JP6684712B2 - Resin-containing sheet, and structure and wiring board using the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a resin-containing sheet having excellent mechanical strength, elastic modulus, and adhesiveness, which is suitable for a wiring board for electronic devices and the like, and a structure and a wiring board using the resin-containing sheet.

  As a wiring board for electronic devices, generally, a prepreg (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 is used. The one in which a circuit is formed by an etching method, which is in close contact with a metal foil, is used. In addition, the wiring board is provided with a solder resist in order to prevent the outflow of solder when mounting the components. Wiring board materials such as these prepregs and solder resists need to be adhered while heating and pressing so that they adhere closely to the metal foil surface or the circuit board formed circuit board without any gaps, and the adhesion at that time is important. Become. In addition, the wiring board is required to have high strength (high elastic modulus) in order to improve mounting reliability, and the prepreg and solder resist, which are its constituent members, are also required to have high elastic modulus. Has been.

  As a conventional technique relating to a wiring board material, for example, in Patent Document 1, resin layers having different strengths (elastic moduli) 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 layers of different resin compositions on both surfaces of the core layer, and there is no disclosure that it is useful for adhesion. Further, Patent Document 2 describes a prepreg having a predetermined elastic modulus. This technique aims to temporarily fix the prepreg sheet and the circuit board, and the elastic modulus is controlled by the composition.

  Further, Patent Document 3 discloses a technique of using two kinds 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 of providing an adhesive layer on the surface of the prepreg in order to improve the adhesiveness to the metal foil.

JP, 2008-0888280, A JP, 2006-179716, A JP, 2010-095557, A JP, 2004-168943, A

  However, the above-mentioned conventional prepreg cannot have sufficient mechanical strength and adhesiveness.

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

As a result of earnest studies to solve the above problems, the present inventors have found out the following.
That is, generally, in a woven fabric or a non-woven fabric made of various fibrous materials, the fibers are entangled or interacted with each other to form an aggregate. Therefore, as shown in FIG. 2A, when tension T is applied in one direction to such an aggregate of fibers 21, the fibers 21 slide at the contact point P, and the fibers 21 move in the direction of arrow D. When pulled apart, the aggregate will fray and eventually break. On the other hand, in the case of the woven fabric, the strength against tension in the fiber direction is high to some extent, but the strength against tension in a direction different from the fiber direction (oblique direction) is low. In the case of a non-woven fabric, the strength against pulling is low in any direction.

  As described above, since the wiring board uses a resin-containing sheet such as a woven cloth such as glass cloth or a non-woven fabric made of aramid fiber and the like and a prepreg made of a resin, it is necessary to secure the strength of the wiring board. In a fiber assembly, it is important to prevent the fibers from slipping. On the other hand, as described above, the resin-containing sheet is also required to have good adhesion to the surface of the metal foil or the surface of the wiring board.

As a result of the above investigation, the present inventors have found that the mechanical strength and the adhesiveness can be balanced by the following constitution.
That is, the resin-containing sheet of the present invention has a fibrous base material, a fixing agent that fixes the fibers in the fibrous base material to each other, and a resin that contacts the fibrous base material and the fixing agent. The storage elastic modulus of 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 to each other with a fixing agent composition, and then impregnating the fixed fiber base material with the resin composition. In this case, the viscosity of the adhesive composition is preferably 1 Pa · s or less. Further, in the resin-containing sheet of the present invention, it is preferable that the fiber base material includes a woven fabric or a non-woven fabric.

  The structure of the present invention is characterized by being 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 above-mentioned 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 a substrate. That is, in the present invention, the storage elastic modulus of the adhesive agent for adhering the fibers in the fiber base material is made higher than the storage elastic modulus of the resin in contact with the fiber base material and the adhesive agent, so that high strength and high strength are achieved. The inventors have found the conditions of materials for obtaining a resin-containing sheet having an improved elastic modulus and improved adhesion. This requires that the resin insulating material for the wiring board 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 is deteriorated. In (1), the problem of this adhesiveness is solved while realizing a high elastic modulus.

It is explanatory drawing which shows the structure of the resin containing sheet of this invention like a model. It is explanatory drawing which shows a model behavior of the case where the fibers are not fixed (a) and the case where they are fixed (b) when the tension T is applied to the fiber aggregate in one direction. .

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 shows an explanatory view showing the structure of the resin-containing sheet of the present invention. The resin-containing sheet of the present invention is a sheet-like body mainly composed of a fiber component and a resin component, and as shown in the figure, a fiber base material 11 and a fixing agent 2 for fixing the fibers 1 in the fiber base material 11 to each other. And a resin 3 that is in contact with the fiber base material 11 and the adhesive 2. The symbol S in the drawing indicates a space in the fiber base material 11 in which neither the fixing agent 2 nor the resin 3 is impregnated. In the resin-containing sheet of the present invention, it can be said that the fibers 1 constituting the fiber base material 11, the adhesive 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 adhesive agent 2 that adheres the fibers 1 to each other is higher than the storage elastic modulus of the resin 3 at any temperature.

  That is, as a result of earnest studies by the present inventors, the role of the resin component contained in the resin-containing sheet is two, and one is to suppress slippage between fibers and to make the resin-containing sheet have high strength and high elasticity. It has been found that it has a role as a fixing agent for rationalization, and the other has a role of bringing the insulating resin layer into close contact with the metal foil surface and the like. From this point of view, as a result of further study by the present inventors, the two roles of the resin component contained in the resin-containing sheet are shared by the adhesive for securing high strength and the resin for securing adhesiveness. Then, it has been found that both of these performances can be satisfactorily ensured by defining the relationship between the storage elastic modulus of the adhesive and the resin. As described above, a technique in which the role of the resin component is divided into two and the high elastic modulus and the good adhesiveness are compatible with each other has not heretofore been known.

  As shown in FIG. 2B, the present invention is conceptually described. In the case where the contact point P of the fiber 1 included in the fiber base material 11 is fixed by the fixing agent 2, the tension T is applied in one direction. However, since slippage does not occur at the contact point P, the fiber base material 11 can have high strength and high elastic modulus. Further, by impregnating the resin 3 so as to contact the fiber base material 11 and the adhesive agent 2, good adhesiveness as a resin-containing sheet can be obtained. Therefore, according to the resin-containing sheet of the present invention, the high elastic modulus required for the fiber base material 11 can be ensured by the adhesive agent 2 and the adhesion to the substrate or the like can be ensured by the resin element 3. It has become possible to obtain a resin-containing sheet having both high strength and good adhesion, which has not been obtained by using such a high elastic modulus material.

[Fiber substrate]
The fiber base material 11 according to the present invention is composed of an aggregate of fibers 1. The fiber 1 is not particularly limited as long as it can form an aggregate and produce a woven or non-woven fabric, and a natural fiber or a chemical fiber can be mainly used. Among the specific examples of the fiber 1, examples of the natural fiber include glass fiber, cellulose fiber, rock fiber, metal fiber, carbon fiber and rock wool, and examples of the chemical fiber include aramid, nylon, vinylon, vinylidene, polyester, Polyolefin (polyethylene terephthalate, modified polyethylene terephthalate, polyethylene, polypropylene, etc.), polyurethane, acrylic, polyvinyl chloride, polyether ether ketone, polyamide imide, polyphenylene sulfide, polyether imide, polytetrafluoroethylene, acetate, triacetate, promix, Examples thereof include rayon, cupra, polynosic rayon, lyocell, tencel, and the like. One of these may be used alone or in combination of two or more. The manufacturing method, fiber content (fiber blending ratio), 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 base material 11 is preferably glass fiber, cellulose fiber, or aramid fiber from the viewpoint of affinity with the adhesive.

  In the present invention, it is particularly preferable to use a woven fabric as the fiber base material 11. By adding a woven fabric, it is possible to obtain the merit of increasing the strength of even a fiber having originally low strength. In addition, in the present invention, even when organic fiber having low strength is used as the fiber base material 11 instead of glass fiber which is originally high in strength, it is possible to obtain high strength by using a fixing agent having high storage elastic modulus. There is also an advantage that it can be realized.

[Adhesive composition]
The adhesive composition for forming the adhesive 2 may be any adhesive that can adhere to the fibers 1 and adhere the fibers 1 to each other, and only adheres to the contact portions where the fibers contact each other. Alternatively, the entire fiber 1 may be covered and fixed. The amount of the adhesive composition used may be such that the fibers 1 can be adhered to each other and the adhesiveness is not adversely affected. In the aggregate in which the fibers 1 are adhered by the adhesive 2, It is preferable that the volume ratio of the fiber 1 to the fixing agent 2 is 99: 1 to 50:50, particularly 99: 1 to 60:40, in terms of solid content excluding the solvent. When the volume ratio of the fiber 1 to the adhesive agent 2 is within this range, the fibers 1 are sufficiently adhered to each other by the adhesive agent, and a desired high strength is obtained, and the subsequent impregnation with the resin 3 is preferable. It is preferable because the adhesion can be secured. In particular, the amount of the adhesive 2 used is preferably such that the film thickness of the fiber base material 11 does not substantially change before and after the application of the adhesive 2. Here, the fact that the film thickness does not substantially change means that the case where the fiber base material 11 swells due to the solvent component of the adhesive composition to increase the apparent thickness is not included in the change of the film thickness. Is. Further, the adhesive composition is preferably a liquid when it is attached to the fibers, and may be a liquid that can be used by changing the temperature or pressure. In particular, the viscosity of the adhesive composition measured at 25 ° C. with an E-type viscometer at a rotor rotation speed of 5 rpm is preferably 1 Pa · s or less, for example, 1 to 0.0001 Pa · s. The adhesive composition can be impregnated even into the inside of the aggregate of the fibers 1, and the fibers can be more reliably fixed to each other.

  Further, as the adhesive composition, one which is cured by heat or light is used. The curing here means a chemical change from a liquid to a solid by heat or light energy. As the adhesive composition, a commonly used component can be used depending on the application, and one kind can be used alone, or two or more kinds can be used in combination. Examples of conventional components used in the adhesive composition include thermosetting resins, curing agents, thermosetting catalysts, photocurable resins, photopolymerization initiators, photoacid generators, photobase generators, and organic solvents. And specifically, the following can be used.

(Thermosetting resin)
The thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, and bisphenol M. Type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin and other bisphenol type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin and other novolac type 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 copolymer epoxy resin, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin, 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, Glycidyl tris (2-hydroxyethyl) isocyanurate, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin and other novolac type phenolic resins, unmodified resole phenolic resin, tung oil, linseed oil, walnut oil, etc. Phenol resin such as resole phenolic resin such as resole phenolic resin, phenoxy resin, urea (urea) resin, triazine ring-containing resin such as melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone resin, benzoxazine Ring-containing resin, norbornene-based resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyazo Chin resins, and polyimide resins. Of these, epoxy resin and polyimide resin are particularly preferable because they have 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, 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 alone or in combination of two or more. Specific examples of the epoxy resin include jER828 manufactured by Mitsubishi Chemical Co., Ltd., but the epoxy resin is not limited thereto.

  When a cured product is formed using an epoxy resin, it is preferable to contain a curing agent in addition to the epoxy resin. Examples of the curing agent include 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) and other imidazole-based curing agents, diethylenetriamine, Amine curing agents such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, metaxylenediamine, isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, N-aminoethylpiperazine, polyamide, vinylphenol, aralkyl. Type phenol resin, phenol phenyl aralkyl resin, phenol biphenyl aralkyl resin and other phenolic curing agents, phthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, methyl terephthalate Lahydrophthalic acid, methyl hexahydrophthalic acid, methyl nadic acid anhydride, dodecyl succinic anhydride, chlorendic acid anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimate), methyl cyclohexene tetra A known curing agent such as an acid anhydride-based curing agent such as a carboxylic acid anhydride, a cyanate ester resin, an active ester resin, an aliphatic or aromatic primary or secondary amine, a polyamide resin, or a polymercapto compound 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. When the compounding amount of the curing agent is 0.1 part by mass or more, the resin composition can be sufficiently cured, and when the compounding amount is 150 parts by mass or less, an effect commensurate with the compounding amount can be efficiently obtained. You can

  Further, as the thermosetting catalyst, for example, 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. Also, 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.

  Examples of the polyimide resin include those obtained through a polyamic acid (polyimide precursor) by a synthetic reaction of a generally known aromatic polyvalent carboxylic acid anhydride or its derivative and an aromatic diamine, Examples include so-called polyimide varnishes in the market, in which a polyamic acid composition is dissolved in an organic solvent.

  Specific examples of the aromatic polycarboxylic acid anhydride include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic 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-di Ruboxylphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride An anhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc. are 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 the aromatic diamine to be reacted with a polyvalent carboxylic acid such as an aromatic polyvalent carboxylic acid anhydride 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-ami) Phenyl) 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-a Nophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3 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) ) 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] diphenyl ether 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] diphenyl sulfone, 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 can be mentioned. These may be used alone or in admixture of two or more. Among these, 4,4'-diaminodiphenyl ether is particularly preferably used as at least one of the components.

  As the polyimide varnish, Rika Coat SN20, Rica Coat PN20, Rica Coat EN20, Toray Co., Ltd., Treney, Ube Kosan Co., Ltd. U-varnish, JSR Co., Ltd. Optomer, Nissan Kagaku Co., Ltd. are available. Examples include SE812 manufactured by Co., Ltd. and CRC8000 manufactured by Sumitomo Bakelite Co., Ltd.

  The polyamic acid solution obtained by the synthetic reaction or put on the market is treated by heating or the like to cyclize the polyamic acid to a polyimide (imidization). The polyamic acid can be imidized by a method involving only heating or a chemical method. In the case of the method of only heating, the polyamic acid is imidized by heating at 200 to 350 ° C., for example. In addition, the chemical method is a method in which a polyamic acid is heat-treated and completely imidized while using a basic catalyst in order to promptly promote imidization. The basic catalyst is not particularly limited, and a conventionally known basic catalyst is used, and examples thereof include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), and various tertiary amines. To be These basic catalysts may be used alone or in combination of two or more.

(Photocurable resin)
The photocurable resin may be a resin that is cured by irradiation with active energy rays and exhibits electrical insulation properties. 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-based oligomers and (meth) acrylate-based oligomers. Examples of (meth) acrylate-based oligomers include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, and epoxy urethane (meth). ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene modified (meth) acrylate and the like. In addition, in this specification, (meth) acrylate is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

  As the photopolymerizable vinyl monomer, known conventional ones, for example, styrene derivatives such as styrene, chlorostyrene, 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-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide (Meth) acrylamides such as luamide 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; Alcohols such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Xyalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol Propylene tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other alkylene polyol poly (meth) acrylates; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate and other polyoxyalkylene glycol poly ( A) acrylates; poly (meth) acrylates such as hydroxybivalic acid neopentyl glycol ester di (meth) acrylates; 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 preferably used. Of these, alicyclic epoxy compounds include 3,4,3 ', 4'-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, 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.

  As the oxetane compound, 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 , (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, and polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohol and novolac resin, poly (p -Hydroxystyrene), cardo type bisphenols Examples include oxetane compounds such as calixarenes, calixresorcinarenes, and etherification products with resins having a hydroxyl group such as silsesquioxane, and copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. .

  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, cyclohexane dimethanol divinyl ether, α and / or β position Include vinyl ether compounds having a substituent such as an alkyl group and an allyl group. It 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.

  When a photocurable resin is used, a photopolymerization initiator, a photoacid generator, a photobase generator, etc. are used in addition to the above-mentioned photocurable resin, and one of these is used alone or Two or more kinds can be used in combination.

  Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoin and benzoin alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy- Acetophenones such as 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 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-butanone Aminoalkylphenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-diisopropylthioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone and other benzophenones; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- , 4,6-phosphine oxide such as trimethyl benzoyl phenyl phosphinothricin Nate; various peroxides, titanocene initiators, and the like oxime ester initiator. These are photosensitizers such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine. You may use together with agents. These photopolymerization initiators can be used alone or in combination of two or more kinds.

  Examples of the photoacid generator include onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, and 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 and 2-methyl-4,6-bis (trichloromethyl) -s-triazine; sulfonic acid 2- Trobenzyl ester; iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivative; N-hydroxyimide = sulfonate; tri (methanesulfonyloxy) benzene derivative; bissulfonyldiazomethanes; sulfonylcarbonylalkanes; sulfonylcarbonyl Examples thereof include diazomethanes, disulfone compounds, iron allene complexes and the like. These photo-acid generators can be used alone or in combination of two or more kinds.

  The photobase generator is a compound that produces one or more basic substances capable of functioning as a catalyst for a polymerization reaction by changing the molecular structure or cleaving the molecule by irradiation with light such as ultraviolet rays or visible light. Is. Examples of the basic substance include secondary amine and tertiary amine. Examples of such photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, and nitrobenzylcarbamate groups. Examples thereof include compounds having a substituent such as alcooxybenzyl carbamate group. These photobase generators can be used alone or in combination of two or more kinds.

  Examples of the organic solvent 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 and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterification products of the above glycol ethers Kinds; alcohols 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, etc. Amides; tetrahydrofuran, dioxane, and other ethers; acetonitrile, benzonitrile, propionitrile, and other nitriles, chloroform, dichloromethane, bromobenzene, dibromobenzene, chlorobenzene, dichlorobenzene, and other halogens, N-methyl-2- Amines such as pyrrolidone, dimethylaniline, dibutylaniline, diisopropylaniline; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, water Examples thereof include petroleum-based solvents such as added 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 adhesive 2 and the fiber base material 11. In the present invention, the resin 3 may cover the outside of the fiber base material 11 as long as it can play a role of ensuring the adhesion. The impregnation rate of the resin composition is not particularly limited as long as the resin-containing sheet can be adhered to a metal foil or the like, but the resin concentration in the resin-containing sheet is 10 to 99% by volume, particularly , 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 good balance.

  The resin composition that forms the resin 3 may include at least one selected from thermosetting resins, photocurable resins, and thermoplastic resins, and one type may be used alone depending on the application. Or, two or more kinds can be used in combination. Of these, thermosetting resins are preferable, and epoxy resins are more preferable, from the viewpoint of the physical properties of the cured product or molded product. 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 adhesive composition should be used appropriately. In the present invention, the resin composition and the adhesive composition may be different from each other. Further, as the thermoplastic resin, the following ones can be used.

(Thermoplastic resin)
Examples of the thermoplastic resin 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. Polymers, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid and other general-purpose plastics, polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultra high molecular weight polyethylene, polybutylene terephthalate, modified polyphenylene ether, polysulfone ( PSF), polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone, polyalley , Engineering plastics such as polyetherimide, polyamideimide, liquid crystal polymer, polyamide 6T, polyamide 9T, polytetrafluoroethylene, polyvinylidene fluoride, polyesterimide, thermoplastic polyimide, olefin series, styrene series, polyester series, urethane series, Examples thereof include amide type, vinyl chloride type and hydrogenated type thermoplastic elastomers. In the present invention, a resin composite can be used, and for example, as a resin composite of a thermosetting resin and a thermoplastic resin, epoxy resin-PSF, epoxy resin-PPS, epoxy resin-PES, etc. can be used.

  A colorant may be added to the adhesive composition and the resin composition according to the present invention as another component.

  As the coloring agent, known and commonly used coloring agents such as coloring pigments and dyes represented by a color index 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, 169, 1 2, 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, 53: 1, 3: 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.

  Further, in the adhesive composition and the resin composition according to the present invention, if necessary, conventional additives such as defoaming / leveling agents, thixotropy-imparting agents / thickeners, coupling agents, dispersants, flame retardants, etc. are added. Agents can be included.

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

  As thixotropy-imparting agents / thickeners, clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, zeolite, amorphous inorganic particles, polyamide-based additives, modified urea-based additives, wax-based additives Etc. can be used.

  The coupling agent is a methoxy group, an ethoxy group, acetyl or the like as an alkoxy group, and a vinyl, methacryl, acryl, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureide, sulfide as a reactive functional group. Isocyanates and the like, for example, vinyl silane, vinyl trimethoxysilane, vinyl trimethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxylane, and other silane compounds, γ-aminopropyltrimethoxylane, Amino-based silane compounds such as Ν-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane and γ-ureidopropyltriethoxysilane, γ-glycid Xypropyl propylamine Silanes, epoxy-based silane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, mercapto-based silane compounds such as γ-mercaptopropyltrimethoxysilane, Ν- Silane coupling agents such as phenylamino-based silane compounds such as phenyl-γ-aminopropyltrimethoxysilane, isopropyltriisostearoylated titanate, tetraoctylbis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate , Isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, te La (1,1-diallyloxymethyl-1-butyl) bis- (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tristearoyl diacryl Titanate coupling agents such as titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, dicumyl phenyloxyacetate titanate, diisostearoyl ethylene titanate, ethylenically unsaturated zirconate containing compounds, neoalkoxy zirconate containing compounds. , Neoalkoxy tris neodecanoyl zirconate, neoalkoxy tris (dodecyl) benzenes Ruphonyl 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) phosphato zirconate, neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphato zirconate, neopentyl (di Ryl) 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-propenolate methyl) Zirconate coupling agents such as butanolato, cyclodi [2,2- (bis2-propenolatomethyl) butanolato] pyrophosphato-O, O, diisobutyl (oleyl) acetoacetylaluminate, alkylacetoacetate Diisopropylate aluminate coupling agents such like.

  Examples of the dispersant include polycarboxylic acid type, naphthalene sulfonic acid formalin condensation type, polyethylene glycol, polycarboxylic acid partial alkyl ester type, polyether type, polyalkylene polyamine type and the like polymeric dispersants, alkyl sulfonic acid type, four A low molecular type dispersant such as a quaternary ammonium type, a higher alcohol alkylene oxide type, a polyhydric alcohol ester type or an alkyl polyamine type can be used.

  Examples of flame retardants include hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound system, bromine compound system, chlorine compound system, phosphate ester. , Phosphorus-containing polyols, phosphorus-containing amines, melamine cyanurate, melamine compounds, triazine compounds, guanidine compounds, silicone polymers and the like can be used.

  The adhesive composition and the resin composition according to the present invention are also inorganic fillers such as barium sulfate, silica and hydrotalcite, nylon powders, organic fillers such as fluorine powder, radical scavengers, ultraviolet absorbers and peroxides. Material decomposition agents, thermal polymerization inhibitors, adhesion promoters, rust preventives, surface treatment agents, surfactants, lubricants, antistatic agents, pH adjusters, antioxidants, dyes, pigments, fluorescent agents, etc. It may be contained within a range that does not impair the object of the invention.

[Storage modulus]
In the present invention, the storage elastic modulus of the adhesive 2 needs to be higher than the storage elastic modulus of the resin 3. Here, the storage elastic modulus of the adhesive agent 2 means the storage elastic modulus of a cured film obtained by curing the composition containing only the components of the adhesive composition without the fiber 1 after the film formation by heat or light. To do. Similarly, regarding the storage elastic modulus of the resin 3, in the case of a curable resin, it means the storage elastic modulus of a cured film cured by heat or light after film formation, and in the case of a thermoplastic resin, a melt film formation. It means the storage elastic modulus of a coating film obtained by removing the solvent later. Further, the storage elastic modulus is an index value of hardness of a sample, and an evaluation called dynamic viscoelasticity measurement in which a cyclic load is applied to the sample while a constant temperature change is applied to detect strain is used. It is a value calculated from the detected strain, and it means that the higher this value is, the more excellent the mechanical strength is. In the present invention, the storage elastic modulus of the adhesive agent 2 may be higher than the storage elastic modulus of the resin 3 at any temperature, and the preferable range thereof is 30 to 30 for the adhesive agent 2. 0.1 GPa, more preferably 20 to 0.5 GPa, the storage elastic modulus of the resin 3 is 10 to 0.001 GPa, more preferably 5 to 0.01 GPa, at any temperature, It is preferable that the storage elastic modulus of the adhesive 2 is larger than that of the resin 3 by 0.1 GPa or more. In particular, it is preferable that the storage elastic modulus of the adhesive 2 is higher than the storage elastic modulus of the resin 3 at any temperature within the range of 150 to 250 ° C., and in 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. As a result, the resin-containing sheet of the present invention can be used even in a high temperature range of 150 to 250 ° C., so that the application is widened, which is preferable.

[Glass-transition temperature]
In the present invention, the glass transition temperature of the adhesive 2 is preferably higher than the glass transition temperature or softening temperature of the resin 3. Here, the glass transition temperature of the adhesive agent 2 means the glass transition temperature of a cured film obtained by curing a composition containing only the components of the adhesive agent composition without including the fiber 1 after the film formation by heat or light. To do. Similarly, regarding the glass transition temperature or softening temperature of the resin 3, in the case of a curable resin, it means the glass transition temperature of a cured film cured by heat or light after film formation, 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 the loss elastic modulus (E ″) obtained from the dynamic viscoelasticity measurement described above. Tangent) is the maximum temperature, and the higher this temperature is, the better the heat resistance is. In the present invention, the upper limit of the glass transition temperature is not particularly limited, but the preferred range is 130 ° C. or higher, more preferably 140 ° C. or higher, particularly preferably 250 ° C. for the glass transition temperature of the adhesive 2. ℃ or 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, and more preferably 80 ° C. or higher. Further, it is preferable that the glass transition temperature of the adhesive 2 is 5 ° C. or more higher than the glass transition temperature or the 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 base material 11 with the adhesive composition to fix the fibers 1 to each other, and then impregnating the fixed fiber base material 11 with the resin composition. it can. The resin-containing sheet of the present invention, for example, in a state where fibers are arranged on an object to be coated such as a carrier film, the adhesive composition and the resin composition are sequentially applied and impregnated to obtain the adhesive composition and the resin composition. It can be produced as a dry film by volatilizing and drying the organic solvent contained therein, and if desired, a cover film may be further laminated thereon. At this time, as long as the resin composition does not impair the fixing performance of the fixing agent composition to the fibers, the coating process of the resin composition may be performed before or after drying the fixing agent. But it's okay.

  In this case, the adhesive composition and the resin composition of the present invention can be coated by adjusting the viscosity suitable for the coating method by blending, dispersing, and diluting each component, if necessary. As described above, the adhesive composition may be one that can be penetrated into the fiber base material 11 to fix the fibers 1 to each other, and the resin composition may be at least one of the fiber base materials 11. Any surface can be adhered to the metal foil or the like, particularly both surfaces.

  A carrier film for a dry film is preferable as the article to be coated, but it may be directly coated on the surface of the metal foil or the surface of the circuit-formed wiring board. 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 method. And various coating methods such as a comma coating method and a film coating method, and various printing methods such as screen printing, spray printing, inkjet printing, letterpress printing, intaglio printing, and lithographic printing.

  As the carrier film and the cover film, known materials used for the dry film can be used, 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 it is preferable that the cover film has a smaller adhesiveness with 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 the substrate. Examples of the substrate include a metal foil substrate and a circuit substrate (circuit-formed wiring board). The resin-containing sheet of the present invention can be thermally adhered to the surface of the substrate to form a resin insulating layer, and by repeating the process, the metal foil layer and the resin insulating layer can be laminated in a plurality of layers. It should be noted that the resin-containing sheet may be laminated with the resin-containing sheets when it is manufactured on the carrier film, or may be laminated with the resin-containing sheets when they are adhered to a metal foil or the like.

  When a structure is produced using the resin-containing sheet of the present invention, when the adhesive composition and the resin composition are a combination of a thermosetting resin or a photocurable resin, only a method of heat curing, the activity A structure can be manufactured by using a method of only irradiation with energy rays, a method of heating and curing after irradiation of active energy rays, or a method of irradiating with active energy rays after heating and curing. When a dry film is used, the cover film is peeled off if there is a cover film, the resin-containing sheet is heat-adhered to the substrate surface, then the carrier film is peeled off, and the composition is cured by the above-mentioned curing method. The body can be manufactured. When a thermosetting resin is used as both the adhesive composition and the resin composition, both heat curing processes of fixing the fibers to each other and impregnating the resin may be performed at the same time. Regarding the heating temperature when performing heating, there is no particular lower limit or upper limit as long as the fibers and the adhesive contained in the target substrate are not decomposed by high heat, and when performing active energy ray irradiation. With respect to the exposure amount, the lower limit and the upper limit are not particularly limited as long as the exposure amount is too low and an uncured portion does not occur.

  Further, when the resin-containing sheet of the present invention is produced, when the resin composition is a thermoplastic resin, a method of heating or heating and press-bonding the pellet-shaped or sheet-shaped thermoplastic resin can also be used. Here, in order to impregnate the thermoplastic resin into the fibrous base material fixed by the fixing agent, it is not essential to apply pressure using a device, but by applying pressure, the fiber base of the thermoplastic resin Penetration into the material becomes easier. When applying pressure, there is no particular upper limit to the pressure as long as the intended shape of the resin-containing sheet is not impaired. The structure can be molded by thermally adhering the resin-containing sheet to the surface of the substrate. Further, when the structure is molded using the dry film, it can be manufactured in the same manner as described above.

  In addition, in the above, as an apparatus used at the time of drying, heat-hardening, or heat-pressurizing, a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, a heating / pressurizing roll, a press machine, etc. can be mentioned. 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, a laser beam or the like can be used as the active energy ray.

  The thickness of the dry film is not particularly limited, with regard to the fiber base material that 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”), and the thickness of the dry film. It can be appropriately selected depending on, but especially for the intermediate, as long as the fibers are fixed to each other by a fixing agent, its thickness is equal to the thickness of the fiber base material, or the fiber It is preferable that the thickness is not more than twice the thickness of the base material. Specifically, it is more preferably within the range of 1 to 1.5 times the thickness of the fiber base material. When the thickness of the intermediate body exceeds twice the thickness of the fiber base material, the physical properties of the adhesive itself are affected, which is not preferable.

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

  The resin-containing sheet of the present invention having the above-described structure can be applied to a wiring board or the like for electronic devices, and is preferably applied to, for example, an interlayer insulating material for a wiring board, a solder resist, or a core material. Therefore, the intended effect of the present invention can be obtained. In addition, for example, the fibers are fixed to each other with a fixing agent composition, the resin is permeated and dried to form a resin insulating layer in a semi-cured state (B stage), and the resin insulating layer and the metal foil are laminated and pressed. Thus, a multi-layer board can be manufactured.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples, but the present invention is not limited to these Examples, Reference Examples and Comparative Examples. In addition, all the compounding amounts in the following tables indicate parts by mass.

[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 that had been replaced with nitrogen, and 4,4′-diaminodiphenyl ether (ODA) (wa Kou Pure Chemical Industries, Ltd.) and 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) (Wako Pure Chemical Industries, Ltd.) were mixed at a molar ratio of 1: 1 at room temperature. After stirring for 16 hours or more, a polyamic acid varnish 1 having a resin solid content ratio of 7.5 mass% was obtained.

[Synthesis of Polyamic Acid Varnish 2]
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 that was purged with nitrogen, and p-phenylenediamine (PDA) (Wako Pure Chemical Industries, Ltd.) Co., Ltd.) and 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride (BPDA) (manufactured by Wako Pure Chemical Industries, Ltd.) at a molar ratio of 1: 1 and mixed at room temperature. After stirring for 16 hours or more, a polyamic acid varnish 2 having a resin solid content ratio of 7.5 mass% was obtained.

[Preparation of adhesive composition or resin composition]
Table 1 below shows the content of the compositions 1 to 4 used as the adhesive 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 multi-component system of the composition 1, the components were blended and then prepared by stirring using a rotation / revolution mixer.

[Preparation of test piece 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.
The composition 1 was dried in a hot air circulation type drying oven at 80 ° C. for 30 minutes under atmospheric conditions and then heated at 150 ° C. for 60 minutes under atmospheric conditions to obtain an epoxy resin cured product. When the copper foil was removed, the thickness was 50 μm. Using this cured product, a test piece for evaluation such as storage elastic modulus having a width of 5 mm and a length of 50 mm was prepared.
With regard to the composition 2, after coating, it was dried in a hot-air circulation type drying oven at 80 ° C. for 30 minutes under atmospheric conditions, and then heated at 250 ° C. for 60 minutes under nitrogen conditions (100 ml / min.) To give an imidized product. Obtained. When the copper foil was removed, the thickness was 50 μm. Then, an evaluation test piece was prepared in the same manner as above.
With respect to the composition 3, a test piece for evaluation was prepared in the same manner as the composition 2 except that the heating operation was performed under a nitrogen condition at 300 ° C. for 60 minutes.
With regard to the composition 4, high-density polyethylene pellets (specific gravity 0.95) were put into a press in an appropriate amount, heated and pressurized at 140 ° C. for 3 MPa for 3 minutes, and then cooled to room temperature to obtain a molded body, which was then cut into individual pieces. As a result, the thickness was 50 μm. Then, an evaluation test piece was prepared in the same manner as above.

[Production of resin-containing sheet and test piece for evaluating storage elastic modulus of sheet]
Tables 2 and 3 below show the configurations of the resin-containing sheets or sheets of Examples, Reference 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, it is dried in a hot air circulation type drying oven at 80 ° C. for 30 minutes under atmospheric conditions, and then heat-cured at 150 ° C. for 60 minutes to remove the glass cloth and the adhesive (cured product of the epoxy resin composition). The following intermediate was prepared.

(Preparation of intermediate of Example 2-A)
Regarding 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 80 in a hot air circulation drying furnace. After drying under atmospheric conditions at 30 ° C. for 30 minutes, it was heated at 250 ° C. for 60 minutes to imidize to prepare an intermediate body composed of glass cloth and a fixing agent (polyimide).

(Preparation of intermediate of Example 3-A)
Regarding 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 80 in a hot air circulation type drying furnace. After drying under atmospheric conditions at 30 ° C. for 30 minutes, it was imidized by heating at 300 ° C. for 60 minutes to prepare an intermediate body composed 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 above composition 1 was used to prepare an intermediate body composed of a glass cloth and a fixing agent (cured product of epoxy resin composition).

  The thickness of each intermediate of Examples 1-A to 3-A and Comparative Example 4-A was 33 to 35 μm, and the increase in the thickness from the thickness of the glass cloth was a slight 3 to 5 μm.

(Preparation of Intermediate of Reference Example 1-B)
Regarding Reference Example 1-B in Table 3 below, the aramid nonwoven fabric was treated in the same manner as in the preparation of the intermediate body of Example 1-A except that an aramid nonwoven fabric (Nomex 410, thickness 50 μm) was used as the fiber. Then, an intermediate body comprising a fixing agent (cured product of epoxy resin composition) was prepared.

(Preparation of Intermediate of Reference Example 2-B)
For Reference Example 2-B in Table 3 below, 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 Reference Example 1-B was used as the fiber. An intermediate body made of a non-woven fabric and a fixing agent (polyimide) was prepared.

(Preparation of Intermediate of Reference Example 3-B)
For Reference Example 3-B in Table 3 below, 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 Reference Example 1-B was used as the fiber. An intermediate body made of a non-woven fabric and a fixing agent (polyimide) was prepared.

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

  The thickness of each intermediate of Reference Examples 1-B to 3-B and Comparative Example 4-B was 53 to 56 μm, and the increase in thickness from the thickness of the aramid non-woven fabric was slight to 3 to 6 μm.

(Production of Resin-Containing Sheet or Sheet of Each Example, Reference Example and Comparative Example)
For Example 1-A and Reference Example 1-B, the composition 4 was put into a press machine, melted at 140 ° C., and then impregnated into each of the intermediates obtained above, and 140 ° C., 3 MPa. After heating and pressurizing for 3 minutes and then cooling to room temperature, a resin-containing sheet in which a resin (high-density polyethylene resin) was impregnated in a glass cloth or aramid nonwoven fabric fixed with a fixing agent (epoxy) was produced.
For Example 2-A, Reference Example 2-B, Example 3-A and Reference Example 3-B, the composition 1 was added to each intermediate obtained above in an appropriate amount so as to spread over the entire fiber. By applying and impregnating with, and heating and curing under the same conditions as in the preparation of the above-mentioned adhesive or resin evaluation test piece, the glass cloth or aramid non-woven fabric fixed with the adhesive (polyimide) is applied to the resin (epoxy resin). A resin-containing sheet impregnated with a cured product) was produced.
The thickness of each resin-containing sheet of Examples 1-A to 3-A and Reference Examples 1-B to 3-B was 5 to 10 μm thicker than the thickness of the intermediate body. Then, for each resin-containing sheet, an evaluation test piece was prepared under the same conditions as 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 spread over the entire fiber, and impregnated with the composition 1 for evaluation of the adhesive or the resin. A sheet was prepared by impregnating a glass cloth or an aramid non-woven fabric containing no fixing agent with a resin (cured product of epoxy resin) by heating and curing under the same conditions as the preparation of the test piece.
For Comparative Example 2-A and Comparative Example 2-B, a glass cloth or an aramid non-woven fabric was coated with and impregnated with the above composition 2 in the same manner as in Comparative Example 1-A, and then 80 ° C. in a hot air circulation drying oven. After drying under atmospheric conditions for 30 minutes, heating at 250 ° C. for 60 minutes under atmospheric conditions to imidize, and a sheet in which a resin (polyimide) was impregnated into a glass cloth or an aramid nonwoven fabric containing no adhesive was produced.
For Comparative Example 3-A and Comparative Example 3-B, the composition 4 was put into a press and melted at 140 ° C., and then impregnated with a glass cloth or an aramid nonwoven fabric, and 140 ° C., 3 MPa, 3 minutes. After heating and pressurizing, cooling to room temperature produced a sheet in which a resin (high-density polyethylene resin) was impregnated in a glass cloth or aramid nonwoven fabric containing no adhesive.
Regarding Comparative Example 4-A and Comparative Example 4-B, except that the glass cloth or aramid non-woven fabric in Comparative Example 2-A and Comparative Example 2-B was used instead of the intermediate having the adhesive agent comprising Composition 1 above. Produced a resin-containing sheet in the same manner as in Comparative Examples 2-A and 2-B.
Then, for each sheet, a test piece for evaluation was prepared in the same manner as above.

  In addition, as shown in Tables 2 and 3 below, the resin component concentrations are about the same for Examples 1-A to 3-A and Comparative Examples 1-A to 4-A, and Reference Example 1- The same was true for B to 3-B and Comparative Examples 1-B to 4-B. Here, the resin content concentration is the amount of adhesive = {1- (volume of fiber base material / volume of intermediate)} × 100 [volume%], amount of resin = {1- (volume of intermediate / resin-containing sheet) Or the volume of the sheet) × 100 [volume%] (volume is converted based on mass and specific gravity).

[Measurement of storage elastic modulus]
Using a test piece for evaluating the storage elastic modulus of the adhesive agent or the resin, using a tensile mode of a DMA viscoelasticity measuring device (manufactured by Hitachi High-Tech Science, DMA7100), a measurement frequency of 1 Hz, a minimum tension and a minimum compression force of 200 mN, The viscoelasticity was measured under atmospheric conditions with a strain amplitude of 10 μm, a temperature rising rate of 5 ° C./minute, and storage elastic moduli at 50 ° C., 150 ° C. and 250 ° C. were obtained, as well as 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, Mitsubishi Chemical Co., Ltd. * 2: 2-Ethyl-4-methylimidazole, Shikoku Kasei Co., Ltd. * 3: Wako Pure Chemical Industries, Ltd. * 4: Specific gravity 0.95

[Evaluation of storage elastic modulus of resin-containing sheet or sheet]
For the resin-containing sheet or the test piece for sheet evaluation, the test piece was attached so that the bias (oblique) direction of the fiber of the glass cloth or aramid nonwoven fabric in the sheet was the tensile direction of the device, and the minimum tension and compression force were 50 mN. The viscoelasticity was measured in the same manner as above except that the storage elastic moduli at 50 ° C., 150 ° C. and 250 ° C. were obtained. Here, the measurement in the bias (oblique) direction is to eliminate the influence of the elastic modulus of the fiber base material as much as possible and to investigate the influence of the elastic modulus improvement due to the sticking effect. In each of the Examples and Reference Examples, when the storage elastic modulus E [GPa] has a large value when compared with the sheet of the Comparative Example to which the adhesive is not attached, the value is ◯, and when the value is small, the value is x.

More specifically, the resin-containing sheet of Example 1-A has a storage elastic modulus at any temperature of 50 ° C., 150 ° C., and 250 ° C. more than that of the sheet of Comparative Example 3-A in which no adhesive was used. Since the value of the rate E [GPa] is large, it was set to “◯”.
Also in Reference Example 1-B, the value of the storage elastic modulus E [GPa] was larger than that of the sheet of Comparative Example 3-B in which no fixing agent was used, and thus was set to “◯”.
Also in the resin-containing sheets of Example 2-A, Reference Example 2-B, Example 3-A, and Reference Example 3-B, the sheets of Comparative Examples 1-A and 1-B in which no adhesive was used were used. Since the value of the storage elastic modulus E [GPa] is large in comparison, it was set to “◯”.
On the other hand, the resin-containing sheet of Comparative Example 4-A has a storage elastic modulus E [GPa at any temperature of 50 ° C., 150 ° C., and 250 ° C. as compared with the sheet of Comparative Example 2-A in which no adhesive was used. Since the value of], becomes small, it was set as “x”.
Also in the resin-containing sheet of Comparative Example 4-B, "x" was given as 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.

  As a reference, when the above measurement was performed using only glass cloth, the value of the storage elastic modulus could not be obtained because the fiber knitted at the start of the measurement was unraveled by the tension in the bias direction.

[Preparation of test piece for adhesion evaluation]
The adhesive composition was applied and impregnated in the same manner as above except that the glass cloth or the aramid non-woven fabric as the fiber base material was placed on the carrier film to produce each intermediate. After that, the resin composition was molded or applied on the surface of the dried adhesive, dried, and then a cover film was attached to obtain a dry film. A surface-untreated copper foil having a thickness of 18 μm was superposed on both sides of this dry film (the carrier film and the cover film were peeled off when they were brought into close contact), and the pressurizing condition was 1 MPa and the heating condition was 150 ° C. × 10 minutes for 1-A and Reference Example 1-B, 250 ° C. × 60 minutes for Example 2-A and Reference Example 2-B, Comparative Examples 4-A and 4-B, Example 3- About A and Reference Example 3-B, it shape | molded at 300 degreeC x 60 minutes, and produced the adhesiveness evaluation test piece which the resin layer and the copper foil adhered. Further, for Comparative Examples 1-A to 3-A and Comparative Examples 1-B to 3-B, dry films were prepared in the same manner except that the adhesive composition was not applied and impregnated, and pressed with a vacuum press, Adhesion evaluation test pieces were prepared under the same temperature conditions as the sheet preparation of 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 at the time of peeling the resin layer and the surface untreated copper foil at the interface was measured at a peel angle of 90 ° and a peel speed of 50 mm / min. The case of m or more was ◯, and the case of less than 0.5 kN / m was x. The results are shown in Tables 2 and 3 below. It can be said that when the peel strength is high, the adhesion to follow unevenness is excellent and the adhesion to the copper foil is excellent.

  As shown in Tables 2 and 3 above, the storage elastic moduli of the adhesives of Examples 1-A to 3-A and Reference Examples 1-B to 3-B are all larger than the storage elastic moduli of the resins, On the other hand, in Comparative Examples 4-A and 4-B, the storage elastic modulus of the adhesive agent is smaller than the storage elastic modulus of the resin. Further, in Comparative Examples 1-A to 3-A and 1-B to 3-B, only the resin was used and the adhesive was not used.

As shown in Tables 2 and 3 above, Examples and Reference Examples in which a glass cloth or an aramid non-woven fabric was fixed using a fixing agent having a storage elastic modulus of the fixing agent higher than that of the resin, and further impregnated with the resin. It can be seen that the resin-containing sheet of No. 2 has excellent adhesiveness and a large storage elastic modulus as compared with the sheet of Comparative Example in which only the resin is impregnated.
For example, as is clear from comparison between Example 1-A and Comparative Example 3-A, the fibers of the glass cloth were fixed to each other by the fixing composition, and the fiber base material was impregnated with the resin composition. It was found that the resin-containing sheet has high storage strength at any temperature as compared with Comparative Example 3-A in which the fibers of the glass cloth are not fixed by the fixing composition, and thus has high mechanical strength.
In particular, the resin-containing sheets of Examples 2-A, 3-A and Reference Examples 2-B, 3-B have a storage elastic modulus at 250 ° C of more than 1 GPa and are also excellent in mechanical strength at high temperature. I understand. On the other hand, in Comparative Example 4-A and Comparative Example 4-B in which the storage elastic modulus of the adhesive 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 also poor.

  From the above, using a resin-containing sheet having a fixing agent for fixing the fibers in the fiber base material and a resin in contact with the fixed fibers, and the storage elastic modulus of the fixing agent is higher than the storage elastic modulus of the resin. It was confirmed that it is possible to realize excellent mechanical strength, elastic modulus and adhesion. The resin-containing sheet of the present invention can be applied to a wiring board for electronic devices and the like, and can be suitably applied to, for example, an interlayer insulating material for wiring boards, a solder resist, and a core material.

1, 21 fiber 2 adhesive 3 resin 11 fiber base material P contact point D direction in which fibers are separated by tension T space S space

Claims (6)

Fiber substrate different from wholly aromatic polyamide fiber,
A fixing agent for fixing the fibers in the fiber base material to each other,
A resin in contact with the fiber base material and the adhesive,
A resin-containing sheet, wherein the storage elastic modulus of the adhesive 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 the softening temperature of the resin.   The resin-containing sheet according to claim 1, which is obtained by fixing the fibers of the fiber base material to each other with a fixing agent composition, and then impregnating the fixed fiber base material with the resin composition.   The resin-containing sheet according to claim 1, wherein the fiber base material includes a woven fabric or a non-woven fabric.   A structure comprising the resin-containing sheet according to claim 1 adhered to a substrate. A wiring board comprising the structure according to claim 5 .

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