1) Commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC" as active ester compounds containing a dicyclopentadiene-type diphenol structure. -8000H "," HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "(manufactured by DIC);" EXB9416- "as an active ester compound containing a naphthalene structure. "70BK", "EXB-8000L-65T", "EXB-8150-65T", "EXB-8200-65T" (manufactured by DIC); "DC808" as an active ester compound containing an acetylated product of phenol novolac (Mitsubishi Chemical Co., Ltd.) (Manufactured by); "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac. Examples of the active ester-based curing agent which is a benzoyl compound include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the (B-1) active ester-based curing agent in the resin composition is not particularly limited, but from the viewpoint of obtaining a cured product exhibiting more excellent alkali resistance, a non-volatile component in the resin composition. When is 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. The upper limit of the content of the (B-1) active ester-based curing agent is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably. It is 15% by mass or less, particularly preferably 10% by mass or less.

<(B-2) Isocyanate-based curing agent>
In the resin composition of the present invention, the (B) curing agent is further added to (B-2) in addition to the (B-1) active ester-based curing agent from the viewpoint of obtaining a cured product having more excellent elasticity. It is preferable to contain an isocyanate-based curing agent. The component (B-2) may be used alone or in combination of two or more.

Examples of the (B-2) isocyanate-based curing agent include polyisocyanate compounds having two or more isocyanato groups (-N = C = O). (B-2) As the isocyanate-based curing agent, one type may be used alone, or two or more types may be used in combination.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexanediisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene-2,4-diisocyanate, and toluene-2,6-diisocyanate. Diisocyanates such as 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-bitrylene-4,4'-diisocyanate, paraphenylenedi isocyanate; 4,4 ', 4''-Triisocyanate such as triphenylmethane triisocyanate and the like can be mentioned.

(B-2) Commercially available isocyanate-based curing agents include, for example, "Duranate 24A-90PX" manufactured by Asahi Kasei Corporation; "Sumijour N-3200-90M" manufactured by Sumitomo Bayer Urethane Co., Ltd., and Mitsui Takeda Chemical Co., Ltd. "Takeda D165N-90X"; "Sumijuru N-3300" and "Sumijuru N-3500" manufactured by Sumitomo Bayer Urethane; "Duranate THA-100", "TLA-100" and "TSA-100" manufactured by Asahi Kasei Corporation. , "TPA-100"; "D-500", "D-550", "D-750", "DN-950", "DN-955", "DN-980", "DN" manufactured by DIC. -981 "and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the (B-2) isocyanate-based curing agent in the resin composition is not particularly limited, but from the viewpoint of obtaining a cured product having more excellent elasticity, the non-volatile component in the resin composition is used. When it is 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit of the content of the (B-2) isocyanate-based curing agent is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20. It is mass% or less, particularly preferably 15 mass% or less.

<Any other hardener>
The resin composition of the present invention may further contain any other curing agent as the (B) curing agent.

The arbitrary curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and for example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. Examples thereof include agents and carbodiimide-based curing agents. Any one type of curing agent may be used alone, or two or more types may be used in combination.

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 Nippon Steel & Sumikin Chemical Co., Ltd. "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" manufactured by DIC. , "TD-2090-60M" and the like.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. 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.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" manufactured by Shikoku Chemicals Corporation. 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 disocyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of them are triazined to form a trimer) 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.

The amount ratio of (A) epoxy resin to (B) curing agent is the ratio of [(A) total number of epoxy groups in epoxy resin]: [(B) total number of reactive groups in curing agent]: 1: The range is preferably 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and even more preferably 1: 0.4 to 1: 1.2. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of non-volatile component masses of each epoxy resin divided by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the curing agent is The value obtained by dividing the non-volatile component mass of each curing agent by the reaction group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the obtained cured product is further improved.

<(C) Compound having rotaxane structure>
The resin composition of the present invention contains (C) a compound having a rotaxane structure.

The rotaxane structure is a structure having a cyclic molecule, a linear axial molecule that is included so as to penetrate the cyclic molecule, and a blocking group that blocks the end of the axial molecule so that the cyclic molecule does not come off.

The component (C) is not particularly limited as long as it has a rotaxane structure, but it is preferably a polyrotaxane having at least one of a cyclic molecule and an axial molecule, and more preferably a polyrotaxane having a plurality of cyclic molecules. preferable. The number of cyclic molecules (inclusion amount) in polyrotaxane is not particularly limited as long as the number of cyclic molecules is within the range of two or more, but for example, in a state where one axial molecule is penetrated by a plurality of cyclic molecules. When the amount of cyclic molecules that are maximally included in one axial molecule (maximum inclusion amount) is 100%, it is preferably 10% or more, more preferably 15% or more, and further preferably 20% or more. It is preferably 90% or less, more preferably 85% or less, and further preferably 80% or less. The amount of inclusion can be determined by the length of the axial molecule and the thickness of the cyclic molecule. For example, when the axis molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount has been experimentally determined (see Macromolecules 1993, 26, 5698-5703).

As the axial molecule in the rotaxane structure, a linear molecule having a molecular weight of 10,000 or more and capable of chemically modifying the terminal with a blocking group can be used. "Linear" means substantially straight, and the shaft molecule may have a branched chain as long as the cyclic molecule through which the shaft molecule penetrates can rotate or move. .. Examples of the shaft molecule include polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid cellulose-based resin, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, and casein. , Gelatin, starch, polyolefin, polyester, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer and other copolymers, acrylic resin, polycarbonate, polyurethane, polyvinyl butyral, polyisobutylene, poly tetrahydrofuran, polyamide, polyimide, polydiene, poly Examples thereof include siloxane, polyurea, polysulfide, polyphosphazene, polyketone, polyphenylene, polyhaloolefin and derivatives thereof. Among these, polyethylene glycol chains are preferably used. These may be mixed in two or more kinds in polyrotaxane.

The length of the axial molecule is not particularly limited as long as the cyclic molecule can be rotated or moved. The length of the shaft molecule can be expressed using the weight average molecular weight. The weight average molecular weight of the shaft molecule is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, preferably 100,000 or less, more preferably 90,000 or less, and further. It is preferably 85,000 or less. The weight average molecular weight of the shaft molecule is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The shaft molecule usually has a structure in which a molecule containing a blocking group is reacted and bonded to the functional group of a molecule having functional groups at both ends. As the functional group, for example, an amide group, a hydroxyl group, a carboxyl group, an acrylic group, a methacryl group, an epoxy group, a vinyl group and the like are preferably mentioned.

The cyclic molecule in the rotaxane structure is a cyclic molecule that can be included in a state in which a shaft molecule is penetrated, and has at least one reactive group (functional group) so as to be able to react with (B) a curing agent. Can be used. A cyclic molecule means a molecule that is substantially cyclic, and "substantially cyclic" means that it includes a molecule that is not completely ring-closed, and one end of the letter "C" and multiple ends are combined. It is a concept that includes those having a spiral structure that does not overlap. Examples of the cyclic molecule include cyclodextrins, crown ethers, cryptands, macrocyclic amines, calixarenes, cyclophanes and the like. Among these, cyclodextrins are preferable. These may be mixed in two or more kinds in polyrotaxane.

Examples of cyclodextrins include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin and glucosylcyclodextrin, derivatives or modified products thereof.

The cyclic molecule preferably contains a reactive group. Examples of the reactive group include a hydroxyl group, a carboxyl group, an acrylic group, a methacryl group, an epoxy group, a vinyl group and the like, and a hydroxyl group is preferable. When the cyclic molecule has a reactive group, the cyclic molecule can be crosslinked with each other or the component (C) and the epoxy resin (A) via a curing agent (B). Further, the reactive group of one cyclic molecule and the reactive group of the other cyclic molecule may be crosslinked. The reaction group may have one type alone or two or more types.

The reactive group does not have to be directly attached to the cyclic molecule. For example, when the cyclic molecule is cyclodextrin, the hydroxyl group existing in the cyclodextrin itself is a reactive group, and when a hydroxypropyl group is added to the hydroxyl group, the hydroxyl group of the hydroxypropyl group is also a reactive group. Furthermore, when ring-opening polymerization of ε-caprolactone is carried out via the hydroxyl group of the hydroxypropyl group and the caprolactone chain is provided, the hydroxyl group located at the opposite end of the polyester moiety in the caprolactone chain is also a reactive group.

The cyclic molecule may have one reactive group per cyclic molecule, or may have two or more reactive groups.

The weight average molecular weight of the cyclic molecule is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, preferably 1,500,000 or less, more preferably 1,400, It is 000 or less, more preferably 1,350,000 or less. The weight average molecular weight of the cyclic molecule is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The blocking group in the rotaxane structure is not particularly limited as long as it has a bulkiness such that the cyclic molecule does not come off. Examples of the blocking group include a cyclodextrin group, an adamantane group, a dinitrophenyl group, a trityl group and the like. Of these, the adamantane group is preferable. These may be contained alone in polyrotaxane, or may be contained in two or more.

(C) The weight average molecular weight of the entire compound having a rotaxane structure is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, and preferably 1,500,000 or less. It is more preferably 1,400,000 or less, still more preferably 1,350,000 or less. (C) The weight average molecular weight of the entire compound having a rotaxane structure is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The hydroxyl value of the compound having a rotaxane structure (C) is preferably 45 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 55 mgKOH / g or more, preferably 120 mgKOH / g or less, and more preferably 115 mgKOH. It is / g or less, more preferably 110 mgKOH / g or less. By setting the hydroxyl value within such a range, the reaction with the reactive groups of the (A) epoxy resin, (B) curing agent, and the other cyclic molecule becomes easier. The hydroxyl value can be measured according to JIS K0070.

The compound having the (C) rotaxane structure may be in a liquid state, but is preferably contained in the resin composition in the form of particles. The particulate component (C) is easily dispersed, and the viscosity of the resin composition can be lowered.

The average particle size of the compound having the (C) rotaxane structure is preferably 100 nm or more, more preferably 500 nm or more, still more preferably 800 nm or more, preferably 50,000 nm or less, more preferably 40,000 nm or less, still more preferably. Is 30,000 nm or less. The compound having the (C) rotaxane structure having such an average particle size is likely to be uniformly dispersed in the resin composition, and the viscosity of the resin composition is likely to decrease. The average particle size can be measured by the same method as the measurement of the average particle size in the inorganic filler (D) described later.

(C) The compound having a rotaxane structure can be synthesized by the methods described in, for example, International Publication No. 01/83566, Japanese Patent Application Laid-Open No. 2005-154675, Japanese Patent No. 4482633 and the like.

(C) As the compound having a rotaxane structure, a commercially available product may be used. As commercially available products, for example, "SH2400B-007", "SH1310P", "SELM Superpolymer A1000" manufactured by Advanced Soft Materials Co., Ltd. can be used. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the compound having the (C) rotaxane structure in the resin composition is not particularly limited, but from the viewpoint of obtaining a cured product having more excellent elasticity, 100 non-volatile components in the resin composition are used. In terms of mass%, it is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit of the content of the compound having the (C) rotaxane structure is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass. % Or less, particularly preferably 38% by mass or less.

<(D) Inorganic filler>
The resin composition of the present invention contains (D) an inorganic filler.

(D) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (D) 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 , Zirconate oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate titnate phosphate and the like. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (D) As the inorganic filler, one kind may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

Usually, the (D) inorganic filler is contained in the resin composition in the form of particles. The average particle size of the inorganic filler (D) is preferably 0.1 μm or more, more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 1.0 μm or more. It is preferably 10 μm or less, more preferably 8.0 μm or less, and particularly preferably 7.0 μm or less. When the average particle size of the inorganic filler (D) is in the above range, the filling property of the inorganic filler (D) in the resin composition is enhanced, and the desired effect of the present invention can be remarkably obtained. Further, since the average particle size of the inorganic filler (D) is in the above range, the surface roughness of the insulating layer can be lowered when the insulating layer is usually formed of a cured product of the resin composition.

(D) The average particle size of the particles of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a laser diffraction / scattering type particle size distribution measuring device can be used to create a particle size distribution of particles on a volume basis, and the average particle size can be measured as a median diameter from the particle size distribution. As the measurement sample, those in which the particles are dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

The specific surface area of the inorganic filler (D) is preferably 1 m ² / g or more, more preferably 5 m ² / g or more, still more preferably 8 m ² / g or more, and particularly preferably 8 m ² / g or more, from the viewpoint of further improving the effect of the present invention. Is 10 m ² / g or more. The upper limit is not particularly limited, but is preferably 50 m ² / g or less, more preferably 20 m ² / g or less, and particularly preferably 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. You can get it.

(D) Examples of the inorganic filler include "ST7030-20" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "MSS-6" and "AC-5V" manufactured by Ryumori Co., Ltd .; "SP60-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. , "SP507-05"; Admatex "YC100C", "YA050C", "YA050C-MJE", "YA010C"; Denka "UFP-30", "SFP-130MC", "FB-7SDC", "FB-5SDC", "FB-3SDC"; Tokuyama Corporation "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatex "SC2500SQ", "SO-C4", Examples thereof include "SO-C2", "SO-C1", and "FE9".

The inorganic filler (D) is preferably surface-treated with an appropriate surface treatment agent. By the surface treatment, the moisture resistance and dispersibility of the (D) inorganic filler can be enhanced. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates. Examples include system coupling agents.

Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-aminooctylrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (Phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent) and the like can be mentioned. Of these, a nitrogen atom-containing silane coupling agent is preferable, an aminosilane-based coupling agent containing a phenyl group is more preferable, and N-phenyl-3-aminoalkyltrimethoxysilane is even more preferable. Further, the surface treatment agent may be used alone or in combination of two or more at an arbitrary ratio.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. Carbon content per unit surface area of the inorganic filler (D) is, (D) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, Particularly preferably, it is 0.2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. Is 0.5 mg / m ² or less.

The amount of carbon per unit surface area of the (D) inorganic filler is determined after the surface-treated (D) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter, may be abbreviated as “MEK”)). , Can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the (D) inorganic filler surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the (D) inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

The content of the (D) inorganic filler in the resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass, based on 100% by mass of the non-volatile component in the resin composition. By mass or more, more preferably 20% by mass or more, particularly preferably 25% by mass or more, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, particularly preferably 30% by mass. % Or less. When the content of the inorganic filler (D) is within the above range, the desired effect of the present invention can be remarkably obtained.

<(E) Hardening accelerator>
The resin composition may contain (E) a curing accelerator as an arbitrary component. By using a curing accelerator, curing can be accelerated when the resin composition is cured.

Examples of the (E) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and 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 amine-based curing accelerator is more preferable. The curing accelerator may be used alone or in combination of two or more.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,5) -Undecene, 4-pyrrolidinopyridine and the like can be mentioned. Of these, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 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-undecyl imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6 -[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')] -Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, imidazole compounds and epoxy resins Adduct body can be mentioned. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation; "2E4MZ" manufactured by Shikoku Chemicals Corporation; and the like.

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. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferable.

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.

The content of the (E) curing accelerator in the resin composition is not particularly limited as long as the effects of the present invention are exhibited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 10% by mass. Hereinafter, it is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of the (E) curing accelerator is not particularly limited, but is, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, and the like. Can be.

<(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 phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and the like. Thermoplastic resins such as polyether 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, Colorants such as carbon black; polymerization retardants such as hydroquinone, catechol, pyrogallol, phenothiazine; leveling agents such as siloxane; thickeners such as Benton and montmorillonite; silicone-based defoaming agents, acrylic defoaming agents, fluorine-based defrosting agents Foaming agents, vinyl resin-based defoaming agents, defoaming agents; organic fillers such as polyethylene particles, polypropylene particles, polystyrene particles, polyphenylene ether particles, silicone particles, tetrafluoroethylene particles; ultraviolet absorption of benzotriazole-based ultraviolet absorbers, etc. Agents; Adhesive improvers such as ureasilane; Adhesive improvers such as silane coupling agents, triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, triazine-based adhesion-imparting agents; Hindered phenol-based antioxidants , Antioxidants such as hindered amine antioxidants; Fluorescent whitening agents such as stillben derivatives; Phosphorus flame retardants (eg phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (eg sulfuric acid) Examples thereof include flame retardants such as melamine), halogen-based flame retardants, and inorganic flame retardants (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 organic solvent (G), known ones can be appropriately used as long as at least a part of the non-volatile component can be dissolved, 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-based solvents such as butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol-based 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, 2-hydroxyisobutyric acid Ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N, N-dimethylformamide, Amid solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxide solvents such as dimethyl sulfoxide; Nitrile solvents such as acetonitrile and propionitrile; hexane, cyclopentane, cyclohexane, methylcyclohexane and the like. An aliphatic hydrocarbon solvent; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene can be mentioned. The organic solvent may be used alone or in combination of two or more in any ratio. The content of the organic solvent (G) can be appropriately set by those skilled in the art.

<Manufacturing method of resin composition>
In one embodiment, the resin composition of the present invention comprises, for example, (A) epoxy resin, (B) curing agent, (C) compound having a rotaxane structure, (D) inorganic filler, in any reaction vessel. Add (E) curing accelerator, (F) other additives as needed, and (G) organic solvent as needed in any order and / or part or all at the same time and mix. Can be manufactured by 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) an epoxy resin, (C) a compound having a rotaxane structure, and (D) an inorganic filler, and (B-1) an active ester-based curing agent, it expands and contracts. A cured product having not only excellent properties but also excellent alkali resistance can be obtained.

Since the resin composition of the present invention contains (C) a compound having a rotaxane structure, for example, a cured product of the dumbbell-shaped No. 1 resin composition of the present invention measured in accordance with Japanese Industrial Standards (JIS K7127). The elongation at break (%) at room temperature (23 ° C.) can be preferably 30% or more, more preferably 35% or more, still more preferably 40% or more, and particularly preferably 45% or more.

Since the resin composition of the present invention contains (C) a compound having a rotaxane structure, for example, a cured product of the dumbbell-shaped No. 1 resin composition of the present invention has a breaking elongation at room temperature (23 ° C.). When a tensile test is performed until the elongation reaches 90%, the length in the tensile direction of the cured product before the test is "L1", and the length in the tensile direction of the cured product 30 minutes after the test is "L2". The expansion / contraction ratio (%) calculated from the following formula can be preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and particularly preferably 80% or more.
Stretch rate (%) = {1- (L2-L1) / (L1)} x 100

Since the resin composition of the present invention contains (B-1) an active ester-based curing agent, for example, 2N of a cured product of the resin composition of the present invention having a rectangular parallelepiped shape with an aspect ratio of 50 mm: 50 mm: 50 μm. The weight loss rate (%) of the cured product after being immersed in an aqueous potassium hydroxide solution at room temperature (23 ° C.) for 1 hour is preferably 2% or less, more preferably 1.5% or less, still more preferably 1.2%. Below, it can be particularly preferably 1% or less.

<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 foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter 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 surface of the support to be joined to the resin composition layer may be matted, corona-treated, or antistatic-treated.

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

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 the adhesion of dust and the like to the surface of the resin composition layer and scratches.

The resin sheet is prepared by applying a resin varnish prepared by dissolving the resin composition as it is or by dissolving the resin composition in an organic solvent, for example, on a support using a die coater or the like, and further drying the resin composition layer. It can be manufactured by forming it.

Examples of the organic solvent include those similar to those mentioned in the above description of the organic solvent (G). 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. ..

In one embodiment, the laminated sheet comprises an insulating layer formed by curing the resin composition and a conductive polymer layer containing a conductive polymer formed on the insulating layer by the method described below. Further, a metal layer made of a metal formed by electrolytic plating or the like may be provided on the conductive polymer layer.

The laminated sheet is a sheet used by bending so that one of the surfaces 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 arbitrary 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, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel-chromium alloy, copper from the viewpoints of versatility, cost, ease of patterning, etc. -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. 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, for example,
(I) Step of laminating the first resin composition layer on the sheet support base material,
(II) A step of curing the first resin composition layer to form a first insulating layer,
(III) The process of drilling holes in the first insulating layer,
(IV) Step of roughening the first insulating layer,
(V) Step of forming a conductor layer on the 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,
May include. In addition, steps (I) and (III) may not be performed. 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 laminating of the sheet supporting 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 supporting 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 appropriately referred to as “heat-bonding member”) include 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 thermosetting 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.

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.

The first resin composition layer may be preheated at a temperature lower than the curing temperature before the first resin composition layer is thermosetting. 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 of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid 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 permanganic acid 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. 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. The plating method may be, for example, a semi-additive method or a full-additive method, but as a preferable example, a conductive polymer layer is formed on the first insulating layer, and if necessary, plating is performed by electrolytic plating. Then, a method of forming a conductor layer having a desired wiring pattern can be mentioned.

Hereinafter, an example of a method for forming the conductive polymer layer will be shown. First, a conductive coating liquid containing a conductive polymer is brought into contact with a portion of the surface of the first insulating layer on which the conductor layer should be formed, and the conductive polymer is adhered to form the conductive polymer layer, and then, if necessary. Accordingly, a metal layer is formed on the conductive polymer layer by electrolytic plating to form a conductor layer having a desired wiring pattern.

As the conductive polymer, known conductive polymers can be widely used, for example, polypyrroles, polyindoles, polycarbazoles, polythiophenes, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, etc. Examples thereof include polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaftens, polythiazyl and copolymers combining them, and polyanilines and polypyrroles are preferable. Further, the conductive coating liquid may contain known thermosetting resins, photocurable resins, thermoplastic resins and the like as long as the conductivity is not impaired. Further, the conductive coating liquid may contain a surfactant for dispersing the conductive polymer as colloidal particles in the liquid. When the conductive polymer is dispersed as colloidal particles, the size of the colloidal particles is, for example, 0.001 to 1 μm. Examples of the solvent or dispersion medium of the conductive polymer include water; alcohol such as methanol and ethanol; and a mixed solution of water and alcohol.

Commercially available thermosetting conductive coating liquids include "S-983", "S-495", "S-948", and "R-801" manufactured by Chukyo Oil & Fat Co., Ltd .; "Seprugida OC-AE" manufactured by Shin-Etsu Polymer Co., Ltd. , "Seprugida AS-H03Q"; "Beam Set E-2" manufactured by Arakawa Chemical Co., Ltd. and the like. Commercially available photo-curable conductive coating liquids include "R-986" and "UVS-542" manufactured by Chukyo Oil & Fat Co., Ltd .; "Seprugida OC-X", "Seprugida OC-U" and "Seprugida OC" manufactured by Shin-Etsu Polymer Co., Ltd. -X ";" Beam set 1700 CP "," Beam set 1800 CP "," Beam set E-1 "manufactured by Arakawa 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 type. Further, the conductive coating liquid may be used by further mixing a commercially available curing agent or other additives.

As a method for forming the conductive polymer layer, a conductive coating liquid is used, for example, flexographic printing method, screen printing method, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating. It is applied on the first insulating layer by a wet coating method such as a method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, or an inkjet method, dried as necessary, and further heated as necessary. It is subjected to a curing treatment or a photocuring treatment to form a conductive polymer layer. The thickness of the conductive polymer layer is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 5 μm, still more preferably 0.1 μm to 2 μm, and particularly preferably 0.2 μm to 1 μm. After forming the conductive polymer layer, if necessary, wash with water, an aqueous sulfuric acid solution, or the like. Then, if necessary, electrolytic plating is performed by a known method using an acidic plating bath such as an electrolytic copper sulfate plating bath to form a metal layer made of metal. By going through the above process, a conductor layer made of a conductive polymer layer or a conductor layer made of a conductive polymer layer and a metal layer can be formed on the first insulating layer.

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 sheet can be performed by the same method 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, (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, as necessary. 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 of 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 sheets are laminated and cured by the steps (VI) to (VII), and if necessary, the insulating layer is drilled and insulated by the steps (VIII) to (X). The laminated sheet may be manufactured by repeatedly carrying out the roughening treatment of the layer and the formation of the conductor layer on the insulating layer. 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 the multilayer flexible substrate may further include any 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 stored in the housing of the semiconductor device by being bent 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 electric 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. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

<Example 1>
Bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ZX1059", 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g / eq.), 10 parts, naphthylene ether type epoxy resin (DIC) , "HP6000", epoxy equivalent 213 g / eq.), Fused spherical silica (manufactured by Admatex, "SC2500SQ", average particle size 0.5 μm, specific surface area 11.2 m ² / g, surface treatment agent (Shinetsu) 20 parts of "KBM573" manufactured by Kagaku Kogyo Co., Ltd., surface-treated with N-phenyl-3-aminopropyltrimethoxysilane), active ester-based curing agent (manufactured by DIC, "EXB-8000L-65M", active group) Equivalent about 220 g / eq., 6 parts of MEK solution with 65% by mass of non-volatile component), polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., 50% solution of methyl ethyl ketone of "SH1310P", shaft molecule contains polyethylene glycol chain, cyclic molecule Mix 50 parts of (including cyclodextrins), 10 parts of polyisocyanate resin (manufactured by DIC, "DN950"), and 0.2 part of amine-based curing accelerator ("DMAP", 4-dimethylaminopyridine), and mix. The resin composition was prepared by uniformly dispersing in.

<Example 2>
A resin composition was prepared in the same manner as in Example 1 except that the amount of fused spherical silica (“SC2500SQ” manufactured by Admatex) was changed from 20 parts to 25 parts.

<Example 3>
10 parts of naphthylene ether type epoxy resin (DIC, "HP6000", epoxy equivalent 213 g / eq.), Bisphenol AF type epoxy resin (Mitsubishi Chemical Co., Ltd., "YX7760", epoxy equivalent about 238 g / eq.) 10 A resin composition was prepared in the same manner as in Example 1 except that the parts were changed to parts.

<Comparative example 1>
6 parts of an active ester-based curing agent (“EXB-8000L-65M” manufactured by DIC, MEK solution having an active group equivalent of about 220 g / eq., 65% by mass of a non-volatile component), and a triazine-containing phenol novolac resin (manufactured by DIC, “ The resin composition was prepared in the same manner as in Example 1 except that it was changed to 10 parts of "LA-7554", a hydroxyl group equivalent of 125 g / eq., A nitrogen content of about 12% by weight, and a solid content of 60% by weight (MEK solution). did.

<Comparative example 2>
10 parts of polyisocyanate resin (DIC, "DN950") was not used, polyrotaxan (advanced soft materials, "SH1310P", 40% solution of methyl ethyl ketone, shaft molecule contained polyethylene glycol chain, cyclic The molecule contains cyclodextrins.) Resin in the same manner as in Example 1 except that 50 parts were changed to 116.7 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., solid content 30% by mass). The composition was prepared.

<Test Example 1: Measurement of elongation at break>
The resin compositions of each Example and Comparative Example were placed on a mold release-treated surface of a release PET film (Lintec Corporation "501010", thickness 38 μm, 240 mm square), and the thickness of the resin composition layer after drying was 50 μm. It 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.

The obtained resin sheet was cured under the curing conditions of 190 ° C. for 90 minutes, and the release PET film was peeled off to obtain a cured product sample.

The obtained cured product sample was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece is subjected to a tensile test of a cured product for evaluation using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with the Japanese Industrial Standards (JIS K7127), and the elongation at break at 23 ° C. is determined. It was measured. This operation was performed three times, the average value was calculated, and the elongation at break (%) was used.

<Test Example 2: Measurement of expansion / contraction rate>
The cured product sample obtained in Test Example 1 was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The length of the test piece in the longitudinal direction is defined as "L1". When a tensile test of the test piece was performed at 23 ° C. using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) and the elongation reached 90% of the elongation at break measured and calculated in Test Example 1. The tensile test was stopped at, and the length of the test piece was measured 30 minutes after the test piece was collected from the device. The length of the test piece in the longitudinal direction after the tensile test is defined as "L2". The expansion / contraction rate (%) was calculated by the following formula.
Stretch rate (%) = {1- (L2-L1) / (L1)} x 100

Those having a stretch ratio of 80% or more were evaluated as "◯", and those having a stretch ratio of less than 80% were evaluated as "x".

<Test Example 3: Measurement of roughening treatment resistance>
A 5 cm × 5 cm sample A was cut out from the cured product sample obtained in Test Example 1, dried at 130 ° C. for 15 minutes, and the mass immediately after the drying was measured. This is used as a sample, and the mass of the sample is defined as "X1". The sample was immersed in a 2N aqueous potassium hydroxide solution at 23 ° C. for 1 hour to obtain a roughened sample. The roughened sample was washed with water and dried at 130 ° C. for 30 minutes, and the mass immediately after that was measured. The mass of the roughened sample immediately after drying is defined as "X2". The weight loss rate (%) due to the roughening treatment of the cured product of the resin composition was determined by the following formula.
Weight loss rate (%) = {(X1-X2) / (X1)} x 100

Those having a weight loss rate of 1% or less were evaluated as "○", and those having a weight loss rate of more than 1% were evaluated as "x".

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

By using a resin composition containing (B-1) an active ester-based curing agent in addition to (A) an epoxy resin, (C) a compound having a rotaxane structure, and (D) an inorganic filler, the elasticity is increased. It was found that a cured product that is not only excellent but also excellent in alkali resistance can be obtained.

<Example 4: Formation of conductor layer>
(1) Adjustment of conductive coating liquid After diluting 10 parts of methanol by adding 10 parts of methanol to 10 parts of conductive polymer (conductive coating "R-801", manufactured by Chukyo Oil & Fat Co., Ltd.), curing agent A (manufactured by Chukyo Oil & Fat Co., Ltd., "P-" 0.5 parts of "795% diluted methanol product" and 2 parts of curing agent B (manufactured by Chukyo Oil & Fat Co., Ltd., 0.95% diluted methanol product of "Q-113") were mixed and uniformly dispersed with a mixer. Then, a conductive coating liquid was prepared.

(2) Preparation of Conductive Polymer Layer The cured product sample obtained in Test Example 1 was uniformly coated with a die coater so that the thickness after drying was 0.5 μm, and at 120 ° C. (average 100 ° C.). It was dried for 10 minutes to form a conductive polymer layer.

(3) Electrolytic Plating Step Next, electrolytic copper plating was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. to form a conductor layer.

Claims (17)

A resin containing (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) an inorganic filler, and (B) a component containing (B-1) an active ester-based curing agent. Composition. The resin composition according to claim 1, wherein the component (C) is polyrotaxane. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 0.1% by mass or more and 10% by mass or less when the non-volatile component of the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein the component (C) is in the form of particles. The resin composition according to claim 4, wherein the average particle size of the component (C) is 100 nm or more and 20,000 nm or less. The resin composition according to any one of claims 1 to 5, wherein the component (C) contains a cyclic molecule containing cyclodextrins. The resin composition according to any one of claims 1 to 6, wherein the component (C) contains a shaft molecule containing a polyethylene glycol chain. The resin composition according to any one of claims 1 to 7, wherein the weight average molecular weight of the shaft molecule in the component (C) is 3,000 or more and 100,000 or less. Any of claims 1 to 8, wherein the inclusion amount of the cyclic molecule in the component (C) is 10% or more and 90% or less, assuming that the maximum inclusion amount of the cyclic molecule in one shaft molecule is 100%. The resin composition according to item 1. The resin composition according to any one of claims 1 to 9, wherein the content of the component (D) is 50% by mass or more when the non-volatile component of the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 10, wherein the component (B) further contains (B-2) an isocyanate-based curing agent. The cured product of the resin composition according to any one of claims 1 to 11. 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 claims 1 to 11. Lamination including an insulating layer formed by curing the resin composition according to any one of claims 1 to 11 and a conductive polymer layer containing a conductive polymer formed on the insulating layer. Sheet. The laminated sheet according to claim 14, further comprising a metal layer made of a metal formed on a conductive polymer layer. A multilayer flexible substrate comprising the laminated sheet according to claim 14 or 15. A semiconductor device comprising the multilayer flexible substrate according to claim 16.