WO2016017368A1 - Resinous sheet, and structure and wiring board each including same - Google Patents

Abstract

Provided are: a resinous sheet which includes a fibrous base having improved mechanical strength and which shows improved adhesion to substrates; and a structure and a wiring board which include the resinous sheet. The resinous sheet comprises a fibrous base (11), a binder (2) with which the fibers (1) in the fibrous base (11) are bonded to one another, and a resin (3) which is in contact with the fibrous base (11) and the binder (2), wherein the binder (2) has a higher storage modulus than the resin (3). The structure is obtained by tenaciously adhering the resinous sheet to a substrate. The wiring board includes this structure.

Description

Resin-containing sheet, and structure and wiring board using the same

The present invention relates to a resin-containing sheet having excellent mechanical strength, elastic modulus and adhesion, and suitable for a wiring board for electronic equipment, and a structure and a wiring board using the same.

As a wiring board for electronic devices, generally, a prepreg (a semi-cured resin insulation layer) obtained by impregnating a substrate made of glass fiber, aramid fiber, cellulose fiber or the like with a resin such as epoxy, A circuit in which a circuit is formed by an etching method in close contact with a metal foil is used. The wiring board is provided with a solder resist in order to prevent the solder from flowing out during component mounting. Wiring board materials such as prepreg and solder resist need to be in close contact with heating and pressurization so that they adhere to the surface of the metal foil or the circuit board on which the circuit is formed, and the adhesion at that time is important. Become. In addition, the wiring board is desired to have high strength (high elastic modulus) in order to improve mounting reliability. Similarly, the prepreg and solder resist, which are constituent members thereof, are also expected to have high elastic modulus. It has been.

As a conventional technique related to a wiring board material, for example, in Patent Document 1, resin layers having different strengths (elastic modulus) are provided on both surfaces of a core layer in order to obtain both functions of insulation reliability and stress relaxation with wiring. A prepreg is described. However, this technique provides different layers of the resin composition on both sides of the core layer, and there is no disclosure that it is useful for adhesion. Patent Document 2 describes a prepreg having a predetermined elastic modulus. This technique is intended to temporarily fix the prepreg sheet and the circuit board, and the elastic modulus is controlled by the composition.

Furthermore, Patent Document 3 discloses a technique using two types of resin compositions in a prepreg. In this prepreg, two kinds of resin compositions are unevenly distributed so that the elastic modulus increases toward the surface side. Furthermore, Patent Document 4 describes a technique in which an adhesive layer is provided on the surface of a prepreg in order to improve adhesion with a metal foil.

JP 2008-088280 A JP 2006-179716 A JP 2010-095557 A JP 2004-168943 A

However, the conventional prepreg described above cannot have sufficient mechanical strength and adhesion.

Therefore, an object of the present invention is to provide a resin-containing sheet that has improved mechanical strength and improved adhesion to a substrate, and a structure and a wiring board using the resin-containing sheet.

As a result of intensive studies to solve the above problems, the present inventors have found the following.
That is, in general, in woven fabrics and nonwoven fabrics made of various fibrous materials, fibers form an aggregate by entanglement and interaction. Therefore, as shown in FIG. 2A, when a tension T is applied in one direction to the aggregate of fibers 21, the fibers 21 slip at the contact point P, and the fibers 21 are aligned in the direction of the arrow D. When pulled apart, the aggregate will fray and eventually break. In this respect, in the case of a woven fabric, the strength against tension in the fiber direction is somewhat high, but the strength against tension in a direction different from the fiber direction (oblique direction) is low. Further, in the case of a nonwoven fabric, the strength against pulling is low in any direction.

As described above, since a resin-containing sheet such as a prepreg made of a woven fabric such as glass cloth or a nonwoven fabric made of aramid fibers and a resin is used for the wiring board, in order to ensure the strength of the wiring board. In the fiber assembly, it is important to prevent slippage between the fibers. On the other hand, as described above, the resin-containing sheet is also required to have good adhesion to the metal foil surface and the wiring board surface.

As a result of the above studies, the present inventors have found that the mechanical strength and adhesion can be balanced by adopting the following configuration.
That is, the resin-containing sheet of the present invention has a fiber base material, a fixing agent that fixes fibers in the fiber base material, and a resin that contacts the fiber base material and the fixing agent, and the fixing agent. The storage elastic modulus of the resin is higher than the storage elastic modulus of the resin.

In the present invention, the glass transition temperature of the fixing agent is preferably higher than the glass transition temperature or softening temperature of the resin. The resin-containing sheet of the present invention can be obtained by fixing the fibers of the fiber base material with the fixing agent composition and then impregnating the fixed fiber base material with the resin composition. In this case, the viscosity of the fixing agent composition is preferably 1 Pa · s or less. Moreover, in the resin containing sheet | seat of this invention, it is preferable that the said fiber base material contains a woven fabric or a nonwoven fabric.

The structure of the present invention is obtained by bringing the resin-containing sheet of the present invention into close contact with a substrate.

Furthermore, the wiring board of the present invention is characterized by having the structure of the present invention.

According to the present invention, it is possible to obtain a resin-containing sheet having improved mechanical strength and improved adhesion to the substrate. That is, in the present invention, the storage elastic modulus of the fixing agent for fixing the fibers in the fiber base material is higher than the storage elastic modulus of the resin in contact with the fiber base material and the fixing agent. The present inventors have found a material condition for obtaining a resin-containing sheet having improved elasticity and improved adhesion. This is because the resin insulating material for wiring boards is required to have high strength. For example, when a high elastic modulus material such as polyimide is used, the adhesion to a metal foil or the like deteriorates. This solves the problem of adhesion while realizing a high elastic modulus.

It is explanatory drawing which shows the structure of the resin containing sheet | seat of this invention as a model. When tension | tensile_strength T is applied to the fiber assembly in one direction, it is explanatory drawing which shows the behavior of the case where the fibers are not adhering (a) and the case where it is adhering (b). .

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In FIG. 1, explanatory drawing which shows the structure of the resin containing sheet | seat of this invention is shown. The resin-containing sheet of the present invention is a sheet-like body mainly formed from a fiber component and a resin component. As shown in the figure, the fiber base material 11 and the fixing agent 2 for fixing the fibers 1 in the fiber base material 11 to each other. And a resin 3 in contact with the fiber base 11 and the fixing agent 2. In addition, the code | symbol S in a figure shows the space in which neither the fixing agent 2 nor the resin 3 is impregnated in the fiber base material 11. FIG. In the resin-containing sheet of the present invention, it can be said that the fibers 1 constituting the fiber base material 11, the fixing agent 2, and the resin 3 form one layer as a whole. In the resin-containing sheet of the present invention, it is important that the storage elastic modulus of the fixing agent 2 that fixes the fibers 1 is higher than the storage elastic modulus of the resin 3 at any temperature.

That is, as a result of intensive studies, the present inventors have two roles of the resin component contained in the resin-containing sheet. One is that the resin-containing sheet is made to have high strength and high elasticity by suppressing slippage between fibers. It has been found that it is a role as a sticking agent for increasing the rate, and the other is a role of bringing the insulating resin layer and the surface of the metal foil into close contact with each other. From this point of view, the present inventors have further studied, and as a result, the two roles of the resin component contained in the resin-containing sheet are assigned to the fixing agent for ensuring high strength and to the resin for ensuring adhesion, respectively. Thus, it has been found that by defining the relationship between the storage elastic modulus of the fixing agent and the resin, both of these performances can be secured satisfactorily. As described above, there has been no known technique that achieves both high elastic modulus and good adhesion by dividing the role of the resin component into two.

As shown in FIG. 2B, the present invention is conceptually explained. When the contact point P of the fiber 1 included in the fiber base material 11 is fixed by the fixing agent 2, a tension T is applied in one direction. However, since slip does not occur at the contact point P, the fiber base material 11 can be increased in strength and elasticity. Furthermore, by impregnating the resin 3 so as to be in contact with the fiber base material 11 and the fixing agent 2, good adhesiveness as a resin-containing sheet can be obtained. Therefore, according to the resin-containing sheet of the present invention, it is possible to ensure the adhesiveness to the substrate or the like with the resin 3 while ensuring the high elastic modulus required for the fiber base material 11 with the resin 3, and simply polyimide It became possible to obtain a resin-containing sheet having both high strength and good adhesion, which could not be obtained by using a high elastic modulus material such as.

[Fiber base]
The fiber base material 11 according to the present invention is composed of an assembly of fibers 1. The fiber 1 is not particularly limited as long as an aggregate can be formed and a woven fabric or a nonwoven fabric can be produced, and natural fibers or chemical fibers can be mainly used. Among the specific examples of the fiber 1, natural fibers include glass fibers, cellulose fibers, rock fibers, metal fibers, carbon fibers, rock wool, etc., and chemical fibers include aramid, nylon, vinylon, vinylidene, polyester, Polyolefin (polyethylene terephthalate, modified polyethylene terephthalate, polyethylene, polypropylene, etc.), polyurethane, acrylic, polyvinyl chloride, polyetheretherketone, polyamideimide, polyphenylene sulfide, polyetherimide, polytetrafluoroethylene, acetate, triacetate, promix, Examples include rayon, cupra, polynosic rayon, lyocell, and tencel. One of these can be used alone, or two or more can be used in combination. The production method, fiber content (fiber content), fiber diameter, fiber length, mass (basis weight) / density (specific gravity), thickness, and woven structure of the woven fabric are appropriately selected according to the purpose. be able to. Among the above, the fiber substrate 11 is preferably glass fiber, cellulose fiber, or aramid fiber from the viewpoint of affinity with the fixing agent.

In the present invention, in particular, it is preferable to use a woven fabric as the fiber base material 11. By adding the weave, it is possible to obtain a merit capable of increasing the strength even if the fiber originally has a low strength. In the present invention, the fiber base material 11 is not a glass fiber that originally has high strength, but an organic fiber having low strength is used. There is also an advantage that can be made.

[Adhesive composition]
The fixing agent composition for forming the fixing agent 2 may be any one that can adhere to the fibers 1 and fix the fibers 1 to each other, and fixes only the contact portions where the fibers contact each other. Alternatively, the whole fiber 1 may be covered and fixed. The amount of the fixing agent composition used may be an amount that can fix the fibers 1 to each other and does not adversely affect the adhesion. In the assembly in which the fibers 1 are fixed by the fixing agent 2, It is preferable that the volume ratio of the fiber 1 to the fixing agent 2 is in the range of 99: 1 to 50:50, particularly in the range of 99: 1 to 60:40, with the solid content excluding the solvent. When the volume ratio between the fiber 1 and the fixing agent 2 is within this range, the fibers 1 are sufficiently fixed to each other by the fixing agent to obtain a desired high strength, and the subsequent impregnation with the resin 3 is favorable. Adhesiveness can be secured, which is preferable. In particular, the amount of the sticking agent 2 used is preferably such an amount that the film thickness of the fiber base material 11 does not substantially change before and after the application of the sticking agent 2. Here, the film thickness does not substantially change means that the change in the film thickness does not include a case where the fiber base 11 is swollen by the solvent component of the fixing agent composition and apparently increases in thickness. It is. Moreover, it is preferable that the fixing agent composition is a liquid when adhering to the fiber, and it may be a liquid that can be used by changing temperature and pressure. In particular, the viscosity of the fixing agent composition measured at 25 ° C. with a rotor speed of 5 rpm in an E-type viscometer is preferably 1 Pa · s or less, for example, 1 to 0.0001 Pa · s. The fixing agent composition can be impregnated to the inside of the aggregate of the fibers 1, and the fibers can be more reliably fixed.

Also, the fixing agent composition that is cured by heat or light is used. The term “curing” as used herein means a chemical change from liquid to solid by heat or light energy. As a fixing agent composition, a usual component can be used according to the use, 1 type can be used individually or in combination of 2 or more types. Examples of conventional components used in the fixing agent composition include a thermosetting resin, a curing agent, a thermosetting catalyst, a photocurable resin, a photopolymerization initiator, a photoacid generator, a photobase generator, and an organic solvent. Specifically, the following can be used.

(Thermosetting resin)
The thermosetting resin may be a resin that is cured by heating and exhibits electrical insulation properties. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M Type epoxy resin, bisphenol P type epoxy resin, bisphenol type epoxy resin such as bisphenol Z type epoxy resin, novolac type epoxy resin such as bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin , Biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, tetraphenylol ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, Enoxy-type epoxy resin, dicyclopentadiene-type epoxy resin, norbornene-type epoxy resin, adamantane-type epoxy resin, fluorene-type epoxy resin, glycidyl methacrylate-copolymerized epoxy resin, copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, epoxy Modified polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4′-diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene Diglycidyl ether of glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, Oil modification modified with glycidyl tris (2-hydroxyethyl) isocyanurate, phenol novolac resin, cresol novolac resin, novolac type phenol resin such as bisphenol A novolac resin, unmodified resole phenol resin, tung oil, linseed oil, walnut oil, etc. Phenol resin such as resole phenol resin such as resole phenol resin, Triazine ring-containing resin such as phenoxy resin, urea resin, melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone resin, benzoxazine Ring-containing resin, norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyazo Chin resins, and polyimide resins. Among these, an epoxy resin or a polyimide resin is particularly preferable because of its excellent reliability as an insulating layer.

As the epoxy resin, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be liquid, and may be solid or semi-solid. Among them, bisphenol A type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin or a mixture thereof is particularly preferable. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the epoxy resin include jER828 manufactured by Mitsubishi Chemical Corporation, but are not limited thereto.

When forming a cured product using an epoxy resin, it is preferable to contain a curing agent in addition to the epoxy resin. Examples of the curing agent include imidazole-based curing agents such as 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), diethylenetriamine, Amine-based curing agents such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, metaxylenediamine, isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, N-aminoethylpiperazine, polyamide, vinylphenol, aralkyl Type phenol resins, phenol phenyl aralkyl resins, phenol biphenyl aralkyl resins, etc., phenolic curing agents, phthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, methyl ester Lahydrophthalic acid, methylhexahydrophthalic acid, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic acid anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexene tetra Known curing agents such as acid anhydride curing agents such as carboxylic acid anhydrides, cyanate ester resins, active ester resins, aliphatic or aromatic primary or secondary amines, polyamide resins, and polymercapto compounds can be used. The compounding amount of the curing agent is preferably 0.1 to 150 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin. By setting the blending amount of the curing agent to 0.1 parts by mass or more, the resin composition can be sufficiently cured, and by setting the blending amount to 150 parts by mass or less, an effect commensurate with the blending amount can be efficiently obtained. Can do.

Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Examples thereof include amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide, and phosphorus compounds such as triphenylphosphine. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used.

As a polyimide resin, what is obtained via a polyamic acid (polyimide precursor) by a synthetic reaction of a generally known aromatic polyvalent carboxylic acid anhydride or derivative thereof and an aromatic diamine, What is marketed as what is called a polyimide varnish of the state by which the polyamic acid composition was melt | dissolved in the organic solvent is mentioned.

Specific examples of the aromatic polycarboxylic acid anhydride include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 ′. -Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3 , 4- Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid Anhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like can be mentioned. These may be used alone or in combination of two or more. Among these, it is particularly preferable to use pyromellitic dianhydride as at least one of the components.

Specific examples of aromatic diamines to be reacted with polyvalent carboxylic acids such as aromatic polycarboxylic anhydrides include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p -Aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) Sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) ( 4-aminophenyl) sulfone, bis (4-a Nophenyl) sulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diamino Diphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1, 1-bis [4- (4-aminophenoxy) phenyl] -ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl ] Ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Minophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-amino Phenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis ( 3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) Bis) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [ 4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) Phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) Benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenylate 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′- Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4 -Aminophenoxy) phenoxy] -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like. These are used individually or in mixture of 2 or more types. Among these, it is particularly preferable to use 4,4'-diaminodiphenyl ether as at least one of the components.

As polyimide varnishes, Rika Coat SN20, Rika Coat PN20, Rika Coat EN20 manufactured by Shin Nippon Rika Co., Ltd., Trenys manufactured by Toray Industries, Inc., U-Varnish manufactured by Ube Industries, Ltd., Optomer manufactured by JSR Corporation, Nissan Chemical Co., Ltd. Examples include SE812 manufactured by Sumitomo Bakelite Co., Ltd. and CRC8000 manufactured by Sumitomo Bakelite Co., Ltd.

The polyamic acid solution obtained by the synthesis reaction or marketed is treated by heating or the like, whereby cyclization (imidization) from the polyamic acid to the polyimide is performed. The polyamic acid can be imidized by a method only by heating or a chemical method. In the case of the method using only heating, the polyamic acid is imidized by heat treatment at 200 to 350 ° C., for example. In addition, the chemical method is a method in which the polyamic acid is heat-treated and completely imidized while using a basic catalyst in order to rapidly advance imidization. The basic catalyst is not particularly limited, and a conventionally known basic catalyst is used. Examples thereof include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), various tertiary amines, and the like. It is done. These basic catalysts may be used alone or in combination of two or more.

(Photo-curing resin)
The photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation, and in particular, a compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers and photopolymerizable vinyl monomers are used.

Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; Alkyl such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Coxyalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri Alkylene polyol poly (meth) acrylates such as methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate Polyoxyalkylene glycol poly, such as ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylates; poly (meth) acrylates such as neopentyl glycol ester di (meth) acrylate of hydroxybivalic acid; isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate Is mentioned.

As the photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, or the like can also be suitably used. Among these, alicyclic epoxy compounds include 3,4,3 ′, 4′-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2-bis (3,4-epoxy). Cyclohexyl) -1,3-hexafluoropropane, bis (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxycyclohexyl)] ethylbenzene, bis (3,4-epoxycyclohexyl) Adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3 ′, 4′-epoxy-6-methylcyclohexanecarboxylate, ethylene -1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester Cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol and alicyclic epoxy compounds having an epoxy group such as 3,4-epoxycyclohexyl ethyl trimethoxy silane.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3- Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate In addition to polyfunctional oxetanes such as (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (p -Hydroxystyrene), cardo type bisphenol Oxetane compounds such as ethers of calixarenes, calixresorcinarenes, or resins having a hydroxyl group such as silsesquioxane, and copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylate It is done.

Examples of vinyl ether compounds include cyclic ether type vinyl ethers such as isosorbite divinyl ether and oxanorbornene divinyl ether (vinyl ethers having a cyclic ether group such as oxirane ring, oxetane ring and oxolane ring); aryl vinyl ethers such as phenyl vinyl ether; n-butyl vinyl ether Alkyl vinyl ethers such as octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexanedimethanol divinyl ether, α and / or β position And vinyl ether compounds having a substituent such as an alkyl group and an allyl group. It is. Examples of commercially available products include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), and triethylene glycol divinyl ether manufactured by Maruzen Petrochemical Co., Ltd.

In the case of using a photocurable resin, in addition to the above-described photocurable resin, a photopolymerization initiator, a photoacid generator, a photobase generator, or the like is used, and one of these is used alone or Two or more kinds can be used in combination.

Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy- Acetophenones such as 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( 4-morpholinyl) phenyl] -1-butano Aminoalkylphenones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone and the like; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro Thioxanthones such as thioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4- Pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl Phosphine oxide such as 2,4,6-trimethylbenzoyl phenyl phosphinate Nate; various peroxides, titanocene initiators, and the like oxime ester initiator. These are photosensitized like tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. You may use together with an agent etc. These photopolymerization initiators can be used alone or in combination of two or more.

Examples of the photoacid generator include diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, onium salts such as pyridinium salts; tris (trihalomethyl) -s-triazine ( For example, 2,4,6-tris (trichloromethyl) -s-triazine), 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Halogenated compounds such as triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine; 2 of sulfonic acid Nitrobenzyl ester; iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivative; N-hydroxyimide = sulfonate; tri (methanesulfonyloxy) benzene derivative; bissulfonyldiazomethanes; sulfonylcarbonylalkanes; sulfonylcarbonyl Examples include diazomethanes; disulfone compounds; iron allene complexes. These photoacid generators can be used alone or in combination of two or more.

A photobase generator is a compound that generates one or more basic substances that can function as a catalyst for a polymerization reaction by changing the molecular structure upon irradiation with light such as ultraviolet rays or visible light, or by cleaving the molecules. It is. Examples of basic substances include secondary amines and tertiary amines. Examples of such photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, Examples thereof include compounds having a substituent such as an alkoxybenzyl carbamate group. These photobase generators can be used alone or in combination of two or more.

Organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers Alcohol such as ethanol, propanol, ethylene glycol, propylene glycol 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide Amides such as tetrahydrofuran, dioxane and the like; Nitriles such as acetonitrile, benzonitrile and propionitrile; Halogens such as chloroform, dichloromethane, bromobenzene, dibromobenzene, chlorobenzene and dichlorobenzene; N-methyl-2 -Amines such as pyrrolidone, dimethylaniline, dibutylaniline, diisopropylaniline; sulfur-containing compounds such as dimethylsulfoxide and sulfolane; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, Examples thereof include petroleum solvents such as hydrogenated petroleum naphtha and solvent naphtha. Among these, N-methyl-2-pyrrolidone and methyl ethyl ketone are preferable because they are easy to handle.

[Resin composition]
In the resin-containing sheet of the present invention, the resin 3 is in contact with the fixing agent 2 and the fiber substrate 11. In the present invention, the resin 3 may cover the outside of the fiber base material 11 as long as it can play the role of ensuring adhesion. The impregnation ratio of the resin composition is not particularly limited as long as the resin-containing sheet can be adhered to the metal foil or the like, but the concentration of the resin in the resin-containing sheet is 10 to 99% by volume, particularly It is preferably 10 to 70% by volume. By setting the impregnation rate of the resin composition within the above range, good adhesion and high strength can be obtained in a balanced manner.

The resin composition that forms the resin 3 can include at least one selected from a thermosetting resin, a photocurable resin, and a thermoplastic resin. , Or a combination of two or more. Among these, from the viewpoint of physical properties of the cured product or molded product, a thermosetting resin is preferable, and an epoxy resin is more preferable. When a thermosetting resin or a photocurable resin is used as the resin composition, the same thermosetting resin, photocurable resin, organic solvent, etc. as those mentioned for the fixing agent composition should be used as appropriate. In the present invention, the resin composition and the fixing agent composition may be different from each other. Moreover, as a thermoplastic resin, what is shown below can be used.

(Thermoplastic resin)
Thermoplastic resins include acrylic, modified acrylic, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer. General-purpose plastics such as polymers, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid, polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultrahigh molecular weight polyethylene, polybutylene terephthalate, modified polyphenylene ether, polysulfone ( PSF), polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone, polyarylene , Polyetherimide, Polyamideimide, Liquid crystal polymer, Polyamide 6T, Polyamide 9T, Polytetrafluoroethylene, Polyvinylidene fluoride, Polyesterimide, Thermoplastic polyimide and other engineering plastics, Olefin, Styrene, Polyester, Urethane, Examples include amide-based, vinyl chloride-based, and hydrogenated thermoplastic elastomers. In the present invention, a resin composite can be used. For example, an epoxy resin-PSF, an epoxy resin-PPS, an epoxy resin-PES, etc. can be used as a resin composite of a thermosetting resin and a thermoplastic resin.

In the fixing agent composition and the resin composition according to the present invention, a colorant can be blended as another component.

As the colorant, a known and conventional one represented by a color index as a color pigment or dye can be used. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 93, 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 16 , 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258 266, 267, 268, 269, 37, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2. , 3: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, and the like.

In addition, the anti-foaming / leveling agent, thixotropy imparting agent / thickening agent, coupling agent, dispersant, flame retardant and the like are added to the fixing agent composition and the resin composition according to the present invention as necessary. An agent can be included.

As the antifoaming agent / leveling agent, compounds such as mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, and the like can be used.

Thixotropic agents and thickeners include clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, zeolite, amorphous inorganic particles, polyamide additives, modified urea additives, wax additives Etc. can be used.

As the coupling agent, alkoxy group is methoxy group, ethoxy group, acetyl, etc., and reactive functional group is vinyl, methacryl, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureido, sulfide, Isocyanates and the like, for example, vinyl silane compounds such as vinyl ethoxylane, vinyl trimethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxylane, γ-aminopropyltrimethoxylane,系 -β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, amino-based silane compounds such as γ-ureidopropyltriethoxysilane, γ-glycid Xylpropyltrimeth Epoxy silane compounds such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxylane, γ-glycidoxypropylmethyldiethoxysilane, mercapto silane compounds such as γ-mercaptopropyltrimethoxysilane, Silane coupling agents such as phenylamino silane compounds such as phenyl-γ-aminopropyltrimethoxysilane, isopropyl triisostearoylated titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, Tora (1,1-diallyloxymethyl-1-butyl) bis- (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltristearoyl diacryl Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, etc., ethylenically unsaturated zirconate-containing compound, neoalkoxy zirconate-containing compound , Neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecyl) benzene Sulfonyl zirconate, neoalkoxy tris (dioctyl) phosphate zirconate, neoalkoxy tris (dioctyl) pyrophosphate zirconate, neoalkoxy tris (ethylenediamino) ethyl zirconate, neoalkoxy tris (m-amino) phenyl zirconate, tetra ( 2,2-diallyloxymethyl) butyl, di (ditridecyl) phosphite zirconate, neopentyl (diallyl) oxy, trineodecanoyl zirconate, neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl zirconate, neopentyl ( Diallyl) oxy, tri (dioctyl) phosphatozirconate, neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphatozirconate, neopentyl ( Allyl) oxy, tri (N-ethylenediamino) ethyl zirconate, neopentyl (diallyl) oxy, tri (m-amino) phenyl zirconate, neopentyl (diallyl) oxy, trimethacryl zirconate, neopentyl (diallyl) oxy, triacryl Zirconate, dineopentyl (diallyl) oxy, diparaaminobenzoyl zirconate, dineopentyl (diallyl) oxy, di (3-mercapto) propionic zirconate, zirconium (IV) 2,2-bis (2-propenolatomethyl) Zirconate coupling agents such as butanolato, cyclodi [2,2- (bis-2-propenolatomethyl) butanolato] pyrophosphato-O, O, diisobutyl (oleyl) acetoacetylaluminate, alkylacetoacetate DOO diisopropylate aluminate coupling agents such like.

Dispersants include polycarboxylic acid-based, naphthalene sulfonic acid formalin condensation-based, polyethylene glycol, polycarboxylic acid partial alkyl ester-based, polyether-based, polyalkylene polyamine-based polymeric dispersants, alkyl sulfonic acid-based, four Low molecular weight dispersants such as secondary ammonium series, higher alcohol alkylene oxide series, polyhydric alcohol ester series and alkylpolyamine series can be used.

Flame retardants include hydrated metal such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester Phosphorus-containing polyol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicone polymer and the like can be used.

The fixing agent composition and the resin composition according to the present invention include other inorganic fillers such as barium sulfate, silica and hydrotalcite, organic fillers such as nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, and peroxides. Product decomposition agents, thermal polymerization inhibitors, adhesion promoters, rust inhibitors, surface treatment agents, surfactants, lubricants, antistatic agents, pH adjusters, antioxidants, dyes, pigments, fluorescent agents, etc. It may be included as long as the object of the invention is not impaired.

[Storage modulus]
In the present invention, the storage elastic modulus of the fixing agent 2 needs to be higher than the storage elastic modulus of the resin 3. Here, the storage elastic modulus of the fixing agent 2 means the storage elastic modulus of a cured film obtained by curing a composition containing only the components of the fixing agent composition by heat or light after film formation without including the fiber 1. To do. Similarly, the storage elastic modulus of the resin 3 also means the storage elastic modulus of a cured film cured by heat or light after film formation in the case of a curable resin, and in the case of a thermoplastic resin, it is a melt film formation. The storage elastic modulus of the coating film obtained by removing the solvent later is meant. The storage elastic modulus is an index value of the hardness of the sample, and an evaluation called dynamic viscoelasticity measurement that detects strain by applying a periodic load to the sample while applying a constant temperature change. This is a value calculated from the detected strain. The higher this value, the better the mechanical strength. In the present invention, it is sufficient that the storage elastic modulus of the fixing agent 2 is higher than the storage elastic modulus of the resin 3 at any temperature. 0.1 GPa, more preferably 20 to 0.5 GPa, and the storage modulus of the resin 3 is 10 to 0.001 GPa, more preferably 5 to 0.01 GPa. It is preferable that the storage elastic modulus of the fixing agent 2 is 0.1 GPa or more larger than the storage elastic modulus of the resin 3. In particular, the storage elastic modulus of the fixing agent 2 is preferably higher than the storage elastic modulus of the resin 3 at any temperature within the range of 150 to 250 ° C., and the fixing agent 2 is fixed at the entire temperature range of 150 to 250 ° C. It is more preferable that the storage elastic modulus of the agent 2 is higher than the storage elastic modulus of the resin 3. Accordingly, the resin-containing sheet of the present invention can be used even in a high temperature region of 150 to 250 ° C., and therefore, the use is widened.

[Glass-transition temperature]
In the present invention, the glass transition temperature of the fixing agent 2 is preferably higher than the glass transition temperature or softening temperature of the resin 3. Here, the glass transition temperature of the fixing agent 2 means the glass transition temperature of a cured film obtained by curing a composition containing only the components of the fixing agent composition by heat or light after film formation without including the fiber 1. To do. Similarly, the glass transition temperature or softening temperature of the resin 3 also means the glass transition temperature of a cured film cured by heat or light after film formation in the case of a curable resin, and in the case of a thermoplastic resin, It means the softening temperature of the coating film obtained by removing the solvent after the melt film formation. The glass transition temperature is a value (loss) calculated from the ratio (E ″ / E ′) of the storage elastic modulus (E ′) and loss elastic modulus (E ″) obtained from the dynamic viscoelasticity measurement described above. This is the temperature when the tangent) is maximum, and the higher the temperature, the better the heat resistance. In the present invention, the upper limit of the glass transition temperature is not particularly limited, but a preferable range thereof is 130 ° C. or higher, more preferably 140 ° C. or higher, particularly preferably 250, for the glass transition temperature of the fixing agent 2. It is above ℃. The higher the glass transition temperature of the fixing agent 2, the higher the storage elastic modulus of the resin-containing sheet of the present invention, which is preferable.
On the other hand, the glass transition temperature or softening temperature of the resin 3 is 70 ° C. or higher, more preferably 80 ° C. or higher. The glass transition temperature of the fixing agent 2 is preferably 5 ° C. or more higher than the glass transition temperature or softening temperature of the resin 3.

[Production of resin-containing sheet]
The resin-containing sheet of the present invention can be obtained by treating the fiber substrate 11 with the fixing agent composition to fix the fibers 1 to each other and then impregnating the fixed fiber substrate 11 with the resin composition. it can. For example, the resin-containing sheet of the present invention is obtained by sequentially applying and impregnating a fixing agent composition and a resin composition in a state in which fibers are arranged on an object to be applied such as a carrier film, thereby fixing the fixing agent composition and the resin composition. A dry film can also be produced by volatile drying of the organic solvent contained therein, and a cover film may be further bonded thereon if desired. At this time, if the resin composition does not hinder the fixing performance of the fixing agent composition to the fiber, the application process of the resin composition may be performed either before or after drying the fixing agent. But you can.

In this case, the fixing agent composition and the resin composition of the present invention can be applied by adjusting the viscosity suitable for the application method by blending, dispersing, and diluting each component as necessary. As described above, the fixing agent composition only needs to be able to permeate the fiber base material 11 and fix the fibers 1 to each other, and the resin composition includes at least one of the fiber base material 11. Any surface may be used as long as both surfaces, particularly both surfaces, can be adhered to a metal foil or the like.

As the object to be coated, a carrier film for a dry film is preferable, but it may be directly coated on the surface of a metal foil or a circuit board on which a circuit is formed. Specific examples of the coating method include a dropping method using a pipette, a dip coating method, a bar coater method, a spin coating method, a curtain coating method, a spray coating method, a roll coating method, a slit coating method, a blade coating method, a lip coating. And various coating methods such as screen printing, spray printing, ink jet printing, letterpress printing, intaglio printing, and planographic printing.

Also, the carrier film and the cover film may be any known materials used for the dry film, and examples thereof include a polyethylene film and a polypropylene film. The carrier film and the cover film may use the same film material or different film materials, but the cover film preferably has a smaller adhesiveness to the resin 3 than the carrier film.

A structure can be obtained by bringing the resin-containing sheet of the present invention into close contact with a substrate. Examples of the substrate include a metal foil substrate and a circuit board (circuit board on which a circuit is formed). The resin insulating layer can be formed by thermally adhering the resin-containing sheet of the present invention to the substrate surface, and the metal foil layer and the resin insulating layer can be laminated in a plurality of layers by repetition thereof. In addition, when manufacturing a resin-containing sheet on a carrier film, you may laminate | stack between resin-containing sheets, and may laminate | stack between resin-containing sheets at the time of contact | adherence with metal foil etc.

When producing a structure using the resin-containing sheet of the present invention, when the fixing agent composition and the resin composition are a combination of a thermosetting resin or a photocurable resin, only a method of heat curing, activity The structure can be manufactured by using a method only with energy ray irradiation, a method in which heat curing is performed after irradiation with active energy rays, or a method in which active energy rays are irradiated after heat curing. In the case of using a dry film, if there is a cover film, the cover film is peeled off, the resin-containing sheet is thermally adhered to the substrate surface, and then the carrier film is peeled off and cured by the above-described curing method. The body can be manufactured. In addition, when using a thermosetting resin as both the fixing agent composition and the resin composition, both heat curing processes of fixing fibers and impregnating the resin may be performed simultaneously. In addition, the heating temperature at the time of heating is not particularly limited as long as the fiber and the fixing agent contained in the target base material are not decomposed by high heat, and there is no particular limitation on the lower limit and the upper limit. As for the exposure amount, there is no particular lower limit and upper limit as long as the exposure amount is too low to produce an uncured portion.

Further, when the resin-containing sheet of the present invention is produced, when the resin composition is a thermoplastic resin, a method of heating, heating, or press-bonding a pellet-shaped or sheet-shaped thermoplastic resin can also be used. Here, in order to impregnate the thermoplastic resin into the fiber base material fixed by the fixing agent, it is not an essential requirement to pressurize using a device, but the fiber base of the thermoplastic resin by performing the pressurization is not necessary. Penetration into the material becomes easier. In the case of applying pressure, there is no particular upper limit for the pressure unless the shape of the intended resin-containing sheet is impaired. The structure can be formed by thermally adhering the resin-containing sheet to the substrate surface. Moreover, when forming a structure using a dry film, it can produce similarly.

In the above, examples of the apparatus used at the time of drying, heat-curing or heat-pressing include a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, a heating / pressurizing roll, and a press machine. Examples of the light source for active energy ray irradiation include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, and a metal halide lamp. In addition, laser beams and the like can also be used as active energy rays.

There is no particular limitation on the thickness of the fiber base material, which is a constituent member of the resin-containing sheet of the present invention, one in which fibers are fixed to each other with a fixing agent (hereinafter also referred to as “intermediate body”), and the purpose of the dry film. The intermediate can be selected as appropriate depending on the thickness of the fiber base material, particularly if the fibers are fixed to each other by a fixing agent. The film thickness is preferably not more than twice the thickness of the substrate. Specifically, it is more preferably within a range of 1 to 1.5 times the thickness of the fiber base material. If the thickness of the intermediate exceeds twice the thickness of the fiber base material, the physical properties of the fixing agent itself are affected, which is not preferable.

The structure obtained by forming the resin-containing sheet of the present invention on the substrate surface and curing or molding can be used as a core material for a wiring board, and an interlayer for wiring boards can be obtained by performing an etching process or the like. It can also be used as an insulating material. In addition, if a resin-containing sheet is formed on the surface of a circuit board on which a circuit is formed, patterning and curing or molding so as to cover only the circuit wiring, it is used as a solder resist that is the outermost layer of the circuit board. You can also

The resin-containing sheet of the present invention having the configuration as described above can be applied to a wiring board for an electronic device, and is preferably applied to, for example, an interlayer insulating material for a wiring board, a solder resist, a core material, or the like. Thus, the intended effect of the present invention can be obtained. In addition, for example, the fibers are fixed with a fixing agent composition, the resin is infiltrated and dried, a semi-cured (B stage) resin insulating layer is formed, and the resin insulating layer and the metal foil are laminated and pressed. Thus, a multilayer board can also be produced.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In addition, all the compounding quantities in the following table | surfaces show a mass part.

[Synthesis of Polyamic Acid Varnish 1]
A dehydrated N-methyl-2-pyrrolidone (NMP) solvent (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a three-necked flask equipped with a stirrer substituted with nitrogen, and 4,4′-diaminodiphenyl ether (ODA) (Japanese) (Made by Kojun Pharmaceutical Co., Ltd.) and 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) (manufactured by Wako Pure Chemical Industries, Ltd.) at a molar ratio of 1: 1, The mixture was stirred for 16 hours or longer to obtain a polyamic acid varnish 1 having a resin solid content ratio of 7.5% by mass.

[Synthesis of Polyamic Acid Varnish 2]
A dehydrated N-methyl-2-pyrrolidone (NMP) solvent (manufactured by Wako Pure Chemical Industries, Ltd.) is placed in a three-necked flask equipped with a stirrer substituted with nitrogen, and p-phenylenediamine (PDA) (Wako Pure Chemical Industries, Ltd.) is added. And 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (BPDA) (manufactured by Wako Pure Chemical Industries, Ltd.) at a molar ratio of 1: 1, and at room temperature The mixture was stirred for 16 hours or more to obtain a polyamic acid varnish 2 having a resin solid content ratio of 7.5% by mass.

[Preparation of fixing agent composition or resin composition]
Table 1 below shows the contents of the compositions 1 to 4 used as the fixing agent composition or the resin composition. Each composition was prepared according to the description of compositions 1 to 4 in Table 1 below. In the case of the multiple component system of Composition 1, each component was blended and then stirred using a rotation / revolution mixer to prepare.

[Preparation of test specimen for evaluation of storage elastic modulus of adhesive or resin]
Each of the compositions 1 to 4 was applied to a copper foil having a thickness of 18 μm using an applicator to obtain a coating film.
Composition 1 was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes and then heated at 150 ° C. for 60 minutes to obtain a cured epoxy resin. When the copper foil was removed, the thickness was 50 μm. A test piece for evaluation such as storage elastic modulus having a width of 5 mm and a length of 50 mm was produced using this cured product.
About composition 2, after application | coating, after drying at 80 degreeC and 30 minute atmospheric conditions with a hot-air circulation type drying furnace, it heats on nitrogen conditions (100 ml / min.) At 250 degreeC for 60 minutes, and imidates Obtained. When the copper foil was removed, the thickness was 50 μm. Thereafter, an evaluation test piece was prepared in the same manner as described above.
For Composition 3, an evaluation test piece was prepared in the same manner as Composition 2 except that the heating operation was performed at 300 ° C. for 60 minutes under nitrogen conditions.
For composition 4, high-density polyethylene pellets (specific gravity 0.95) are put into a press machine, and after heating and pressing at 140 ° C., 3 MPa, 3 minutes, and cooled to room temperature, a molded product is obtained. As a result, the thickness was 50 μm. Thereafter, an evaluation test piece was prepared in the same manner as described above.

[Preparation of resin-containing sheet and test piece for storage elastic modulus evaluation of sheet]
Tables 2 and 3 below show the structures of the resin-containing sheets or sheets of the examples and comparative examples.

(Preparation of intermediate of Example 1-A)
For Example 1-A in Table 2 below, a glass cloth (type 1035 (IPC standard), thickness 30 μm) was used as the fiber substrate, and the composition 1 (viscosity 0.0005 Pa · s) was added thereto. After impregnation, after drying at 80 ° C. for 30 minutes in a hot air circulation drying oven and then heating and curing at 150 ° C. for 60 minutes, the glass cloth and the fixing agent (cured product of epoxy resin composition) An intermediate was produced.

(Preparation of intermediate of Example 2-A)
For Example 2-A in Table 2 below, the same glass cloth as in Example 1-A was impregnated with the above composition 2 (viscosity 0.001 Pa · s), and then heated in a hot-air circulating drying furnace. After drying under atmospheric conditions of 30 ° C. for 30 minutes, the mixture was heated and imidized at 250 ° C. for 60 minutes to produce an intermediate composed of glass cloth and a fixing agent (polyimide).

(Preparation of intermediate of Example 3-A)
For Example 3-A in Table 2 below, the same glass cloth as in Example 1-A was impregnated with the above composition 3 (viscosity 0.001 Pa · s), and then heated in a hot air circulating drying furnace. After drying under atmospheric conditions of 30 ° C. for 30 minutes, the mixture was imidized by heating at 300 ° C. for 60 minutes to prepare an intermediate made of glass cloth and a fixing agent (polyimide).

(Preparation of Intermediate of Comparative Example 4-A)
In the same manner as in Example 1-A, the composition 1 was used to produce an intermediate composed of a glass cloth and a fixing agent (cured product of the epoxy resin composition).

The thicknesses of the intermediates of Examples 1-A to 3-A and Comparative Example 4-A were 33 to 35 μm, and the increase from the thickness of the glass cloth was 3 to 5 μm.

(Preparation of intermediate of Example 1-B)
For Example 1-B in Table 3 below, an aramid nonwoven fabric was treated in the same manner as in the preparation of the intermediate of Example 1-A, except that an aramid nonwoven fabric (Nomex 410, thickness 50 μm) was used as the fiber. And the intermediate body which consists of fixing agent (hardened | cured material of an epoxy resin composition) was produced.

(Preparation of intermediate of Example 2-B)
For Example 2-B in Table 3 below, the aramid was treated in the same manner as in the preparation of the intermediate of Example 2-A, except that the same aramid nonwoven fabric as in Example 1-B was used as the fiber. The intermediate body which consists of a nonwoven fabric and fixing agent (polyimide) was produced.

(Preparation of intermediate of Example 3-B)
For Example 3-B in Table 3 below, an aramid was treated in the same manner as in the preparation of the intermediate of Example 3-A, except that the same aramid nonwoven fabric as in Example 1-B was used as the fiber. The intermediate body which consists of a nonwoven fabric and fixing agent (polyimide) was produced.

(Preparation of Intermediate of Comparative Example 4-B)
In the same manner as in Example 1-B, the composition 1 was used to prepare an intermediate composed of a glass cloth and a fixing agent (cured product of the epoxy resin composition).

The thicknesses of the intermediates of Examples 1-B to 3-B and Comparative Example 4-B were 53 to 56 μm, and the increase in thickness from the thickness of the aramid nonwoven fabric was only 3 to 6 μm.

(Preparation of resin-containing sheet or sheet of each example and comparative example)
For Example 1-A and Example 1-B, the composition 4 was charged into a press machine and melted at 140 ° C., and then impregnated into each of the intermediates obtained above. After heating and pressurizing for 3 minutes, the resin-containing sheet was prepared by impregnating a glass cloth or an aramid nonwoven fabric fixed with a fixing agent (epoxy) with a resin (high-density polyethylene resin) by cooling to room temperature.
For Example 2-A, Example 2-B, Example 3-A and Example 3-B, an appropriate amount of the above composition 1 is applied to each of the intermediates obtained above so as to spread over the entire fiber. The glass cloth or aramid nonwoven fabric fixed with the fixing agent (polyimide) is cured by heating and curing under the same conditions as in the preparation of the test piece for evaluation of the fixing agent or resin. A resin-containing sheet impregnated with a cured product was prepared.
The thicknesses of the resin-containing sheets in Examples 1-A to 3-A and Examples 1-B to 3-B were 5 to 10 μm thicker than the thickness of the intermediate. Then, about each resin containing sheet, the test piece for evaluation was produced on the conditions similar to the above.

For Comparative Example 1-A and Comparative Example 1-B, the composition 1 was applied to a glass cloth or an aramid nonwoven fabric in an appropriate amount so as to reach the entire fiber, impregnated, and used for evaluation of the fixing agent or resin. A sheet in which a glass cloth or an aramid non-woven fabric containing no fixing agent was impregnated with a resin (cured epoxy resin) was produced by heating and curing under the same conditions as in the production of the test piece.
For Comparative Example 2-A and Comparative Example 2-B, the composition 2 was coated and impregnated on a glass cloth or an aramid nonwoven fabric in the same manner as in Comparative Example 1-A, and then heated at 80 ° C. in a hot air circulating drying oven. After drying under atmospheric conditions for 30 minutes, it was imidized by heating under atmospheric conditions at 250 ° C. for 60 minutes to prepare a sheet in which a resin cloth (polyimide) was impregnated with a glass cloth or an aramid nonwoven fabric not containing a fixing agent.
For Comparative Example 3-A and Comparative Example 3-B, the composition 4 was charged into a press machine and melted at 140 ° C., and then impregnated into a glass cloth or an aramid nonwoven fabric at 140 ° C., 3 MPa, 3 minutes. After heating and pressurizing, the sheet was cooled to room temperature to prepare a sheet in which a glass cloth or aramid non-woven fabric containing no fixing agent was impregnated with a resin (high-density polyethylene resin).
For Comparative Example 4-A and Comparative Example 4-B, except that the glass cloth or the aramid nonwoven fabric in Comparative Example 2-A and Comparative Example 2-B was used instead of the intermediate having the fixing agent composed of Composition 1 above. Produced a resin-containing sheet in the same manner as in Comparative Examples 2-A and 2-B.
Thereafter, for each sheet, an evaluation test piece was prepared in the same manner as described above.

As shown in Tables 2 and 3 below, the resin content concentrations were similar for Examples 1-A to 3-A and Comparative Examples 1-A to 4-A. The same was true for B to 3-B and Comparative Examples 1-B to 4-B. Here, the resin content concentration is as follows: amount of fixing agent = {1− (volume of fiber substrate / volume of intermediate)} × 100 [volume%], resin amount = {1− (volume of intermediate / resin-containing sheet) Or the volume of the sheet)} × 100 [volume%] (volume is calculated based on mass and specific gravity), respectively.

[Measurement of storage modulus, etc.]
Using a test piece for evaluating the storage elastic modulus of the fixing agent or the resin, using a tensile mode of a DMA viscoelasticity measuring apparatus (DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.), measuring frequency 1 Hz, minimum tension and minimum compressive force 200 mN, Viscoelasticity was measured under the conditions of strain amplitude 10 μm, heating rate 5 ° C./min, and atmospheric conditions to obtain storage elastic moduli at 50 ° C., 150 ° C. and 250 ° C., and a glass transition temperature or a softening temperature. The results are shown in Table 1 below.

＊１：ｊＥＲ８２８，三菱化学（株）製
＊２：２－エチル－４－メチルイミダゾール，四国化成（株）製
＊３：和光純薬工業（株）製
＊４：比重０．９５

* 1: jER828, manufactured by Mitsubishi Chemical Corporation * 2: 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Co., Ltd. * 3: manufactured by Wako Pure Chemical Industries, Ltd. * 4: specific gravity 0.95

[Evaluation of storage modulus of resin-containing sheet or sheet]
For the resin-containing sheet or the test piece for sheet evaluation, the test piece is attached so that the bias (diagonal) direction of the fiber of the glass cloth or the aramid nonwoven fabric in the sheet is the tensile direction of the apparatus, and the minimum tension and the compression force are 50 mN. Except for the above, viscoelasticity was measured in the same manner as described above, and storage elastic moduli at 50 ° C, 150 ° C and 250 ° C were obtained. Here, the reason for measuring in the bias (diagonal) direction is to eliminate the influence of the elastic modulus of the fiber substrate itself as much as possible, and to examine the influence of the elastic modulus improvement due to the fixing effect. About each Example, when it compared with the sheet | seat of the comparative example which has not adhered the sticking agent, when the value of the storage elastic modulus E [GPa] was large, it was set as (circle), and when small, it was set as x.

Specifically, the resin-containing sheet of Example 1-A has a storage elasticity higher than that of the sheet of Comparative Example 3-A in which no fixing agent was used at any temperature of 50 ° C., 150 ° C., and 250 ° C. Since the value of the rate E [GPa] is large, it was set as “◯”.
Also in Example 1-B, since the value of the storage elastic modulus E [GPa] was larger than that of the sheet of Comparative Example 3-B in which no sticking agent was used, “◯” was given.
Also in the resin-containing sheets of Examples 2-A, 2-B, 3-A, and 3-B, the storage elastic modulus was compared with the sheets of Comparative Examples 1-A and 1-B in which no fixing agent was used. Since the value of E [GPa] is large, it was set as “◯”.
On the other hand, the resin-containing sheet of Comparative Example 4-A has a storage elastic modulus E [GPa] higher than the sheet of Comparative Example 2-A that did not use the fixing agent at any temperature of 50 ° C., 150 ° C., and 250 ° C. ] Is small, so “×” was assigned.
Also in the resin-containing sheet of Comparative Example 4-B, “x” was given compared with the sheet of Comparative Example 2-B in which no fixing agent was used.
The results are shown in Tables 2 and 3 below.

For reference, when the above measurement was carried out using only a glass cloth, the value of the storage elastic modulus could not be obtained because the knitted fiber was unwound at the start of the measurement by pulling in the bias direction.

[Preparation of test specimen for adhesion evaluation]
Each intermediate was prepared by applying and impregnating the fixing agent composition in the same manner as described above except that a glass cloth or an aramid nonwoven fabric as a fiber base material was disposed on the carrier film. Thereafter, the resin composition was molded or coated on the surface of the adhesive after drying and dried, and then a cover film was bonded to obtain a dry film. A surface untreated copper foil having a thickness of 18 μm was superposed on both surfaces of this dry film (the carrier film and the cover film were peeled off when they were brought into close contact with each other). 150 ° C. × 10 minutes for 1-A and 1-B, 250 ° C. × 60 minutes for Examples 2-A and 2-B and Comparative Examples 4-A and 4-B, Examples 3-A and 3-B About B, it shape | molded as 300 degreeC x 60 minutes, and produced the test piece for adhesive evaluation in which the resin layer and copper foil contact | adhered. For Comparative Examples 1-A to 3-A and Comparative Examples 1-B to 3-B, a dry film was prepared in the same manner except that the fixing agent composition was not applied and impregnated, and pressurized with a vacuum press. Test specimens for adhesion evaluation were prepared under the same temperature conditions as those for Comparative Examples 1-A to 3-A and Comparative Examples 1-B to 3-B.

[Evaluation of adhesion]
Using the test piece for adhesion evaluation, the peel strength when peeling both at the interface between the resin layer and the untreated copper foil was measured at a peel angle of 90 ° and a peel speed of 50 mm / min. The case of m or more was marked as ◯, and the case of less than 0.5 kN / m was marked as x. The results are shown in Tables 2 and 3 below. When peel strength is high, it can be said that it is excellent in adhesiveness following unevenness and excellent in adhesiveness with copper foil.

As shown in Tables 2 and 3 above, the storage elastic moduli of the fixing agents of Examples 1-A to 3-A and Examples 1-B to 3-B are both larger than the storage elastic modulus of the resin. On the other hand, in Comparative Examples 4-A and 4-B, the storage elastic modulus of the fixing agent is smaller than the storage elastic modulus of the resin. In Comparative Examples 1-A to 3-A and 1-B to 3-B, only the resin is used and no fixing agent is used.

As shown in Tables 2 and 3 above, using a fixing agent whose storage elastic modulus is higher than the storage elastic modulus of the resin, the glass cloth or the aramid nonwoven fabric is fixed, and the resin contained in the example impregnated with the resin It can be seen that the sheet is excellent in adhesion and has a large storage elastic modulus as compared with the sheet of the comparative example impregnated only with the resin.
For example, as apparent from the comparison between Example 1-A and Comparative Example 3-A, the glass cloth fibers were fixed to each other with the fixing composition, and the fiber base material was impregnated with the resin composition. It was found that the resin-containing sheet has high mechanical strength because it has a higher storage elastic modulus at any temperature than Comparative Example 3-A in which the fibers of the glass cloth are not fixed to each other by the fixing composition.
In particular, the resin-containing sheets of Examples 2-A and 3-A and Examples 2-B and 3-B have a storage elastic modulus at 250 ° C. exceeding 1 GPa and excellent mechanical strength at high temperatures. I understand that. On the other hand, in Comparative Example 4-A and Comparative Example 4-B in which the storage elastic modulus of the fixing agent is lower than the storage elastic modulus of the resin, the storage elastic modulus as the resin-containing sheet was low and the adhesion was inferior.

As described above, use of a resin-containing sheet having a fixing agent for fixing fibers in a fiber base and a resin in contact with the fixed fiber, and having a storage elastic modulus of the fixing agent higher than a storage elastic modulus of the resin. Thus, it was confirmed that excellent mechanical strength, elastic modulus and adhesion can be realized. Such a resin-containing sheet of the present invention can be applied to a wiring board for an electronic device, and can be suitably applied to, for example, an interlayer insulating material for a wiring board, a solder resist, a core material, or the like.

1,21 Fiber 2 Fixing agent 3 Resin 11 Fiber base material P Contact point D Direction in which fibers are separated by tension T Space S

Claims (7)

A fiber substrate;
A fixing agent for fixing fibers in the fiber base;
Having a resin in contact with the fiber base material and the fixing agent,
The resin-containing sheet, wherein the storage elastic modulus of the fixing agent is higher than the storage elastic modulus of the resin. The resin-containing sheet according to claim 1, wherein the glass transition temperature of the fixing agent is higher than the glass transition temperature or softening temperature of the resin. The resin-containing sheet according to claim 1, obtained by fixing the fibers of the fiber base material with a fixing agent composition and then impregnating the fixed fiber base material with a resin composition. 4. The resin-containing sheet according to claim 3, wherein the adhesive composition has a viscosity of 1 Pa · s or less. The resin-containing sheet according to claim 1, wherein the fiber base material includes a woven fabric or a non-woven fabric. A structure obtained by bringing the resin-containing sheet according to claim 1 into close contact with a substrate. A wiring board comprising the structure according to claim 6.

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