KR102338789B1 - Resinous sheet, and structure and wiring board each including same - Google Patents

Abstract

Provided are a resin-containing sheet having improved adhesion to a substrate while improving the mechanical strength of a fiber substrate, and a structure and a wiring board using the same. It has a fiber base 11, a fixing agent 2 for fixing the fibers 1 in the fiber base 11, and a resin 3 in contact with the fiber base 11 and the fixing agent 2, and a fixing agent (2) is a resin-containing sheet whose storage elastic modulus is higher than the storage elastic modulus of the resin (3). It is a structure obtained by making this resin-containing sheet|seat closely_contact|adhere to a board|substrate. It is a wiring board which has this structure.

Description

A sheet containing resin, and a structure and a wiring board using the same

The present invention relates to a resin-containing sheet having excellent mechanical strength, elastic modulus and adhesiveness and suitable for wiring boards for electronic devices and the like, and to structures and wiring boards using the same.

As a wiring board for electronic devices, in general, a prepreg (resin insulating layer in a semi-cured state) obtained by impregnating a substrate containing glass fibers, aramid fibers, cellulose fibers, etc. with a resin such as epoxy is applied to a metal foil such as copper. What was made to adhere|attach and the circuit formed by the etching method is used. Moreover, in order to prevent the outflow of the solder at the time of component mounting, the soldering resist is provided in the wiring board. It is necessary to make these wiring board materials, such as a prepreg and a soldering resist, closely_contact|adhere with respect to the metal foil surface or the circuit-formed wiring board surface without a gap, heat-pressing, and adhesiveness at that time becomes important. Moreover, in order to improve mounting reliability, what is high strength (high modulus of elasticity) is desired for a wiring board, and high modulus-ization is aimed at similarly also about the prepreg and soldering resist which are the structural members.

As a prior art related to a wiring board material, for example, Patent Document 1 describes a prepreg in which resin layers of different strengths (modulus of elasticity) are provided on both surfaces of a core layer in order to obtain both functions of insulation reliability and stress relaxation with wiring. has been However, this technique provides layers of a different resin composition on both surfaces of a core layer, and there is no indication that it is useful for adhesiveness. In addition, Patent Document 2 describes a prepreg having a predetermined elastic modulus. This technique is for the purpose of temporarily fixing a prepreg sheet and a circuit board, and controlling the elastic modulus with a composition.

Moreover, patent document 3 discloses the technique of using 2 types of resin compositions in a prepreg. In this prepreg, two types of resin compositions are unevenly distributed so that the elastic modulus becomes large as the surface side. Furthermore, Patent Document 4 describes a technique for providing an adhesive layer on the surface of a prepreg in order to improve adhesion with metal foil.

Japanese Patent Laid-Open No. 2008-088280 Japanese Patent Laid-Open No. 2006-179716 Japanese Patent Laid-Open No. 2010-095557 Japanese Patent Laid-Open No. 2004-168943

However, the conventional prepreg could not have sufficient mechanical strength and adhesion.

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

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following, as a result of earnestly examining in order to solve the said subject.

That is, in general, in a woven fabric or nonwoven fabric containing various fibrous materials, fibers are entangled or interact to form an aggregate. Therefore, as shown in Fig. 2(a), when a tension T is applied to such an aggregate of fibers 21 in one direction, the fibers 21 slide at the contact point P, and the fibers 21 in the direction of the arrow D. ) are separated, and disorder occurs in the aggregate, and eventually breaks. In this respect, in the case of a woven fabric, the strength with respect to tension in the fiber direction is somewhat high, but the strength with respect to tension in a direction different from the fiber direction (warp direction) is low. Moreover, in the case of a nonwoven fabric, also in any direction, the intensity|strength with respect to tension is low.

As described above, since the wiring board uses a woven fabric such as glass cloth, a nonwoven fabric containing aramid fibers, etc., and a resin-containing sheet such as a prepreg containing a resin, in order to secure the strength of the wiring board, in the aggregate of fibers, It becomes important to prevent the fibers from sliding between each other. 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 said examination, the present inventors discovered that mechanical strength and adhesiveness could be balanced by setting it as the following structures.

That is, the resin-containing sheet of the present invention has a fiber substrate, a fixing agent for fixing the fibers in the fiber substrate to each other, and a resin in contact with the fiber substrate and the fixing agent, and the storage elastic modulus of the fixing agent is higher than the storage elastic modulus of the resin. it is characterized by

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 with a fixing agent composition, and then impregnating the fixed fiber base with a 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 characterized in that it is obtained by bringing the resin-containing sheet of the present invention into close contact with a substrate.

Further, the wiring board of the present invention is characterized in that it has the above-described structure of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, it became possible to obtain the resin containing sheet|seat which improved adhesiveness with a board|substrate, improving mechanical strength. That is, in the present invention, by making the storage elastic modulus of the fixing agent for fixing the fibers in the fiber base material to each other higher than the storage elastic modulus of the resin in contact with the fiber substrate and the fixing agent, high strength and high modulus of elasticity are achieved, and the resin in which adhesion is also improved. The material conditions for obtaining the containing sheet were discovered. This is because high strength is required for resin insulating materials for wiring boards, but for example, when a high modulus material such as polyimide is used, the adhesion to metal foil is deteriorated. In the present invention, while realizing high modulus of elasticity, this It solves the adhesion problem.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows modelly the structure of the resin containing sheet|seat of this invention.
Fig. 2 is an explanatory view modelly showing the behavior of fibers (a) and (b) when fibers are not fixed to each other when a tension T is applied to an aggregate of fibers in one direction.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail, referring drawings.

Fig. 1 is an explanatory diagram 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 formed of a fiber component and a resin component, and as shown in the figure, a fiber base 11 and a fixing agent 2 for fixing the fibers 1 in the fiber base 11 and the 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 which is not impregnated in neither the fixing agent 2 nor the resin 3 in the fiber base material 11. As shown in FIG. In the resin-containing sheet of the present invention, it can be said that the fibers 1 constituting the fiber base 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 for fixing the fibers 1 to each other is higher than the storage elastic modulus of the resin 3 at any one temperature.

That is, as a result of intensive studies by the present inventors, there are two roles of the resin component contained in the resin-containing sheet, and one is a role as a fixing agent for suppressing slipping between fibers and making the resin-containing sheet high strength and high modulus of elasticity. , found that the other was the role of bonding the insulating resin layer to the surface of the metal foil, etc. From this point of view, as a result of further investigation by the present inventors, the two roles of the resin component contained in the resin-containing sheet are assigned to the fixing agent for securing high strength and to the resin for securing adhesion, respectively, and By prescribing the relationship of the storage elastic modulus, it has discovered that both these performances can be ensured favorably. Thus, the technique which divided the role of a resin component into two and made the high elastic modulus and favorable adhesiveness compatible is not known conventionally.

As shown in Fig. 2 (b), when the present invention is conceptually described, by fixing the contact point P of the fiber 1 included in the fiber base 11 with the fixing agent 2, a tension T is applied in one direction. Even in a case, since slippage does not generate|occur|produce at the contact point P, the fiber base material 11 can be made into high strength and high modulus of elasticity. Furthermore, by impregnating the resin 3 so as to be in contact with the fiber base 11 and the fixing agent 2, good adhesion as a resin-containing sheet can also be obtained. Therefore, according to the resin-containing sheet of the present invention, adhesiveness to a substrate or the like can be ensured by the resin 3 while ensuring the high elastic modulus required for the fiber base 11 by the fixing agent 2, It became possible to obtain the resin-containing sheet|seat which had both high strength and favorable adhesiveness, which was not obtained by using high elastic modulus material, such as a mid|middle.

[Fiber base]

The fiber base 11 according to the present invention includes 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 nonwoven fabric, and mainly natural fibers or chemical fibers can be used. Among the specific examples of the fiber (1), natural fibers include glass fibers, cellulose fibers, rock fibers, metal fibers, carbon fibers, and rock wool, and chemical fibers include aramid, nylon, vinylon, vinylidene, and polyester. , polyolefin (polyethylene terephthalate, modified polyethylene terephthalate, polyethylene, polypropylene, etc.), polyurethane, acrylic, polyvinyl chloride, polyether ether ketone, polyamideimide, polyphenylene sulfide, polyetherimide, polytetrafluoro ethylene, acetate, triacetate, promix, rayon, cupra, polynosic rayon, lyocell, tencel, and the like, and one of these may be used alone or in combination of two or more. In addition, about the manufacturing method, fiber content (fiber compounding ratio), fiber diameter, fiber length, mass (basic weight), density (specific gravity), thickness, and the woven structure of a woven fabric, it can select suitably according to the objective. As the fiber base material 11, glass fiber, a cellulose fiber, and an aramid fiber are preferable from a viewpoint of affinity with a fixing agent among the above.

In the present invention, in particular, it is preferable to use a woven fabric as the fiber base 11, and by adding weaving, an advantage of increasing the strength of even a fiber having a low original strength is obtained. Further, in the present invention, even when an organic fiber having a low strength is used as the fiber base material 11 instead of a glass fiber having high strength, there is also an advantage that strength can be increased by using a fixing agent having a high storage elastic modulus.

[Fixing agent composition]

The fixing agent composition for forming the fixing agent 2 may be any material that can adhere to the fibers 1 and allow the fibers 1 to adhere to each other, or may only adhere to contact portions where the fibers are in contact with each other, or the fibers 1 It may cover and fix the whole of. As the amount of the fixing agent composition used, it is sufficient that the fibers 1 can be fixed to each other and the adhesiveness is not adversely affected. As a solid content, it is preferable that the volume ratio of the fiber (1) and the fixing agent (2) is in the range of 99:1 to 50:50, especially in the range of 99:1 to 60:40. When the volume ratio of the fibers (1) to the fixing agent (2) is within this range, the fibers (1) are sufficiently fixed by the fixing agent to obtain a desired high strength, and good adhesion is achieved by subsequent impregnation of the resin (3). It is preferable to be something that can be secured. In particular, it is preferable that the amount of use of the fixing agent 2 is such that the film thickness of the fiber base 11 does not substantially change before and after application of the fixing agent 2 . Here, the fact that the film thickness does not substantially change means that the change in the film thickness does not include the case where the fiber base 11 swells with the solvent component of the fixing agent composition to increase the apparent thickness. Moreover, it is preferable that it is a liquid when making a fixing agent composition adhere to a fiber, and what can be used as a liquid by changing temperature or pressure may be sufficient. In particular, it is preferable that the viscosity of the fixing agent composition measured at 25° C. with a rotor rotation speed of 5 rpm in an E-type viscometer is 1 Pa·s or less, for example, 1 to 0.0001 Pa·s, whereby the fibers (1 ), the fixing agent composition can be impregnated to the inside of the aggregate, and fibers can be more reliably fixed to each other.

Also, the fixing agent composition is cured by heat or light. Curing here means chemical change from a liquid to a solid by the energy of heat or light. As a fixing agent composition, a conventional component can be used according to the use, and can be used individually by 1 type or in combination of 2 or more type. Common components used in the fixing agent composition include, for example, thermosetting resins, curing agents, thermosetting catalysts, photocurable resins, photoinitiators, photoacid generators, photobase generators, organic solvents, and the like. Specifically, What is shown below can be used.

(thermosetting resin)

The thermosetting resin should just be a resin which is hardened by heating and shows electrical insulation, for example, bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol Novolak-type epoxy resins, such as bisphenol-type epoxy resins, such as P-type epoxy resin and bisphenol Z-type epoxy resin, bisphenol A novolak-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolac epoxy resin, biphenyl-type epoxy resin , Biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, tetraphenylolethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin Resin, adamantane-type epoxy resin, fluorene-type epoxy resin, glycidyl methacrylate copolymerized epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymerized 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 , diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, Resol-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A novolac resin, unmodified resol phenol resin, oil-modified resol phenol resin modified with tung oil, linseed oil, walnut oil, etc. Phenolic resin such as phenol resin, phenoxy resin, urea resin, triazine ring-containing resin such as melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone resin, resin having a benzoxazine ring, norbor Nene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyazomethine resin, polyimide water and the like. Among these, especially, since it is excellent in reliability as an insulating layer, an epoxy resin and polyimide resin are preferable.

As an epoxy resin, the well-known and usual polyfunctional epoxy resin which has at least two epoxy groups in 1 molecule can be used. Liquid phase may be sufficient as an epoxy resin, and solid or semi-solid may be sufficient as it. Especially, a bisphenol A epoxy resin, a naphthalene-type epoxy resin, a phenol novolak-type epoxy resin, or a mixture thereof is especially 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, for example, jER828 manufactured by Mitsubishi Chemical Co., Ltd., but is not limited thereto.

When forming hardened|cured material using an epoxy resin, it is preferable to contain a hardening|curing agent other than an epoxy resin. Examples of the curing agent include imida such as 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), and 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ). Sol-based curing agent, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, metaxylenediamine, isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, N-aminoethyl Amine curing agents such as piperazine, phenolic curing agents such as polyamide, vinylphenol, aralkyl phenol resin, phenolphenyl aralkyl resin, and phenol biphenyl aralkyl resin, phthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, methyl Tetrahydrophthalic acid, methylhexahydrophthalic acid, methylnadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimate), methylcyclohexene A known curing agent such as an acid anhydride curing agent such as tetracarboxylic anhydride, a cyanate ester resin, an active ester resin, an aliphatic or aromatic primary or secondary amine, a polyamide resin, and a polymercapto compound can be used. To [ the compounding quantity of a hardening|curing agent / 100 mass parts of said epoxy resins ] Preferably it is 0.1-150 mass parts, More preferably, it is 0.5-100 mass parts. When the compounding quantity of a hardening|curing agent shall be 0.1 mass part or more, a resin composition can fully be hardened, and by setting it as 150 mass parts or less, the effect commensurate with a compounding quantity can be acquired efficiently.

Moreover, as a thermosetting catalyst, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, for example, are imidazole derivatives such as sol, 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid S-triazine derivatives, such as an adduct, can also be used.

As the polyimide resin, one obtained via a polyamic acid (polyimide precursor) by a synthetic reaction of a generally known aromatic polyhydric carboxylic acid anhydride or a derivative thereof and an aromatic diamine, and a polyamic acid composition already added to an organic solvent What is marketed as a so-called polyimide varnish in a dissolved state is mentioned.

Specific examples of the aromatic polyhydric carboxylic acid anhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 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-dicarboxyphenyl) )-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 dianhydride Water, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc. are mentioned. These are used individually or in mixture of 2 or more types. Among these, it is particularly preferable to use pyromellitic dianhydride as at least one of the components.

As a specific example of polyhydric carboxylic acid, such as aromatic polyhydric carboxylic acid anhydride, and aromatic diamine made to react, For example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-amino Benzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis(3-aminophenyl)sulfide, (3-amino Phenyl) (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-aminophenyl)sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(3-aminophenoxy) Cy)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-aminophenoxy)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-aminophenoxy)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]sulfide cy)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-amino) Phenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethyl Benzyl)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 the polyimide varnish, Rika Coat SN20, Rica Coat PN20, Rica Coat EN20, manufactured by Shin Nippon Rica Co., Ltd., Toray Varnish manufactured by Toray Co., Ltd., U-varnish manufactured by Ube Kosan Co., Ltd., and JSR Co., Ltd. product are used as polyimide varnishes. Optmer, SE812 manufactured by Nissan Chemical Co., Ltd., and CRC8000 manufactured by Sumitomo Bakelite Co., Ltd. are mentioned.

Cyclization (imidization) from a polyamic acid to a polyimide is performed by treating a polyamic acid solution obtained or released by the synthesis reaction by heating or the like. The polyamic acid can be imidized by a method only by heating or by a chemical method. In the case of the method by only heating, polyamic acid is imidated by heat-processing at 200-350 degreeC, for example. In addition, the chemical method is a method of completely imidizing polyamic acid by heat-treating it while using a basic catalyst to accelerate imidization. It does not specifically limit as said basic catalyst, A conventionally well-known basic catalyst is used, For example, pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), various tertiary amines, etc. are mentioned. These basic catalysts may be used independently and may use 2 or more types together.

(photocurable resin)

The photocurable resin may be a resin that is cured by irradiation with an active energy ray and exhibits electrical insulation, and a compound having one or more ethylenically unsaturated bonds in the molecule is particularly preferably used. As a compound which has an ethylenically unsaturated bond, a well-known and usual photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. are used.

As a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of the (meth)acrylate oligomer include epoxy (meth)acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate, urethane (meth) Acrylate, epoxyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc. are mentioned. In addition, in this specification, (meth)acrylate is a term which generically names an acrylate, a methacrylate, and a mixture thereof, and it is the same also about other similar expression.

As a photopolymerizable vinyl monomer, A well-known and usual thing, For example, Styrene derivatives, such as styrene, chlorostyrene, (alpha)-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl isobutyl ether, vinyl-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 vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; (acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc.) meth)acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoboronyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) ) esters of (meth)acrylic acid such as acrylates; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, and alkylene polyol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(es) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate meth) acrylates; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate; Isocyanurate-type poly(meth)acrylates, such as tris [(meth)acryloxyethyl] isocyanurate, etc. are mentioned.

As a photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, etc. can also be used suitably. Among them, examples of the alicyclic epoxy compound 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, 3,4 - The alicyclic epoxy compound etc. which have epoxy groups, such as epoxycyclohexyl ethyl trimethoxysilane, are mentioned.

Examples of the oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, and 1,4-bis[(3- methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methylacrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or an oligomer thereof; or In addition to polyfunctional oxetanes such as copolymers, oxetane alcohol and novolak resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or silsesquioxanes Oxetane compounds, such as an ether product with resin which has a hydroxyl group, and the copolymer of the unsaturated monomer which has an oxetane ring, and alkyl (meth)acrylate, are mentioned.

Examples of the vinyl ether compound include cyclic ether-type vinyl ethers such as isosorbite divinyl ether and oxanorbornene divinyl ether (vinyl ethers having cyclic ether groups such as oxirane ring, oxetane ring, and oxolane ring); aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and 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, and cyclohexane dimethanol divinyl ether; The vinyl ether compound etc. which have are mentioned. As a commercial item, Maruzen Sekiyu Chemical Co., Ltd. product 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), tri Ethylene glycol divinyl ether etc. are mentioned.

When a photocurable resin is used, in addition to the photocurable resin described above, a photopolymerization initiator, a photoacid generator, a photobase generator, etc. are used, and one of these may be used alone or in combination of two or more. .

As a photoinitiator, For example, benzoin and benzoin alkyl ethers, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. of acetophenones; 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone- aminoalkylphenones such as 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; or xanthone; (2,6-dimethoxybenzoyl)-2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine phosphine oxides such as oxide and ethyl-2,4,6-trimethylbenzoylphenylphosphinate; and various peroxides, titanocene-based initiators, and oxime ester-based initiators. These are used in combination with a photosensitizer 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 can do it. These photoinitiators can be used individually or in combination of 2 or more types.

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 (eg 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-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, etc. halogenated compounds; 2-nitrobenzyl ester of sulfonic acid; iminosulfonates; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N-hydroxyimide=sulfonate; tri(methanesulfonyloxy)benzene derivatives; bissulfonyldiazomethanes; sulfonylcarbonylalkanes;sulfonylcarbonyldiazomethanes; disulfone compounds; An iron allene complex etc. are mentioned. These photoacid generators can be used individually or in combination of 2 or more types.

A photobase generator is a compound which produces|generates one or more types of basic substances which can function as a catalyst of a polymerization reaction when a molecular structure is changed or a molecule|numerator is cleaved by light irradiation, such as an ultraviolet-ray or visible light. As a basic substance, a secondary amine and a tertiary amine are mentioned, for example. As such a photobase generator, for example, an α-aminoacetophenone compound, an oxime ester compound, an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzylcarbamate group, or an alkoxy The compound etc. which have substituents, such as a benzyl carbamate group, are mentioned. These photobase generators can be used individually or in combination of 2 or more types.

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, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether glycol ethers such as; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esters of the above glycol ethers; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N,N-dimethylformamide , amides such as acetamide and N-methylacetamide; ethers such as tetrahydrofuran and dioxane; nitriles such as acetonitrile, benzonitrile and propionitrile; halogens such as chloroform, dichloromethane, bromobenzene, dibromobenzene, chlorobenzene and dichlorobenzene; amines such as N-methyl-2-pyrrolidone, dimethylaniline, dibutylaniline, and diisopropylaniline; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; aliphatic hydrocarbons such as octane and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc. are mentioned. Among these, N-methyl-2-pyrrolidone and methyl ethyl ketone are preferable because handling is easy.

[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 base (11). In the present invention, the resin 3 may cover the outer side of the fiber base 11 as long as it can exhibit the role of ensuring adhesiveness. The impregnation rate of the resin composition is not particularly limited as long as the resin-containing sheet can adhere to the metal foil or the like, but the concentration of the resin in the resin-containing sheet is preferably 10-99 vol%, particularly 10-70 vol%. By making the impregnation rate of a resin composition into the said range, favorable adhesiveness and high strength can be obtained in a well-balanced manner.

The resin composition for forming the resin (3) may contain at least one selected from a thermosetting resin, a photocurable resin, and a thermoplastic resin, and may be used alone or in combination of two or more depending on the use. can be used by Among them, from the viewpoint of the physical properties of the cured product or the molded product, a thermosetting resin is preferable, and it is more preferable to use an epoxy resin. As the resin composition, when using a thermosetting resin or a photocurable resin, it is possible to appropriately use the same thermosetting resin, photocurable resin, organic solvent, etc. as mentioned for the fixing agent composition, and in the present invention, the resin composition and The fixing agent composition may be different from each other. In addition, as a thermoplastic resin, what is shown below 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 General-purpose plastics such as copolymer, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid, polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polybutylene terephthalate, Modified polyphenylene ether, polysulfone (PSF), polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone, polyarylate, polyetherimide, polyamideimide, liquid crystal polymer, polyamide 6T Engineering plastics such as polyamide 9T, polytetrafluoroethylene, polyvinylidene fluoride, polyesterimide, and thermoplastic polyimide, olefinic, styrene, polyester, urethane, amide, vinyl chloride, hydrogenated Thermoplastic elastomers, such as a system, are mentioned. In the present invention, a resin composite may be used, for example, as the resin composite of a thermosetting resin and a thermoplastic resin, an epoxy resin-PSF, an epoxy resin-PPS, an epoxy resin-PES, or the like can be used.

A coloring agent can also be mix|blended with the fixing agent composition and resin composition which concern on this invention as another component.

As a colorant, a well-known and usual thing expressed by a color index as a color pigment, dye, etc. 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, 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, 53:1, 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 fixing agent composition and the resin composition according to the present invention may contain, if necessary, conventional additives such as an antifoaming/leveling agent, a thixotropic agent/thickening agent, a coupling agent, a dispersing agent, and a flame retardant.

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 the thixotropic agent and thickener, clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, and zeolite, amorphous inorganic particles, polyamide-based additives, modified urea-based additives, wax-based additives, and the like can be used.

As the coupling agent, the alkoxy group is a methoxy group, ethoxy group, acetyl, etc., and the reactive functional group is vinyl, methacryl, acryl, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureide, sulfide, isocyanate, etc. For example, vinyl-based silane compounds such as vinylethoxysilane, vinyltrimethoxysilane, vinyl tris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltri Aminos such as methoxysilane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-aminopropylmethyldimethoxysilane, and γ-ureidepropyltriethoxysilane Epoxy silane compounds such as silane compounds, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ -mercapto-based silane compounds such as mercaptopropyltrimethoxysilane, silane coupling agents such as phenylamino-based silane compounds such as N-phenyl-γ-aminopropyltrimethoxysilane, isopropyltriisostearoylated titanate; Tetraoctylbis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, isopropyltridodecylbenzenesulfonyltitanate, isopropyltris(dioctylpyrophosphate)titanate, Tetraisopropylbis(dioctylphosphite)titanate, tetra(1,1-diallyloxymethyl-1-butyl)bis-(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)ethylenetita Nate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tristearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate titanate-based coupling agents such as titanate, dicumylphenyloxyacetate titanate, and diisostearoyl ethylene titanate, ethylenically unsaturated zirconate-containing compound, neoalkoxyzirconate-containing compound, neoalkoxytrisneodecanoylzir Conate, neoalkoxytris(dodecyl)benzenesulfonylzirconate, neoalkoxytris(dioctyl)phosphate zirconate, neoalkoxytris(dioctyl)pyrophosphate zirconate, Neoalkoxytris(ethylenediamino)ethyl zirconate, neoalkoxytris(m-amino)phenyl zirconate, tetra(2,2-diallyloxymethyl)butyl, di(ditridecyl)phosphitozirconate , 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 (diallyl) oxy, tri (N-ethylenediamino) ethyl zirconate, neo Pentyl (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-propenol) Zirconate-based coupling agents such as latomethyl)butanolato, cyclodi[2,2-(bis2-propenolatomethyl)butanolato]pyrophosphato-O,O, diisobutyl (oleyl) Aluminate type coupling agents, such as acetoacetyl aluminate and alkylacetoacetate aluminum diisopropylate, etc. can be used.

Examples of the dispersing agent include polymeric dispersants such as polycarboxylic acids, naphthalenesulfonic acid condensed formalin, polyethylene glycol, polycarboxylic acid partial alkyl esters, polyethers, polyalkylene polyamines, alkylsulfonic acids, quaternary ammonium; Low molecular weight dispersants, such as a higher alcohol alkylene oxide type, polyhydric alcohol ester type, an alkyl polyamine type, etc. can be used.

Examples of the flame retardant include hydrated metals 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, a melamine compound, a triazine compound, a guanidine compound, a silicone polymer, etc. can be used.

The fixing agent composition and the resin composition according to the present invention are other inorganic fillers such as barium sulfate, silica and hydrotalcite, organic fillers such as nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposing agents, and prohibition of thermal polymerization Agents, adhesion promoters, rust inhibitors, surface treatment agents, surfactants, lubricants, antistatic agents, pH adjusters, antioxidants, dyes, pigments, fluorescent agents, etc. may be included in a range that does not impair the object of the present invention.

[Storage Modulus]

In the present invention, it is necessary that the storage elastic modulus of the fixing agent 2 is 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 mixture of only the components of the fixing agent composition without the fibers 1 by heat or light after film formation. Similarly, with respect to the storage modulus of the resin 3, in the case of a curable resin, it means the storage modulus of a cured film cured by heat or light after film formation, and in the case of a thermoplastic resin, the solvent is removed after melt film formation. means the modulus of elasticity. In addition, the storage modulus is an index value of the hardness of the sample, and is a value calculated from the detected distortion by performing an evaluation called dynamic viscoelasticity measurement in which a periodic load is applied to the sample to detect distortion while applying a constant temperature change. , which means that the higher the value, the better the mechanical strength. In the present invention, at any one temperature, the storage elastic modulus of the fixing agent 2 may be higher than the storage elastic modulus of the resin 3, and the suitable range is 30 to 0.1 GPa with respect to the storage elastic modulus of the fixing agent 2, and , more preferably 20 to 0.5 GPa, with respect to the storage modulus of the resin (3) is 10 to 0.001 GPa, more preferably 5 to 0.01 GPa, at any one temperature, the storage modulus of the fixing agent (2) It is preferable that it is 0.1 GPa or more larger than the storage elastic modulus of this resin (3). In particular, at any one temperature within the range of 150 to 250 ° C., it is preferable that the storage elastic modulus of the fixing agent 2 is higher than the storage elastic modulus of the resin 3, and in the entire temperature range of 150 to 250 ° C., the fixing agent ( It is more preferable that the storage elastic modulus of 2) is higher than the storage elastic modulus of resin (3). Thereby, since the resin-containing sheet|seat of this invention can be used also in the high temperature range of 150-250 degreeC, since a use spreads, it is preferable.

[Glass Transition Temperature]

In the present invention, it is preferable that the glass transition temperature of the fixing agent (2) is 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 mixture of only the components of the fixing agent composition without containing the fibers 1 by heat or light after film formation. Similarly, about 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, the solvent is removed after melt film formation It means the softening temperature of the coating film obtained by doing this. In addition, the glass transition temperature is the temperature when the value (loss tangent) calculated from the ratio (E"/E') of the storage elastic modulus (E') and the loss elastic modulus (E") obtained by the above-mentioned dynamic viscoelasticity measurement (loss tangent) is maximum. , and it means that excellent heat resistance is exhibited, so that this temperature is high. In the present invention, the upper limit of the glass transition temperature is not particularly limited, but a suitable range thereof is 130°C or higher for the glass transition temperature of the fixing agent (2), more preferably 140°C or higher, and particularly preferably 250°C. ℃ or higher. Since the storage elastic modulus of the resin containing sheet|seat of this invention becomes high so that the glass transition temperature of the fixing agent 2 is high, it is preferable.

On the other hand, about the glass transition temperature or softening temperature of resin (3), it is 70 degreeC or more, More preferably, it is 80 degreeC or more. Moreover, it is preferable that the glass transition temperature of the fixing agent (2) is 5 degreeC or more larger 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 base 11 with a fixing agent composition to fix the fibers 1 to each other, and then impregnating the fixed fiber base 11 with the resin composition. In the resin-containing sheet of the present invention, for example, in a state in which fibers are disposed on an object to be coated such as a carrier film, a fixing agent composition and a resin composition are sequentially applied and impregnated to volatilize the organic solvent contained in the fixing agent composition and the resin composition. By drying, it can also be manufactured as a dry film, and if desired, you may bond a cover film further on it. At this time, as long as the resin composition does not impair the fixing performance of the fixing agent composition to the fibers, the application process of the resin composition may be either before or after drying of the fixing agent.

In this case, the fixing agent composition and the resin composition of the present invention can be applied by blending, dispersing, and diluting each component as needed, and adjusting the viscosity to a suitable viscosity for the coating method. As described above, the fixing agent composition should just be one that can penetrate the fiber base 11 to fix the fibers 1 to each other, and for the resin composition, at least one surface of the fiber base 11, especially both. What is necessary is just to be able to closely_contact|adhere the surface of with respect to metal foil etc.

As a to-be-coated object, although the carrier film for dry films is preferable, you may apply|coat directly to the surface of a metal foil or the circuit-formed wiring board surface. Specific examples of the coating method include a drip coating method using a pipette or the like, dip coating method, bar coater method, spin coating method, curtain coating method, spray coating method, roll coating method, slit coating method, blade coating method, lip coating method, comma Various coating methods, such as a coating method and a film coating method, and various printing methods, such as screen printing, spray printing, inkjet printing, iron plate printing, intaglio printing, and lithographic printing, are mentioned.

In addition, as a carrier film and a cover film, any well-known thing can be used as a material used for a dry film, For example, a polyethylene film, a polypropylene film, etc. are mentioned. Although the same film material may be used for a carrier film and a cover film and different film materials may be used, it is preferable about a cover film that adhesiveness with resin 3 is smaller than a carrier film.

A structure can be obtained by making the resin-containing sheet of the present invention adhere to a substrate. As a board|substrate, a metal foil board|substrate, a circuit board (a circuit-formed wiring board), etc. are mentioned. By thermally bonding the resin-containing sheet of the present invention to the surface of a substrate, a resin insulating layer can be formed, and by repetition thereof, a metal foil layer and a resin insulating layer can be laminated in multiple layers, respectively. Note that, when the resin-containing sheet is manufactured on a carrier film, the resin-containing sheet may be laminated with each other, or the resin-containing sheet may be laminated with each other in close contact with metal foil or the like.

When a structure is produced using the resin-containing sheet of the present invention, in the case where the fixing agent composition and the resin composition are a combination of a thermosetting resin or a photocurable resin, heat curing only method, active energy ray irradiation only, active energy ray irradiation The structure can be produced by using the method of heat-hardening later, or the method of irradiating an active energy ray after heat-hardening. In addition, 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 curing method, constructs can be made. In addition, when using a thermosetting resin as both a fixing agent composition and a resin composition, you may perform the fixing process of fibers, impregnation of resin, and both heat-hardening processes simultaneously. In addition, about the heating temperature at the time of heating, there is no restriction|limiting in particular as long as the fiber or fixing agent contained in the target base material is a range which does not decompose|disassemble by high heat, There is no restriction|limiting in particular, The exposure amount at the time of performing active energy ray irradiation Also, if the exposure amount is too low and an uncured part does not generate|occur|produce, there is no restriction|limiting in particular of a lower limit and an upper limit.

Moreover, when producing the resin containing sheet|seat of this invention, when the resin composition is a thermoplastic resin, the method of heating or heating and crimping|bonding a thermoplastic resin in pellet form or a sheet form can also be used. Here, in order to impregnate a thermoplastic resin into the fiber base material fixed with a fixing agent, it is not an essential requirement to pressurize using an apparatus, but penetration into the fiber base material of a thermoplastic resin becomes easier by performing pressurization. When pressurizing, there is no upper limit in particular of a pressure, unless the shape of the resin containing sheet|seat made into the objective is impaired. By thermally bonding this resin-containing sheet to the surface of the base, the structure can be molded. In addition, when shaping|molding a structure using a dry film, it can produce similarly to the above.

In the above, examples of the apparatus used during drying, heat curing, or heat pressurization include a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, a heating/pressurizing roll, and a press machine. Moreover, as a light source of active energy ray irradiation, a low-pressure mercury-vapor lamp, a medium-pressure mercury-vapor lamp, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. are mentioned. In addition, a laser beam etc. can be used as an active energy ray.

The thickness of the fiber base, which is a component of the resin-containing sheet of the present invention, in which fibers are fixed with a fixing agent (hereinafter also referred to as "intermediate"), and the dry film are not particularly limited, and may be appropriately selected according to the purpose, , especially for the intermediate, since the fibers are fixed to each other by a fixing agent, the thickness is preferably equal to the thickness of the fiber base material or a film thickness not exceeding twice the thickness of the fiber base material. Specifically, it is more preferable to exist in the range of 1-1.5 times the thickness of a fiber base material. When the thickness of the intermediate exceeds twice the thickness of the fiber base material, the physical properties of the fixing agent itself are affected, so it 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 can be used as a core material for a wiring board, and can also be used as an interlayer insulating material for a wiring board by performing etching treatment or the like. In addition, when a resin-containing sheet is formed on the surface of a circuit-formed wiring board, patterned to cover only the circuit wiring, cured or molded to obtain a structure, it can also be used as a solder resist or the like as the outermost layer of the wiring board.

The resin-containing sheet of the present invention having the configuration as described above can be applied to a wiring board for electronic devices, etc., for example, can be suitably applied to an interlayer insulating material for a wiring board, a solder resist, a core material, etc. The desired effect of the invention can be obtained. In addition, for example, by fixing the fibers with a fixing agent composition, permeating and drying the resin, forming a resin insulating layer in a semi-hardened state (B stage), and laminating and pressing the resin insulating layer and metal foil, a multilayer plate is formed can also be produced.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited by these Examples and Comparative Examples. In addition, all the compounding quantities in the following table|surface 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 nitrogen-substituted 3-neck flask with a stirrer, and 4,4'-diaminodiphenyl ether (ODA) ) (manufactured by Wako Junyaku Kogyo Co., Ltd.) and 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) (manufactured by Wako Junyaku Kogyo Co., Ltd.) in a molar ratio of 1:1, It stirred at room temperature for 16 hours or more, and obtained the polyamic-acid varnish 1 whose resin solid content ratio is 7.5 mass %.

[Synthesis of polyamic acid varnish 2]

In a 3-neck flask equipped with a stirrer purged with nitrogen, a dehydrated N-methyl-2-pyrrolidone (NMP) solvent (manufactured by Wako Pure Chemical Industries, Ltd.) was put, and p-phenylenediamine (PDA) (Wako Pure Chemical Industries, Ltd.) was added. Kogyo Co., Ltd.) and 3,3',4,4'-biphenyltetracarboxylic anhydride (BPDA) (manufactured by Wako Junyaku Kogyo Co., Ltd.) were mixed in a molar ratio of 1:1, and at room temperature It stirred for 16 hours or more, and obtained the polyamic-acid varnish 2 whose resin solid content ratio is 7.5 mass %.

[Preparation of fixing agent composition or resin composition]

In Table 1 below, the formulation contents of the compositions 1 to 4 used as the fixing agent composition or the resin composition are shown. 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 Composition 1, after each component was blended, it was prepared by stirring using a rotating/revolutionary mixer.

[Production of test pieces for evaluation such as storage modulus of fixing agent or resin]

Each composition 1-4 was respectively apply|coated to 18-micrometer-thick copper foil using the applicator, and the coating film was obtained.

About Composition 1, after drying under atmospheric conditions for 30 minutes at 80 degreeC in a hot-air circulation drying furnace, it heated under atmospheric conditions for 150 degreeC, 60 minutes, and obtained the epoxy resin hardened|cured material. When the copper foil was removed, the thickness was 50 µm. Using this hardened|cured material, the test piece for evaluation, such as storage elastic modulus of width 5mm and length 50mm, was produced.

About Composition 2, after application|coating, it dried in 80 degreeC, atmospheric condition for 30 minutes in a hot-air circulation drying furnace, and heated under nitrogen conditions (100ml/min.) for 250 degreeC, 60 minutes, and obtained the imidide. When the copper foil was removed, the thickness was 50 µm. Then, it carried out similarly to the above, and produced the test piece for evaluation.

About composition 3, except having performed heating operation under nitrogen conditions for 300 degreeC and 60 minutes, it carried out similarly to composition 2, and produced the test piece for evaluation.

For Composition 4, an appropriate amount of high-density polyethylene pellets (specific gravity 0.95) was put into a press machine, and after heating and pressing at 140 ° C., 3 MPa, 3 minutes, cooled to room temperature to obtain a molded article, and then divided into pieces, the thickness was 50 µm. Then, it carried out similarly to the above, and produced the test piece for evaluation.

[Preparation of test pieces for evaluation of storage modulus of resin-containing sheets and sheets]

In Tables 2 and 3 below, the structures of the resin-containing sheets and sheets of Examples and Comparative Examples are shown.

(Preparation of the intermediate of Example 1-A)

For Example 1-A in Table 2 below, using a glass fiber (type 1035 (IPC standard), thickness 30 µm) as a fiber substrate, and impregnating it with the composition 1 (viscosity 0.0005 Pa·s), After drying under atmospheric conditions at 80 ° C. for 30 minutes in a hot air circulation drying furnace, heat curing was performed at 150 ° C. for 60 minutes to prepare an intermediate containing glass fibers and a fixing agent (cured product of an epoxy resin composition).

(Preparation of the intermediate of Example 2-A)

For Example 2-A in Table 2 below, the same glass fiber as Example 1-A was impregnated with the composition 2 (viscosity of 0.001 Pa·s), and then in a hot air circulation drying furnace at 80° C., waiting for 30 minutes. After drying under the conditions, it was imidized by heating at 250° C. for 60 minutes to prepare an intermediate containing glass fiber and a fixing agent (polyimide).

(Preparation of the intermediate of Example 3-A)

For Example 3-A in Table 2 below, the same glass fiber as Example 1-A was impregnated with the composition 3 (viscosity 0.001 Pa·s), and then in a hot air circulation drying furnace at 80° C., waiting for 30 minutes. After drying under the conditions, it was imidized by heating at 300° C. for 60 minutes to prepare an intermediate containing glass fiber and a fixing agent (polyimide).

(Preparation of the intermediate of Comparative Example 4-A)

In the same manner as in Example 1-A, an intermediate containing glass fibers and a fixing agent (cured product of an epoxy resin composition) was prepared using the composition 1 above.

Each of the intermediates of Examples 1-A to 3-A and Comparative Example 4-A had a thickness of 33 to 35 µm, and the increase in thickness from the thickness of the glass fiber was only 3 to 5 µm.

(Preparation of the intermediate of Example 1-B)

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

(Preparation of the intermediate of Example 2-B)

For Example 2-B in Table 3 below, except for using the same aramid nonwoven fabric as Example 1-B as a fiber, it was treated in the same manner as in the preparation of the intermediate of Example 2-A, and the aramid nonwoven fabric and the fixing agent (polyimide ) was prepared containing an intermediate.

(Preparation of the intermediate of Example 3-B)

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

(Preparation of the intermediate of Comparative Example 4-B)

In the same manner as in Example 1-B, an intermediate containing glass fibers and a fixing agent (cured product of an epoxy resin composition) was prepared using the composition 1 above.

The thickness of each intermediate of 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 nonwoven fabric was only 3 to 6 µm.

(Preparation of resin-containing sheets or sheets of each Example and Comparative Example)

For Example 1-A and Example 1-B, the composition 4 was put into a press machine, melted at 140° C., then impregnated with each intermediate body obtained above, after heating and pressing at 140° C., 3 MPa, 3 minutes , by cooling to room temperature, a resin-containing sheet in which a resin (high-density polyethylene resin) was impregnated in a glass fiber or aramid nonwoven fabric fixed with a fixing agent (epoxy) was produced.

For Example 2-A, Example 2-B, Example 3-A and Example 3-B, for each intermediate obtained above, apply an appropriate amount to spread evenly over the entire fiber, By impregnating the glass fiber or aramid nonwoven fabric fixed with the fixing agent (polyimide) by heat curing under the same conditions as in the preparation of the test piece for evaluation of the fixing agent or resin, the resin (hardened epoxy resin) is impregnated with a resin-containing sheet produced.

The thickness of each resin-containing sheet of Examples 1-A to 3-A and Examples 1-B to 3-B was 5 to 10 µm thicker than the thickness of the intermediate body. Then, about each resin-containing sheet|seat, 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 is applied to the glass fiber or aramid nonwoven fabric in an appropriate amount so as to spread evenly over the entire fiber, and impregnated, and the test piece for evaluation of the fixing agent or resin By heating and curing under the same conditions as the production, a sheet in which a resin (hardened epoxy resin) was impregnated into a glass fiber or aramid nonwoven fabric containing no fixing agent was prepared.

For Comparative Example 2-A and Comparative Example 2-B, the glass fiber or aramid nonwoven fabric was coated with the above composition 2 in the same manner as in Comparative Example 1-A, impregnated, then in a hot air circulation drying furnace at 80 ° C., waiting for 30 minutes After drying under the conditions, it was imidized by heating at 250° C. under atmospheric conditions for 60 minutes to prepare a sheet in which a resin (polyimide) was impregnated in a glass fiber or aramid nonwoven fabric containing no fixing agent.

For Comparative Example 3-A and Comparative Example 3-B, the composition 4 was put into a press machine, melted at 140 ° C., then impregnated with glass fiber or aramid nonwoven fabric, 140 ° C., 3 MPa, after heating and pressing for 3 minutes , by cooling to room temperature, a sheet in which a resin (high-density polyethylene resin) was impregnated in a glass fiber or aramid nonwoven fabric containing no fixing agent was prepared.

For Comparative Example 4-A and Comparative Example 4-B, the glass fiber or aramid nonwoven fabric in Comparative Example 2-A and Comparative Example 2-B was replaced with an intermediate having a fixing agent containing the composition 1, except that it was used , A resin-containing sheet was produced in the same manner as in Comparative Examples 2-A and 2-B.

Then, about each sheet, the test piece for evaluation was produced similarly to the above.

In addition, as shown in Table 2 and Table 3 below, the resin content concentration is about the same for Examples 1-A to 3-A and Comparative Examples 1-A to 4-A, and Examples 1-B to 3 -B and Comparative Examples 1-B to 4-B were about the same. Here, the resin content concentration is the amount of fixing agent = {1- (volume of the fiber base / volume of the intermediate body)} x 100 [volume %], the amount of resin = {1- (volume of the intermediate / volume of the resin-containing sheet or sheet)} Each was calculated|required from x100 [volume%] (volume is converted based on mass and specific gravity).

[Measurement of storage modulus, etc.]

Using a test piece for evaluation such as storage modulus of a fixing agent or resin, using the tensile mode of a DMA viscoelasticity measuring device (DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.), measurement frequency 1 Hz, minimum tension and minimum compressive force 200 mN, distortion amplitude 10 The viscoelasticity was measured in micrometer, the temperature increase rate of 5 degreeC/min, and atmospheric condition, while obtaining the storage modulus at 50 degreeC, 150 degreeC, and 250 degreeC, the glass transition temperature or softening temperature was obtained. The results are shown in Table 1 below.

*1: jER828, manufactured by Mitsubishi Chemical Co., Ltd.

*2: 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd.

*3: Wako Junyaku High School Co., 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 installed so that the bias (inclination) direction of the fiber of the glass fiber or aramid nonwoven fabric in the sheet is the tensile direction of the device, and the minimum tension and compressive force are 50 mN, except that The viscoelasticity was measured similarly to the above, and the storage modulus in 50 degreeC, 150 degreeC, and 250 degreeC was obtained. Here, the measurement in the bias (inclination) direction is to exclude the influence of the elastic modulus of the fiber base itself as much as possible, and to investigate the influence of the improvement of the elastic modulus by the fixing effect. About each Example, compared with the sheet|seat of the comparative example to which the fixing agent was not attached, the case where the value of the storage elastic modulus E [GPa] was large was set to ○, and when it was small, it was set as X.

More specifically, the resin-containing sheet of Example 1-A has a storage modulus E [GPa] than the sheet of Comparative Example 3-A in which the fixing agent was not used at any temperature of 50°C, 150°C, and 250°C. Since it was this large, it was set as "(circle)".

Also in Example 1-B, since the value of the storage elastic modulus E [GPa] was large compared with the sheet|seat of the comparative example 3-B which did not use a fixing agent, it was set as "circle".

Also in the resin-containing sheets of Examples 2-A, 2-B, 3-A, and 3-B, the storage modulus E [GPa] compared to the sheets of Comparative Examples 1-A and 1-B in which no fixing agent was used, respectively. Since the value of was large, it was set as "circle".

On the other hand, the resin-containing sheet of Comparative Example 4-A has a smaller storage elastic modulus E [GPa] than the sheet of Comparative Example 2-A in which no fixing agent is used at any temperature of 50° C., 150° C., and 250° C. , was denoted by “x”.

Also in the sheet|seat containing resin of Comparative Example 4-B, it was set as "x" compared with the sheet|seat of Comparative Example 2-B which did not use a fixing agent.

The results are shown in Tables 2 and 3 below.

Note that, for reference, when the measurement was carried out using only glass fibers, the storage modulus value was not obtained because the braided fibers were unwound at the start of the measurement due to tension in the bias direction.

[Production of test pieces for adhesion evaluation]

Except having arranged the glass fiber or aramid nonwoven fabric as a fiber base material on the carrier film, it carried out similarly to the above, it apply|coated and impregnated the fixing agent composition, and each intermediate body was produced. Then, on the surface of the fixing agent after drying, after shape|molding or apply|coating and drying a resin composition, the cover film was bonded together and the dry film was obtained. 18 μm thick untreated copper foil was superimposed on both surfaces of this dry film (the carrier film and the cover film were peeled off when adhered), and with a vacuum press, pressurization conditions were 1 MPa, heating conditions were set to Example 1-A and 150° C.×10 min for 1-B, Examples 2-A and 2-B, and 250° C.×60 min for Comparative Examples 4-A and 4-B, Examples 3-A and 3-B It shape|molded as 300 degreeC x 60 minutes, and the test piece for adhesive evaluation which the resin layer and copper foil closely_contact|adhered was produced. In Comparative Examples 1-A to 3-A and Comparative Examples 1-B to 3-B, a dry film was similarly prepared and pressurized with a vacuum press except that the fixing agent composition was not applied and impregnated, and Comparative Example 1 -A to 3-A and Comparative Examples 1-B to 3-B, under the same temperature conditions as the sheet preparation, the test piece for adhesive evaluation was produced.

[Evaluation of adhesion]

When using the test piece for adhesive evaluation, the peeling strength at the time of peeling both at the interface of a resin layer and surface untreated copper foil is measured as 90 degree peeling angle, peeling rate 50 mm/min, 0.5 kN/m or more was made into ○, and the case of less than 0.5 kN/m was made into x. The results are shown in Tables 2 and 3 below. When peeling strength is high, it is excellent in the adhesiveness following an unevenness|corrugation, and it can be said that it is excellent in adhesiveness with copper foil.

As shown in Tables 2 and 3 above, the storage modulus of the fixing agents of Examples 1-A to 3-A and Examples 1-B to 3-B were all larger than the storage modulus of the resin, and on the other hand, Comparative Example 4- In A and 4-B, the storage elastic modulus of a fixing agent is both small compared with the storage elastic modulus of resin. In Comparative Examples 1-A to 3-A and 1-B to 3-B, only the resin was used and no fixing agent was used.

As shown in Tables 2 and 3, the resin-containing sheet of Examples in which the storage elastic modulus of the fixing agent is higher than the storage elastic modulus of the resin is used to fix the glass fiber or aramid nonwoven fabric, and the resin-impregnated sheet is impregnated with only the resin It turns out that it is excellent in adhesiveness and the storage elastic modulus is large compared with the sheet|seat of the made comparative example.

For example, when Example 1-A and Comparative Example 3-A are compared, as is clear, the resin-containing sheet of Examples in which the fibers of glass fibers are fixed with the fixing composition and the fiber base is impregnated with the resin composition Compared with Comparative Example 3-A in which the fibers of the glass fiber were not fixed by the fixing composition, it was found that the storage elastic modulus was high at any temperature, and thus the mechanical strength was high.

In particular, it can be seen that the resin-containing sheets of Examples 2-A and 3-A and Examples 2-B and 3-B had a storage elastic modulus of more than 1 GPa at 250° C. and excellent mechanical strength at high temperature. . On the other hand, in Comparative Example 4-A and Comparative Example 4-B in which the storage elastic modulus of the fixing agent was lower than the storage elastic modulus of the resin, the storage elastic modulus as a resin-containing sheet was low, and the adhesiveness was also inferior.

From the above, excellent mechanical strength, elastic modulus and adhesiveness are realized by using a resin-containing sheet having a fixing agent for fixing the fibers in the fiber base, 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. I was able to see what was possible. The resin-containing sheet of the present invention can be applied to a wiring board for an electronic device or the like, and for example, can be suitably applied to an interlayer insulating material for a wiring board, a solder resist, a core material, and the like.

1, 21: fiber
2: Fixing agent
3: Resin
11: fiber base
P: contact
D: The direction in which the fibers are separated by the tension T
S: space

Claims (7)

a fiber base (except for a wholly aromatic polyamide fiber base);
A fixing agent for fixing the fibers in the fiber base to each other;
It has a resin in contact with the fiber base and the fixing agent,
A resin-containing sheet, wherein a storage elastic modulus of the fixing agent is higher than a 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, wherein after the fibers of the fiber base are fixed with a fixing agent composition, the fixed fiber substrate is impregnated with a resin composition. The resin-containing sheet according to claim 3, wherein the fixing agent composition has a viscosity of 1 Pa·s or less. The resin-containing sheet according to claim 1, wherein the fiber base 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 having the structure according to claim 6 .

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