JP6679849B2 - Resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a resin composition useful as a high dielectric constant insulating material for electronic parts, particularly electronic parts used in a high frequency region, and a high dielectric constant insulating material for fingerprint sensors. The present invention also relates to a sheet-like laminated material using the resin composition, and an electronic component such as a multilayer printed wiring board having an insulating layer formed of a cured product of the resin composition.

  In recent years, information and telecommunications equipment has become more and more highly functional and highly functional, and electronic parts used in information and telecommunications equipment have been required to be compact and have high density. Attention is focused on high dielectric constant insulating materials.

  For example, in information communication equipment, a large amount of chip capacitors are mounted on a wiring board in order to prevent malfunction and noise of electronic parts such as digital ICs. A method is known in which a capacitor is built in a multilayer printed wiring board by providing a high dielectric constant insulating layer between layers (Patent Document 1). Further, in a fingerprint sensor, a member composed of a large number of metal electrodes arranged in an array and a high dielectric constant insulating layer formed so as to cover the metal electrodes is formed, and a fingerprint when a finger comes into contact with the high dielectric insulating layer is formed. There is known a method of detecting the difference in electrostatic capacitance between the concave portion and the convex portion (Patent Document 2).

  Examples of the insulating material for forming the high-dielectric-constant insulating layer include a material in which dielectric powder is dispersed in a resin composition. However, depending on the combination with a resin, the dispersibility of the dielectric powder may be increased. Poor, and because of its large specific gravity, the dielectric powder may settle in the resin composition (particularly in the varnished resin composition). For this reason, when a resin composition layer for an insulating layer is formed from the resin composition, projections due to agglomerates of dielectric powder may occur, and it may not be possible to form a resin composition layer having uniform properties. Since the insulating layer obtained by curing the resin composition layer having such an aggregate cannot make the insulating layer thickness equal to or smaller than the size of the aggregate, a desired static electricity is not required in the multilayer printed wiring board having the insulating layer. There is a problem that the electric capacity cannot be obtained. Further, in the fingerprint sensor, the electrostatic capacitance of the high dielectric insulating layer is different between the agglomerate portion and the other portions and is not constant, which causes a problem that the fingerprint cannot be correctly authenticated.

JP, 2008-274002, A JP, 2003-050994, A

  In view of the above circumstances, the problem to be solved by the present invention is to provide a resin composition capable of forming a high dielectric constant insulating layer in which the generation of aggregates of dielectric powder is suppressed at a high level. .

  The present inventor, as a result of extensive studies to solve the above problems, found that by using a nonionic surfactant, the dispersibility of the dielectric powder is significantly improved, and the present invention was completed based on such findings. Came to do.

That is, the present invention is as follows.
[1] A resin composition containing (A) epoxy resin, (B) dielectric powder, (C) nonionic surfactant, and (D) curing agent.
[2] The resin composition according to the above [1], wherein the nonionic surfactant (C) has a polyoxyalkylene skeleton.
[3] The resin composition according to the above [1] or [2], wherein the nonionic surfactant (C) contains an ether type nonionic surfactant.
[4] The resin composition according to any one of the above [1] to [3], wherein the (C) nonionic surfactant has a number average molecular weight of 400 or more.
[5] The (B) dielectric powder is one selected from the group consisting of barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, zirconium titanate, zinc titanate and titanium dioxide. Alternatively, the resin composition according to any one of the above [1] to [4], which contains two or more kinds.
[6] The resin composition according to any one of the above [1] to [5], wherein the (B) dielectric powder is barium titanate.
[7] The resin composition according to any one of the above [1] to [6], wherein the (B) dielectric powder is treated with (C) a nonionic surfactant.
[8] The above-mentioned [1] to [7], wherein the (D) curing agent contains one or more selected from the group consisting of a phenol-based curing agent, a cyanate ester-based curing agent and an active ester-based curing agent. The resin composition according to any one of 1.
[9] The resin composition according to any one of the above [1] to [8], which is a resin composition for forming a capacitor in a multilayer printed wiring board.
[10] The resin composition according to any one of the above [1] to [8], which is a fingerprint sensor resin composition.
[11] A resin composition varnish made of the resin composition according to any one of [1] to [8].
[12] A sheet-shaped laminated material obtained by using the resin composition according to any one of the above [1] to [8].
[13] A multilayer containing a capacitor, wherein an insulating layer made of a cured product of the resin composition according to any one of the above [1] to [6] is sandwiched between two conductive layers to form a capacitor. Printed wiring board.

According to the present invention, it is possible to obtain a resin composition for forming a high-dielectric-constant insulating layer, which contains a dielectric powder, in which generation of aggregates of the dielectric powder is suppressed at a high level and which is also excellent in storage stability. You can
Further, according to the present invention, it is possible to form a resin composition layer having no protrusions and the like and excellent in property uniformity.
Further, according to the present invention, a high dielectric constant insulating layer having high insulation reliability can be formed.
Further, according to the present invention, it is possible to obtain a multilayer printed wiring board having a highly reliable capacitor in which a high dielectric constant insulating layer having high insulation reliability is sandwiched between two conductive layers.
Further, according to the present invention, it is possible to realize a fingerprint sensor with high fingerprint authentication accuracy.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention is mainly characterized by containing (A) epoxy resin, (B) dielectric powder, (C) nonionic surfactant, and (D) curing agent.

  Generally, when the insulating layer is formed of an epoxy resin composition containing an epoxy resin and a curing agent, etc., the resin composition is dissolved or dispersed in an organic solvent to form a varnish (hereinafter, such a "varnish state resin composition" The term "resin composition varnish" is used herein. It is also simply referred to as "varnish".), The varnish is applied, and the organic solvent is dried by heating, blowing hot air or the like to form a resin composition layer, An insulating layer is formed by thermosetting the resin composition layer.

  Also when forming an insulating layer from the resin composition of the present invention, usually, it is the same as the method of forming an insulating layer by the above-described general epoxy resin composition, the resin composition in a varnish state, varnish coating, An insulating layer is formed by forming a resin composition layer by drying and thermosetting the resin composition layer. The insulating layer formed of the resin composition of the present invention becomes an insulating layer having high insulation reliability and high dielectric constant, as will be described later in detail.

<(A) Epoxy resin>
The "epoxy resin" used in the present invention means a thermosetting resin having two or more epoxy groups in one molecule and having an epoxy equivalent of 6000 g / eq or less. A phenoxy resin, which is an example of a polymer resin described later, may have an epoxy group similarly to an epoxy resin, but is a thermoplastic resin having an epoxy equivalent of more than 6000 g / eq and is distinguished from an epoxy resin. The epoxy equivalent of the epoxy resin is preferably 2000 g / eq or less, more preferably 80 to 1000 g / eq, and particularly preferably 100 to 800 g / eq. The "epoxy equivalent" is the number of grams (g / eq) of a resin containing 1 gram equivalent of epoxy group, and is measured according to the method specified in JIS K7236.

  Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, tert-butyl catechol. Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin , Biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, and halogenated epoxy resins. Among them, bisphenol A type epoxy resin, bixylenol type epoxy resin, naphthol type epoxy resin, naphthalene type tetrafunctional epoxy resin, and biphenylaralkyl type epoxy resin are preferable. Epoxy resin can use 1 type (s) or 2 or more types.

  The content of the (A) epoxy resin in the resin composition is 3 based on the total amount of the nonvolatile components in the resin composition, from the viewpoints of the adhesion of the resin composition to the base material and the conductor layer, the mechanical properties of the resin composition, and the like. -40 mass% is preferred, and 5-30 mass% is more preferred.

<(B) Dielectric powder>
Examples of the dielectric powder used in the present invention include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, zirconium titanate, zinc titanate and titanium dioxide. Barium titanate is preferred. Most of these are usually synthetic products, and commercially available dielectric powders can be used. The dielectric powder preferably has a relative dielectric constant in the range of 20 to 20,000 at 25 ° C. and a measurement frequency of 5.8 GHz, and more preferably in the range of 40 to 20,000. The average particle size of the dielectric powder is preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm, and particularly preferably 0.02 to 2 μm.

  The average particle diameter of the dielectric powder can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the dielectric powder on a volume basis with a laser diffraction type particle size distribution measuring device and setting the median diameter as the average particle diameter. As a measurement sample, a dielectric powder dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, LA-500 manufactured by Horiba Ltd. can be used.

Moreover, as the dielectric powder in the present invention, for example, a dielectric powder having a BET specific surface area of 1 to 50 m ² / g can be used. The BET specific surface area is measured according to the BET method using a specific surface area measuring device (Macsorb HM Model-1210 manufactured by Mountech Co., Ltd.). The specific surface area of the dielectric powder can be adjusted by firing conditions (temperature, time), atomization by pulverization, and the like.

  The particle shape of the dielectric powder is not particularly limited, and may be amorphous or spherical, but spherical dielectric powder is preferable, and the content in the resin composition can be increased, thereby, The dielectric constant of the insulating layer obtained by curing the resin composition can be further increased.

  As the dielectric powder, one kind or two or more kinds can be used. The content of the dielectric powder in the resin composition is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, based on the entire nonvolatile content of the resin composition.

<(C) Nonionic surfactant>
In the present invention, a nonionic surfactant is used as a dispersant. The nonionic surfactant is not particularly limited, and various types can be used.

  Examples of the nonionic surfactant suitable for the present invention include, for example, ether type, ester type, sorbitan ester type, sorbitan ester / ethylene oxide addition type, diester type, monoglyceride type, monoglyceride / ethylene oxide addition type, triglyceride / ethylene oxide addition type, Solbit ester / ethylene oxide addition type, polyglycerin alkyl ester type, polyether amine type, alkanolamide type, alkanolamide / ethylene oxide addition type, amine oxide type, polyethylene glycol / polypropylene glycol / block ether type (polyoxyethylene / polyoxypropylene -Block polymer type), ethylenediamine base type, phenol type, etc., and preferably ether type

The ether type nonionic surfactant is typically
General formula (1):

A polyoxyalkylene alkyl ether represented by
General formula (2):

And a polyoxyalkylene alkyl phenyl ether represented by

In the formulas (1) and (2), R ¹ represents an alkyl group or an alkenyl group, and the carbon number thereof is preferably 6 to 22, more preferably 8 to 18, and particularly preferably 10 to 15. The alkyl group may be a single alkyl group or a mixed alkyl group. A represents an alkylene group and X represents a phenylene group. n represents an integer of 1 to 70, preferably 10 to 30. The oxyalkylene group represented by A-O may be composed of one kind of oxyalkylene group such as an ethylene oxide group and a propylene oxide group, or two kinds such as an ethylene oxide group and a propylene oxide group. May be composed of a plurality of types of oxyalkylene groups such as

  Specific examples of the polyoxyalkylene alkyl ether include, for example, polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene dodecyl ether (other names). : Polyoxyethylene lauryl ether), polyoxyethylene tetradecyl ether, polyoxyethylene hexadecyl ether (also known as polyoxyethylene cetyl ether), polyoxyethylene octadecyl ether (also known as polyoxyethylene oleyl ether), polyoxyethylene eico Syl ether, polyoxyethylene oleyl ether, coconut oil reduced alcohol ethylene oxide adduct, tallow reduced alcohol ethi Emissions oxide adducts, polyoxyethylene - polyoxypropylene - dodecyl ether (aka: polyoxyethylene - polyoxypropylene - lauryl ether), polyoxypropylene dodecyl ether (aka: polyoxypropylene lauryl ether) and the like. Among them, polyoxyethylene dodecyl ether, polyoxypropylene dodecyl ether, polyoxyethylene-polyoxypropylene-dodecyl ether and the like are preferable.

  Specific examples of polyoxyalkylene alkyl phenyl ethers include, for example, polyoxyethylene hexyl phenyl ether, polyoxyethylene heptyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene decyl phenyl ether, and polyoxyethylene decyl phenyl ether. Oxyethylene dodecyl phenyl ether (also known as polyoxyethylene lauryl phenyl ether), polyoxyethylene tetradecyl phenyl ether, polyoxyethylene hexadecyl phenyl ether, polyoxyethylene octadecyl phenyl ether, polyoxyethylene eicosyl phenyl ether, etc. .

A commercially available product can be used as the nonionic surfactant in the present invention.
As the ether type, for example, “NONION K-204” (polyoxyethylene lauryl ether), “NONION K-220” (polyoxyethylene lauryl ether), “NONION K-230”, and “NONION K-230” manufactured by NOF CORPORATION are available. "Persoft NK-60", "Persoft NH-90C", "Persoft NK-100", "Persoft NK-100", "Nonion EAD-13" (above, polyoxyethylene alkyl ether), "Nonion P" -208 "," Nonion P-210 "," Nonion P-213 "(above, polyoxyethylene cetyl ether)," Nonion E-202 "," Nonion E-202 "," Nonion E-202S "," Nonion ". E-205 "," Nonion E-205S "," Nonion E-212 "," Nonion E-21 " , "Nonion E-230" (above, polyoxyethylene oleyl ether), "Nonion S-202", "Nonion S-207", "Nonion S-215", "Nonion S-220" (above, polyoxy Ethylene stearyl ether), "Nonion ID-203", "Nonion ID-206", "Nonion ID-209" (above, polyoxyethylene isodecyl ether), "Nonion EH-204" (polyoxyethylene 2-ethylhexyl ether) ), "Nonion EH-208" (polyoxyethylene 2-ethylhexyl ether), "Polyoxydispanol TOC", "Nonion ET-505", "Nonion ET-507", "Nonion ET-510", "Nonion ET". -512 "," Nonion ET-515 "," No ON ET-518 "(above, polyoxyethylene-polyoxypropylene-alkyl ether)," Unilube MS-70K "(polyoxypropylene stearyl ether)," Dispanol 16 "," Dispanol 16A "," Dispanol LS " -100 "," Nonion MN-811 "," Dispanor WI-106 "," Dispanor WI-115 "," Dispanor W1-133 ", etc. are mentioned.

  In addition, "LB-220", "LB-53B", "LB-720", "LB-820", "LB-54C", "LB-83", "LB-93", and "LB-220" manufactured by ADEKA CORPORATION. "LB-103", "LB-1220", "LB-1520" (above, polyoxyalkylene lauryl ether), "LA-675B," LA-775 "," LA-875 "," LA-975 "," LA-1275 "(above, polyoxyethylene lauryl ether)," OA-7 "(polyoxyethylene oleyl ether)," TN-40 "," TN-80 "," TN-100 "," TO-120 ". , "UA-70N", "UA-90N", "LO-3", "LO-7" (above, primary alcohol ethoxylate), "SO-80", "SO-105", "SO-". 120 "," S -135 "," SO-145 "," SO-160 "(or, secondary alcohol ethoxylate), and the like.

  Examples of the ester type include “NONION L-2”, “NONION L-4” (above, polyoxyethylene monolaurate), “NONION S-2”, and “NONION S-4” manufactured by NOF CORPORATION. , "NONION S-6", "NONION S-15", "NONION S-15K", "NONION S-15.4", "NONION S-15.4V", "NONION S-40" (above, poly Oxyethylene monostearate), "nonion O-2", "nonion O-3", "nonion O-4", "nonion O-6" (above, polyoxyethylene monooleate) and the like, manufactured by ADEKA CORPORATION "OEG-102" (polyoxyethylene monooleate) and the like.

  Examples of the sorbitan ester type include “NONION CP-08R” (sorbitan monocaprylate), “Food additive nonion CP-08R” (sorbitan monocaprylate) and “NONION LP-20R” (sorbitan) manufactured by NOF CORPORATION. Monolaurate), "Nonion LP-20R food additive" (Sorbitan monolaurate), "Nonion MP-30R" (Sorbitan monomyristate), "Nonion PP-40R pellet" (Sorbitan monopalmitate), "Nonion SP" "-60R pellet" (sorbitan monostearate), "nonion OP-80R" (sorbitan monooleate), "nonion OP-83RAT" (sorbitan sesquioleate), "nonion OP-85R" (sorbitan trioleate), etc. Company "Adeka" S 20 "(sorbitan lauryl ester)," S-60 "(sorbitan stearyl ester)," S-80 "(sorbitan oleyl ester), and the like.

  Examples of the sorbitan S-ethylene oxide addition type include "NONION LT-221" (polyoxyethylene sorbitan monolaurate), "NONION ST-221" (polyoxyethylene sorbitan monostearate) manufactured by NOF CORPORATION. Nonion OT-221 "(polyoxyethylene sorbitan monooleate)," Willsurf TF-20 "(polyoxyethylene sorbitan monolaurate)," Willsurf TF-60 "(polyoxyethylene sorbitan monostearate)," Will " Surf TF-80 "(polyoxyethylene sorbitan monooleate) and the like," T-81 "(polyoxyethylene sorbitan monooleate) manufactured by ADEKA CORPORATION and the like can be mentioned.

  Examples of the diester type include "UNISTAR E-275" (ethylene glycol distearate), "NONION DS-60HN" (polyethylene glycol distearate), and "NONION DO-4" (polyethylene glycol) manufactured by NOF CORPORATION. Diole), "Nonion DO-6" (polyethylene glycol dioleate), "Unisafe NKL-9520" (polypropylene glycol distearate), "Unisafe NUL-6589" (polypropylene glycol disuccinate) and the like.

  Examples of the monoglyceride type include “Monoguri D” (glyceryl monostearate), “Monoguri MB” (glyceryl monostearate), and “Monoguri M-14” (glyceryl monomyristate) manufactured by NOF CORPORATION. Etc.

  Examples of the monoglyceride / ethylene oxide addition type include “UNIGURI MK-207” (polyoxyethylene coconut fatty acid glyceryl), “UNIGURI MK-230” (polyoxyethylene coconut fatty acid glyceryl), and “UNIGURI MK-” manufactured by NOF CORPORATION. 278 "(polyoxyethylene coconut fatty acid glyceryl)," NK-3 "," NK-4 "," NK-7 "(above, glyceride ethylene oxide adduct) manufactured by ADEKA CORPORATION.

  Examples of the triglyceride / ethylene oxide addition type include “UNIOX HC-8”, “UNIOX HC-40”, “UNIOX HC-60” (above, polyoxyethylene hydrogenated castor oil) manufactured by NOF CORPORATION. Can be mentioned.

  Examples of the sorbit ester / ethylene oxide addition type include “UNIOX ST-30E”, “UNIOX ST-40E”, and “UNIOX ST-60E” (above, polyoxyethylene tetraoleic acid) manufactured by NOF CORPORATION. Etc.

  Examples of the polyglycerin alkyl ester type include “UNIGURI GO-102R” (polyglycerin oleic acid ester), “UNIGURI GO-106” (polyglycerin oleic acid ester), and “UNIGLI GL-106” manufactured by NOF CORPORATION. (Polyglycerin lauric acid ester), "Unigli GS-106" (polyglycerin stearic acid ester), etc. are mentioned.

  As the polyether amine type, for example, “Nymeen L-201” (N-hydroxyethyllaurylamine), “Nymeen L-202”, “Nymeen L-207” (above, polyoxyethylene lauryl) manufactured by NOF CORPORATION. Amine), "Nymeen L-703" (polyoxyethylene-polyoxypropylene-laurylamine), "Nymeen F-202", "Nymeen F-215" (above, polyoxyethylene alkyl (coconut) amine), "Nymeen" "S-202", "Nymeen S-204", "Nymeen S-210", "Nymeen S-215", "Nymeen S-220" (above polyoxyethylene stearylamine), "Nymeen O-205" (polyene Oxyethylene oleylamine), "Nymeen 2-202 ”,“ Nymeen T2-210 ”,“ Nymeen T2-230 ”(above, polyoxyethylene tallow alkylamine),“ Nymeen T2-230 ”,“ Nymeen DT-203 ”,“ Nymeen DT-208 ”( And polyoxyethylene-alkylpropylene-diamine).

  Examples of the alkanolamide type include "STAFOAM F" (coconut oil fatty acid diethanolamide, 1: 2 type), "STAFOAM T" (beef tallow fatty acid diethanolamide, 1: 2 type) manufactured by NOF CORPORATION. Stahome DL "(lauric acid diethanolamide)," stahome DF-1 "," stahome DF-2 "," stahome DF-4 "," stahome DFC "(above, coconut oil fatty acid diethanolamide), "STAH HOME DO", "STAH HOME DOS" (above oleic acid diethanolamide), "STAH HOME MF pellets" (coconut oil fatty acid monoethanolamide), "Tahome LIPA" (lauric acid isopropanolamide), etc., and ADEKA CORPORATION Made "CO" (coconut oil fatty acid diethanolamide 1: 2 type), "COA" (coconut oil Fatty acid diethanolamide, 1: 1 type) and the like.

  Examples of the alkanolamide / ethylene oxide addition type include “Nymid MF-203”, “Nymid MF-210”, and “Nymid MT-215” (above, polyoxyethylene fatty acid-monoethanolamide) manufactured by NOF CORPORATION. Is mentioned.

  Examples of the amine oxide type include “Unisafe A-LM” (dimethyllauryl-amine oxide aqueous solution), “Unisafe A-SM” (dimethylstearyl-amine oxide aqueous solution), and “Unisafe A-LE” manufactured by NOF CORPORATION. (Dihydroxyethyllauryl-amine oxide aqueous solution), "Unisafe WHS-10" (dihydroxyethyllauryl-amine oxide aqueous solution), etc. are mentioned.

  Examples of the polyethylene glycol / polypropylene glycol / block ether type (polyoxyethylene / polyoxypropylene / block polymer type) include, for example, "Pronon # 102", "Pronone # 104", and "Pronone # 201" manufactured by NOF CORPORATION. , "Pronone # 202B", "Pronone # 204", "Pronone # 208", "Unilube 70DP-600B", "Unilube 70DP-950B" (above, polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer), etc. And "L-23", "L-31", "L-44", "L-61", "L-62", "L-64", "L-71", and "L-23" manufactured by ADEKA CORPORATION. L-72 "," L-101 "," L-121 "," P-84 "," P-85 "," P-103 ", F-68 "," F-88 "," F-108 "and the like (above, polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer)," 25R-1 "," 25R-2 "," 17R- " 2 ”,“ 17R-3 ”,“ 17R-4 ”(above, polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymer) and the like.

  Examples of the ethylenediamine base type include "TR-701", "TR-702", and "TR-704" (above, an adduct of ethylenediamine polyoxyethylene polyoxypropylene block copolymer). To be

  In addition, polyethylene glycol is also a nonionic surfactant suitable for the present invention. The number average molecular weight of polyethylene glycol is preferably 150 to 30,000, more preferably 200 to 20,000. A commercially available product can be used as polyethylene glycol, and for example, "PEG-200", "PEG-300", "PEG-400", "PEG-600", "PEG-1000", "" manufactured by ADEKA CORPORATION. Examples thereof include PEG-1500, PEG-1540, PEG-4000, PEG-6000, and PEG-20000.

  Further, a polymer compound having a side chain having an oxyalkylene group or a polyoxyalkylene group, such as a compound having a segment represented by the following general formula (3), is also a nonionic surfactant suitable for the present invention.

(In the formula, A ¹ represents an alkylene group, R ² represents a hydrogen atom, an alkyl group, or an aryl group, and n represents an integer of 1 to 100. Note that the oxyalkylene group represented by A ¹ -O is , An ethylene oxide group, a propylene oxide group or the like, or may be composed of a plurality of types of oxyalkylene groups such as two kinds of ethylene oxide group and propylene oxide group. It may be one.)

  As the compound having a segment represented by the general formula (3), a commercially available compound can be used, and specifically, a Marialim (registered trademark) series manufactured by NOF CORPORATION (the general formula (3 ), A polymer compound having a repeating structural unit composed of a segment derived from maleic anhydride and a segment derived from styrene). Such a Marialim series has a repeating structure composed of "Marialim AKM1511-60" and "Marialim AKM0531" (a segment represented by the general formula (3), a segment derived from maleic anhydride and a segment derived from styrene). A polymer compound having units, in which the alkylene group represented by A is an ethylene group, the substituent represented by R is a methyl group, and n is 11), "Marialim AFB-1521" (A polymer compound having a repeating structural unit composed of a segment represented by the general formula (3), a segment derived from maleic anhydride, and a segment derived from styrene, wherein the alkylene group represented by A is An ethylene group, the substituent represented by R is an ethyl group, and n is 28), "Marialim -60 "," MALIALIM A-20 ", and the like.

  In the present invention, the nonionic surfactant is preferably a nonionic surfactant having a polyoxyalkylene skeleton, and the polyoxyalkylene skeleton in the nonionic surfactant having a polyoxyalkylene skeleton is a polyoxyethylene skeleton and / or A polyoxypropylene skeleton is preferred.

  In the present invention, the molecular weight of the nonionic surfactant (excluding polyethylene glycol) is not particularly limited, but the number average molecular weight (Mn) is preferably 400 or more. The number average molecular weight (Mn) is preferably 50,000 or less, more preferably 20,000 or less.

  The number average molecular weight (Mn) of the nonionic surfactant in the present invention refers to a value measured by gel permeation chromatography (GPC). LC-9A / RID-6A (manufactured by Shimadzu Corp.) was used as the GPC, and Shodex K-800P / K-804L / K-804L (manufactured by Showa Denko KK) was used as a column, and chloroform and THF (eluents were used as eluents. (Tetrahydrofuran) and the like, and the setting temperature of the column oven is set to 40 ° C. for measurement. A calibration curve of standard polystyrene is used to calculate the number average molecular weight (Mn).

  In the present invention, one kind or two or more kinds of nonionic surfactants can be used. The content of the nonionic surfactant in the resin composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the (B) dielectric powder.

In the resin composition of the present invention, the (B) dielectric powder is preferably treated with (C) a nonionic surfactant. The term "treated" as used herein means that the surface of the dielectric powder (B) is partially or wholly coated with the nonionic surfactant (C) in the preparation of the resin composition varnish. . If the surface of the dielectric powder (B) is partially or entirely coated with the nonionic surfactant (C) in the resin composition, whatever the treatment, it is "treated" in the present application. ”, For example,
1) Before mixing the dielectric powder (B) with a resin component such as the epoxy resin (A), the dielectric powder (B) is previously mixed with the nonionic surfactant (C),
2) The nonionic surfactant (C) is mixed with at least a part of the resin component such as the epoxy resin (A) and the dielectric powder (B) in the coexistence thereof,
Including etc.

<(D) Curing agent>
The (D) curing agent used in the present invention is not particularly limited, but from the viewpoints of insulation reliability of an insulating layer made of a cured product of a resin composition, heat resistance, storage stability of an adhesive film, etc., a phenolic curing agent, It is preferable to include one or more selected from cyanate ester-based curing agents and active ester-based curing agents.

  The phenol-based curing agent is not particularly limited, but is selected from biphenyl-type curing agents, naphthalene-type curing agents, phenol novolac-type curing agents, naphthylene ether-type curing agents, and triazine skeleton-containing phenol-type curing agents, or It is preferable to use two or more kinds. Specifically, biphenyl type curing agents, MEH-7700, MEH-7810, MEH-7851 (all are manufactured by Meiwa Kasei Co., Ltd.), naphthalene type curing agents, NHN, CBN, GPH (or more. , All manufactured by Nippon Kayaku Co., Ltd., SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (all are manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Co., Ltd.). , TD2090 (manufactured by DIC Corporation) which is a phenol novolac type curing agent, EXB-6000 (manufactured by DIC Corporation) which is a naphthylene ether type curing agent, and LA3018, LA7052, LA7054 which are triazine skeleton-containing phenol type curing agents. , LA1356 (all of which are manufactured by DIC Corporation) and the like. These can use 1 type (s) or 2 or more types.

  The cyanate ester curing agent is not particularly limited, but is a novolac type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester curing agent, dicyclopentadiene type cyanate ester curing agent, bisphenol type (bisphenol A type, bisphenol C type ester hardeners such as F type and bisphenol S type, and prepolymers obtained by partially converting these to triazine. The weight average molecular weight of the cyanate ester-based curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000. Specific examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether. , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolacs, phenolic resins containing a dicyclopentadiene structure, prepolymers obtained by partially converting these cyanate resins into triazines, etc. These can be used alone or in combination of two or more. As the cyanate ester resin, a phenol novolac type polyfunctional cyanate ester resin (manufactured by Lonza Japan Co., Ltd., PT30S, cyanate equivalent 124), and a part or all of bisphenol A dicyanate are triazined to form a trimer. Examples include prepolymers (BA230S, cyanate equivalent 232, manufactured by Lonza Japan Co., Ltd.), cyanate ester resins containing a dicyclopentadiene structure (DT-4000, DT-7000, manufactured by Lonza Japan Co., Ltd.) and the like.

  The active ester-based curing agent is not particularly limited, but in general, an ester group having a high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, and ester of heterocyclic hydroxy compound is contained in one molecule. Compounds having two or more of them are preferably used. The active ester type curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. The active ester curing agent may be used alone or in combination of two or more. As the active ester-based curing agent, specifically, an active ester-based curing agent containing a dicyclopentadienyl diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent that is an acetylated product of phenol novolac. An active ester-based curing agent that is a benzoylated product of phenol novolac is preferable, and an active ester-based curing agent containing a dicyclopentadienyldiphenol structure is more preferable because of its excellent improvement in peel strength. As the active ester curing agent, the active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. As commercial products, those containing a dicyclopentadienyl diphenol structure, such as EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (all of which are manufactured by DIC Corporation, active group equivalent: 223), acetyl of phenol novolac. As an active ester-based curing agent that is a compound, DC808 (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent: about 149), as an active ester-based curing agent that is a benzoyl compound of phenol novolac, YLH1026 (manufactured by Mitsubishi Chemical Co., active Group equivalent of about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 245) and the like.

  More specifically, examples of the active ester type curing agent containing a dicyclopentadienyl diphenol structure include compounds of the following formula (I).

(In the formula, R represents an aryl group, k represents 0 or 1, and n is an average of repeating units of 0.05 to 2.5.)

  Examples of the aryl group of R include a phenyl group and a naphthyl group, and from the viewpoint of improving the heat resistance of the cured product, R is preferably a naphthyl group, while k is preferably 0 and n is 0.25. ~ 1.5 is preferred.

  The (D) curing agent can be used alone or in combination of two or more, and the content of the (D) curing agent is determined by the adhesion of the insulating layer made of the cured product of the resin composition to the base material and the conductor circuit, and the mechanical property. From the viewpoint of dynamic strength and the like, when the nonvolatile component in the resin composition is 100% by mass, 20% by mass or less is preferable, and 15% by mass or less is more preferable.

  The ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent in the resin composition is preferably 1: 0.2 to 1: 2, and 1: 0.25 to 1: 1. 5 is more preferable, and 1: 0.3-1: 1 is still more preferable. The total number of epoxy groups of the epoxy resin, the value obtained by dividing the solid content mass of each epoxy resin present in the resin composition by the epoxy equivalent is a total value for all epoxy resins, the reactive group of the curing agent. The total number is a value obtained by summing the values obtained by dividing the solid content mass of each curing agent present in the resin composition by the reactive group equivalent for all curing agents.

(E) Polymer Resin The polymer composition of the present invention may further contain a polymer resin. By including the polymer resin, the mechanical strength of the cured product can be improved. Further, when the resin composition is used in the form of an adhesive film, the film forming ability can be improved. Examples of the polymer resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Among them, phenoxy resin and polyvinyl acetal resin are preferable, and phenoxy resin is more preferable. The polymer resin may be used alone or in combination of two or more.

  The weight average molecular weight of the polymer resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 12,000 to 100,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). The weight average molecular weight by the GPC method is specifically LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured by using chloroform as a mobile phase at a column temperature of 40 ° C and using a calibration curve of standard polystyrene.

  When the polymer resin is added to the resin composition, the amount of the polymer resin is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the whole nonvolatile components in the resin composition. preferable. Within this range, the effect of improving the film molding ability of the resin composition and the mechanical strength of the cured product is exhibited.

(F) Curing accelerator The epoxy resin and the curing agent can be efficiently cured by further containing a curing accelerator in the resin composition of the present invention. The curing accelerator is not particularly limited, and examples thereof include an amine curing accelerator, a guanidine curing accelerator, an imidazole curing accelerator, a phosphonium curing accelerator, and a metal curing accelerator. These may be used alone or in combination of two or more.

  The amine curing accelerator is not particularly limited, but trialkylamine such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl). Examples thereof include amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

  The guanidine curing accelerator is not particularly limited, but includes dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine. , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide , 1-cyclohexyl biguanide, 1-allyl biguanide, 1-fe Rubiguanido, 1-(o-tolyl) biguanide, and the like. These may be used alone or in combination of two or more.

  The imidazole-based curing accelerator is not particularly limited, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium tri Meritate 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1 Dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

  The phosphonium-based curing accelerator is not particularly limited, but includes triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like can be mentioned. These may be used alone or in combination of two or more.

  When a curing accelerator (excluding a metal-based curing accelerator) is added to the resin composition, the range of 0.005 to 1 part by mass is preferable with respect to 100 parts by mass of the total amount of the epoxy resin and the curing agent, The range of 0.01 to 0.5 parts by mass is more preferable. Within this range, the thermosetting can be made more efficient and the storage stability of the varnish is improved.

  The metal-based curing accelerator is not particularly limited, and examples thereof include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. And the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  When a metal-based curing accelerator is added to the resin composition, the content of the metal based on the metal-based curing catalyst is preferably in the range of 25 to 500 ppm, and preferably in the range of 40 to 200 ppm, based on the entire nonvolatile components in the resin composition. Is more preferable. Within this range, a conductor layer having excellent adhesion to the surface of the insulating layer is formed and the storage stability of the varnish is also improved.

  If necessary, the resin composition of the present invention may contain components other than the above-mentioned components (A) to (F) within a range that does not impair the effects of the present invention. Other components include thermosetting resins such as vinylbenzyl compounds, acrylic compounds, maleimide compounds, blocked isocyanate compounds; organic fillers such as silicone powder, nylon powder, fluororesin powder, rubber particles; silica, alumina, water. Inorganic fillers such as aluminum oxide, magnesium hydroxide, aluminum hydroxide, zinc borate, aluminum borate, antimony oxide, calcium carbonate, magnesium carbonate, magnesium oxide, and boron nitride; thickeners such as Orben and Benton, silicone-based agents , Fluorine-based, polymer-based defoaming agents or leveling agents; phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black, and other coloring agents; phosphorus compounds, flame retardants such as metal hydroxides, etc. To list It can be.

  When the resin composition contains an inorganic filler, the average particle diameter of the inorganic filler is not particularly limited, but from the viewpoint of filling property, insulation reliability, etc., 10 μm or less is preferable, 5 μm or less is more preferable, and 2 μm or less Is more preferable. On the other hand, when the resin composition is a varnish, 0.01 μm or more is preferable, 0.03 μm or more is more preferable, and 0.05 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and the handleability from decreasing. The above is more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter can be used as the average particle diameter for measurement. As the laser diffraction / scattering type particle size distribution measuring device, LA-950 manufactured by Horiba Ltd. can be used.

  The resin composition of the present invention is prepared by appropriately mixing the above components, and if necessary, kneading or mixing by a kneading means such as a three-roll, a ball mill, a bead mill, a sand mill, or a stirring means such as a super mixer or a planetary mixer. It is prepared by Further, the resin composition can be prepared as a varnish by dissolving or dispersing the above components in an organic solvent, and by further adding an organic solvent to the resin composition prepared without adding an organic solvent. It can also be prepared as a varnish. The content of the organic solvent in the varnish is preferably 15 to 60% by mass, and more preferably 20 to 50% by mass, based on the entire varnish.

  The resin composition of the present invention can be used as a cured product obtained by thermosetting. The conditions for thermosetting may be appropriately selected depending on the type and content of the resin component in the resin composition, but preferably 90 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably 150 ° C to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. Further, the heat curing may be performed in two or more stages. The cured product of the resin composition of the present invention becomes an insulator having a high dielectric constant with a relative dielectric constant (23 ° C.) of 5 or more. Therefore, a high-capacity capacitor can be formed by interposing the cured product of the resin composition of the present invention between the two conductor layers.

  Here, the relative permittivity is a value measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonance method. As the measuring device, for example, a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd., a network analyzer E8362B manufactured by Agilent Technology Co., Ltd., or the like can be used.

  The cured product has an average coefficient of linear thermal expansion of 3 to 60 ppm (preferably 3 to 40 ppm) from 25 ° C to 150 ° C.

<Sheet-like laminated material>
The resin composition of the present invention can be used for forming an insulating layer by applying it to a circuit board in a varnish state, but industrially, it is used for forming an insulating layer in the form of a sheet material such as an adhesive film or prepreg. Is preferred. That is, it is preferable that an adhesive film, a prepreg or the like is produced using the resin composition of the present invention, and the adhesive film, the prepreg or the like is laminated on a circuit board to form an insulating layer. Since sheet-like materials such as adhesive films and prepregs using the resin composition of the present invention are used after being laminated (laminated) on a circuit board, they will be referred to as “sheet-like laminated materials”.

(Adhesive film)
The adhesive film of the present invention is a resin composition layer formed by the resin composition of the present invention on a support layer, a method known to those skilled in the art, for example, the resin composition is dissolved or dispersed in an organic solvent. The varnish prepared above is applied to the support layer using a die coater or the like, and further, the organic solvent is dried by heating or blowing hot air to form a resin composition layer on the support layer. You can

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, acetic acid esters such as cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitol such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

  The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

  The thickness of the resin composition layer formed in the adhesive film is not particularly limited, but it is preferable that the resin composition layer has a thickness of 100 μm or less from the viewpoint of increasing the capacitance and reducing the thickness of the substrate. . From the viewpoint of thinning, the thickness is more preferably 50 μm or less, further preferably 30 μm or less.

  As the support layer, a film of polyolefin such as polyethylene, polypropylene or polyvinyl chloride, a film of polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), a film of polyester such as polyethylene naphthalate, a polycarbonate film, a polyimide film Various plastic films such as, release paper, metal foil such as copper foil and aluminum foil, or metal vapor deposition film in which a metal vapor deposition layer (for example, copper vapor deposition layer) is formed on a releasable plastic film subjected to release treatment. Is mentioned. The support layer may be subjected to surface treatment such as matte treatment and corona treatment. Further, the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. When the support layer is a metal foil or a metal vapor deposition film, the metal foil or the metal vapor deposition layer can form one electrode of the capacitor.

  The thickness of the plastic film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

  As the metal foil, a copper foil is particularly preferable, and as the copper foil, an electrolytic copper foil, a rolled copper foil, an ultrathin copper foil with a carrier, or the like can be used. The thickness of the copper foil is preferably 9 to 35 μm, more preferably 12 to 18 μm. The thickness of the ultrathin copper foil in the ultrathin copper foil with a carrier is preferably 1 to 5 μm. In the case of a metal vapor deposition film, the thickness of the vapor deposition layer is usually 100Å to 5000Å.

  When the support layer is a metal foil, it is preferable that the surface of the metal foil on which the resin composition layer is formed is roughened in order to improve the adhesive strength due to the anchoring effect. The method of roughening treatment is not particularly limited, but when the metal foil is a copper foil, for example, a method of roughening by etching or immersing the copper foil in an aqueous solution of copper sulfate, depositing copper by electrolysis, and fine Known methods such as a method of forming fine copper particles on the surface of the copper foil can be used. In addition, after the surface roughening treatment, a rust preventive treatment may be performed, or a treatment such as a chromate treatment or a blackening treatment for improving adhesiveness with a resin may be performed. From the viewpoint of suppressing transmission loss, the surface roughness (Rz) of the copper foil is preferably 6.0 μm or less, more preferably 4.0 μm or less, and further preferably 3.0 μm or less. The surface roughness (Rz) is defined by the ten-point average roughness (Rz) of JIS B 0601-1994 “Definition and display of surface roughness”.

  Commercially available copper foil can be used as it is, for example, JTC-LP foil, JTC-AM foil (all manufactured by JX Nippon Mining & Metals Corporation), GTS-MP foil, F2-WS foil (all are available. Furukawa Electric Co., Ltd. etc. are mentioned.

  A protective film conforming to the support layer can be further laminated on the surface of the resin composition layer to which the support layer is not adhered. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and prevent scratches. The adhesive film may be wound into a roll and stored.

(Prepreg)
The prepreg of the present invention can be produced by impregnating the sheet-shaped reinforcing base material with the resin composition of the present invention by a hot melt method or a solvent method, and heating and semi-curing the resin composition. That is, the prepreg of the present invention is a prepreg obtained by impregnating a sheet-shaped reinforcing base material with the resin composition of the present invention. As the sheet-like reinforcing base material, for example, a material composed of fibers commonly used as prepreg fibers such as glass cloth and aramid fiber can be used.

  In the hot melt method, the resin composition is not dissolved in an organic solvent and is once coated on a support and then laminated on a sheet-like reinforcing base material, or directly applied to the sheet-like reinforcing base material by a die coater. It is a method of manufacturing a prepreg by performing the above. In the solvent method, a resin is dissolved in an organic solvent in the same manner as the adhesive film to prepare a varnish, a sheet-shaped reinforcing base material is immersed in this varnish, the sheet-shaped reinforcing base material is impregnated, and then dried. Is the way. Further, the prepreg can be prepared by continuously heat-bonding the adhesive film from both sides of the sheet-shaped reinforcing base material under heating and pressurizing conditions. A support, a protective film, etc. can be used similarly to the adhesive film. That is, the prepreg of the present invention includes a prepreg with a support (support / pre-preg laminate), a support and a prepreg with a protective film (support / prepreg / protective film laminate), and such a support is practically used. A prepreg with a prepreg, a support and a prepreg with a protective film are preferable. The thickness of the prepreg is not particularly limited, but is usually 5 to 100 μm, and preferably 10 to 50 μm from the viewpoint of mechanical strength and thinning.

<Multilayer printed wiring board>
The resin composition of the present invention is used for forming an insulating layer in a multilayer printed wiring board. As described above, the cured product of the resin composition of the present invention becomes an insulator having a high dielectric constant. Therefore, the resin composition of the present invention is particularly used for forming an insulating layer sandwiched between two conductive layers in order to obtain a multilayer printed wiring board containing a capacitor. Further, as described above, the resin composition of the present invention can be used for forming an insulating layer by applying it in a varnish state on a circuit board, but industrially, it is a form of a sheet-like laminated material such as an adhesive film and a prepreg. It is preferable to use it for forming an insulating layer.

  Hereinafter, an example of a method for manufacturing a multilayer printed wiring board using a sheet-shaped laminated material will be described.

  First, the sheet-shaped laminated material is laminated (laminated) on one side or both sides of the circuit board using a vacuum laminator. Examples of the substrate used as the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The term "circuit board" as used herein refers to a board on which a patterned conductor layer (circuit) is formed on one side or both sides. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one or both outermost layers of the multilayer printed wiring board are patterned conductor layers (circuits). It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-shaped laminated material has a protective film, after removing the protective film, the sheet-shaped laminated material and the circuit board are preheated if necessary, and the sheet-shaped laminated material is pressurized and Laminate on circuit board while heating. In the sheet-shaped laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are not particularly limited, but for example, the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (lamination pressure) is preferably 1 to 11 kgf / cm ² (9.8 ×). 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using rolls. The vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nichigo Morton Co., Ltd., vacuum pressure laminators manufactured by Meiki Co., Ltd., roll type dry coaters manufactured by Hitachi Industries Co., Ltd., Hitachi AIC Co., Ltd. ) Vacuum laminator etc. made by the above).

  After laminating the sheet-shaped laminated material on the circuit board and then cooled to around room temperature, if the support is peeled off, the resin composition in the sheet-shaped laminated material is thermally cured to form a cured product. An insulating layer can be formed on the circuit board. The conditions for heat curing are as described above. After the insulating layer is formed, if the support is not peeled off before curing, it may be peeled off here if necessary. The support layer is peeled off when the support layer is a plastic film or a release paper, and when the support layer is a metal foil or a metal vapor deposition film, the support layer is not peeled off.

  After the step of laminating the sheet-shaped laminated material, a smoothing step of heating and pressing the sheet-shaped laminated material with a metal plate or a metal roll to smooth it can be performed. Specifically, it is performed by heating and pressurizing the sheet-shaped laminated material with a metal plate such as a heated SUS mirror plate under normal pressure (under atmospheric pressure). The heating and pressurizing conditions can be the same as those in the laminating step. The smoothing step can be continuously performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd. and a vacuum applicator manufactured by Nichigo Morton Co., Ltd.

Further, the sheet-shaped laminated material can be laminated on one side or both sides of the circuit board by using a vacuum heat press. The pressing conditions are such that the degree of pressure reduction is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. The heating and pressurizing can be performed in one step, but it is preferable to perform the heating in two steps or more from the viewpoint of controlling the exudation of the resin. For example, when it is performed in one step, the temperature is preferably 150 to 200 ° C., the pressure is preferably 9.8 × 10 ^{4 to} 2.0 × 10 ⁵ Pa, and the time is preferably 30 to 120 minutes. When performing in two steps, the temperature of the first step is 70 to 130 ° C., the pressure is in the range of 9.8 × 10 ^{4 to} 2.9 × 10 ⁵ Pa, and the second step is 150 to 130 ° C. It is preferable to carry out at 200 ° C. and a pressure in the range of 9.8 × 10 ^{4 to} 4.9 × 10 ⁵ Pa. The time of each step is preferably 30 to 120 minutes. By thus laminating the sheet-shaped laminated material on the circuit board with the vacuum heat press, the sheet-shaped laminated material is thermoset at the same time. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.) and the like.

  In addition, when the support layer of the sheet-shaped laminated material is peeled off in the above step, the electrode material (for example, a metal foil such as copper foil, a metal vapor deposition layer (for example, a copper vapor deposition layer or the like) on the insulating layer is formed on the insulating layer. 2) is laminated with a metal vapor deposition film). The lamination is the same as the conditions described above.

  After that, the electrode material is processed into a pattern including a portion to be one electrode of the capacitor (for example, when the electrode sheet material is a copper foil or a copper vapor deposition film, an aqueous solution of iron (III) chloride or hydrogen peroxide). A multilayer printed wiring board (circuit board) in which a capacitor is formed by sandwiching a part of an insulating layer formed by using a sheet-like laminated material between two electrodes (conductive layers) by etching with an aqueous solution or the like). A part of the conductor layer (circuit) on the surface constitutes the other electrode of the capacitor). The electrodes may be formed by plating (subtractive method, semi-additive method).

  According to the method of the present invention, a multilayer printed wiring board having a built-in capacitor having an electrostatic capacity of about 0.1 to 3000 pF can be manufactured. The thickness of the insulating layer sandwiched between the two conductive layers (electrodes) in the capacitor is usually 1 to 100 μm, preferably 2 to 30 μm. In particular, since the insulating layer made of the cured product of the resin composition of the present invention has high insulation reliability, it is possible to obtain a multilayer printed wiring board incorporating a highly reliable capacitor.

<Fingerprint sensor>
In the fingerprint sensor of the present invention, a member composed of a plurality of metal electrodes arranged in an array and a high dielectric constant insulating layer formed so as to cover the metal electrodes is formed, and when a finger contacts the high dielectric insulating layer. The difference in capacitance between the concave and convex portions of the fingerprint is detected. The resin composition of the present invention can be used for forming an insulating layer by applying it in a varnish state on a metal electrode, but industrially, an insulating film is formed in the form of a sheet-like laminated material such as an adhesive film and a prepreg. It is preferable to use

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the “equivalent weight” means a value obtained by dividing the molecular weight of a compound having a functional group, which is a target of the equivalent weight, by the number of functional groups of the compound, that is, the molecular weight per one functional group.

[Measurement method / Evaluation method]
First, various measuring methods and evaluation methods will be described.

<Measurement of relative permittivity>
The varnishes obtained in the examples and comparative examples were coated with a die-coated PET film (“PET501010” manufactured by Lintec Co., Ltd.) so that the thickness of the resin composition layer after drying was 40 μm. It was evenly coated with a coater and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed at 200 degreeC for 90 minute (s), and peeled from the support body, and the hardened material film was obtained. The cured film was cut into a length of 80 mm and a width of 2 mm to give an evaluation sample. The relative permittivity of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B device manufactured by Agilent Technologies. The measurement was performed on two test pieces, and the average value was calculated.

<Evaluation of linear thermal expansion coefficient>
The varnishes obtained in the examples and comparative examples were coated with a die-coated PET film (“PET501010” manufactured by Lintec Co., Ltd.) so that the thickness of the resin composition layer after drying was 40 μm. It was evenly coated with a coater and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed at 200 degreeC for 90 minute (s), and peeled from the support body, and the hardened material film was obtained. The cured film was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Corporation. . After mounting the test piece on the apparatus, measurement was performed twice continuously under the conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the average coefficient of linear thermal expansion from 25 ° C to 150 ° C was calculated.

<Evaluation of uniformity of varnish>
The aggregates in the varnishes obtained in Examples and Comparative Examples were observed with a microscope (VH-2250, manufactured by KEYENCE CORPORATION) at an observation magnification of 1000 times, and aggregates of 10 μm or more in 3 fields of view. Less than 6 pieces were evaluated as ◯ (good), and 6 or more pieces were evaluated as x (not good).

<Evaluation of film uniformity>
The resin composition layer obtained in Examples and Comparative Examples had an aggregate in the adhesive film having a thickness of 40 μm observed with a microscope (VH-2250, manufactured by KEYENCE CORPORATION) at an observation magnification of 1000 times. When less than 3 aggregates of 10 μm or more in 10 fields of view were evaluated as ◯ (good) and 3 aggregates or more were evaluated as x (impossible).

<Evaluation of dispersion stability of varnish>
After the varnishes obtained in Examples and Comparative Examples were stored at 5 ° C. for 3 days, the sedimentation of the filler, that is, the case where the separation of the resin component and the filler content was not observed, was ◯ (good), and the case where it was observed was x ( No)

<Evaluation of capacitance error>
The 10 μm thick adhesive films obtained in Examples and Comparative Examples were heat-treated at 200 ° C. for 90 minutes to obtain a cured product with a support. The cross-section of the obtained cured product with a support was observed at 10 positions in a range of 30 μm in width and 20 μm in depth using FIB-SEM (“SMI3050SE” manufactured by SII NanoTechnology Co., Ltd.), and an image was obtained. From the analysis, the average thickness (d _ave ) of the cured product (resin composition layer after curing) including the aggregate portion was determined. When the average thickness d _ave including the aggregated portion of the cured product is taken as the standard thickness (d _flat ) of the cured product-free portion, the electrostatic charge of the cured product due to the presence of the aggregated substance The capacitance error is expressed by the following equation (1).

Capacitance error due to the presence of aggregates (%)
= 100 × (1-C _ave / C _flat )
= 100 * (1-d _flat / d _ave ) (1)

The meanings of the symbols in formula (1) are as follows.
C _flat = ε _r ε ₀ S / d _flat
C _ave = ε _r ε ₀ S / d _ave
C _flat : Capacitance when there is no protrusion derived from aggregates and the film thickness is uniform C _ave : Capacitance when average film thickness is increased due to protrusions derived from aggregates ε _r : Insulating layer (curing) Specific permittivity of later resin composition layer ε ₀ : Dielectric constant of vacuum S: Area of electrode plate

  When the error of the electrostatic capacity calculated by the calculation formula (1) is 1% or less, it is judged as good (◯), and when it exceeds 1%, it is judged as unacceptable (x).

<Method of evaluating insulation reliability of insulation layer>
(1) Preparation of inner layer substrate Both sides of the glass cloth substrate epoxy resin double-sided copper clad laminate with a circuit formed (copper foil thickness 18 μm, substrate thickness 0.3 mm, “R1515A” manufactured by Panasonic Corporation) The copper surface was roughened by etching with a microetching agent (“CZ8100” manufactured by MEC Co., Ltd.) to 1 μm.

(2) Lamination of Copper Foil with Resin The varnishes obtained in Examples and Comparative Examples were coated on MT18Ex foil manufactured by Mitsui Metal Industry Co., Ltd. so that the thickness of the resin composition layer after drying was 40 μm. Was uniformly applied and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. This resin-coated copper foil was laminated on both sides of the inner layer substrate using a batch type vacuum pressure laminator (2-stage build-up laminator CVP700 manufactured by Nichigo Morton Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate. . The lamination was carried out by depressurizing for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then pressure-bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of copper foil with resin A resin composition was cured on the laminated copper foil with resin at 90 ° C. for 90 minutes to form a cured body with copper foil.

A circular conductor pattern having a diameter of 10 mm was formed on the copper foil side of the cured product with copper foil obtained in (3) above. Then, the circular conductor side was used as a + electrode, and the circuit conductor (copper) side of the inner layer circuit board was used as a-electrode, using an advanced accelerated life test device (“PM422” manufactured by ETAC), at 130 ° C, 85% relative humidity, 3 The insulation resistance value when 300 hours passed under the condition of applying a DC voltage of 3 V was measured with an electrochemical migration tester (“ECM-100” manufactured by J-RAS Co., Ltd.) (n = 5). When the resistance value was 10 ⁹ Ω or more in all of the 5 tests, it was evaluated as ◯ (good), and when it was less than 10 ⁹ Ω even once, it was evaluated as × (impossible).

[Example 1]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate ("HBT-030F" manufactured by Sinocera, average particle diameter 0.55 µm, BET specific surface area 3.68 m ² / g, specific gravity 6.02 g / cm ³ ) 400 parts, ether type nonionic surfactant (ADEKA, Inc.). "LB-1520", 4 parts of polyoxyalkylene lauryl ether) are mixed and uniformly mixed with a high-speed rotary mixer. Then, a varnish was prepared by dispersing the varnish on polyethylene terephthalate (thickness: 38 μm) by a die coater so that the resin composition after drying had a thickness of 10 μm and 40 μm. It was dried for 6 minutes at 120 ° C. (100 ° C. on average) (residual solvent amount: about 2%), and then wound on a roll while winding a 15 μm-thick polypropylene film on the surface of the resin composition layer. The film was slit into a width of 507 mm, and a sheet-like adhesive film having a size of 507 mm × 336 mm was obtained from this.

[Example 2]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, Mitsubishi Chemical Co., Ltd. “jER828US”) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, Mitsubishi Chemical KK “YX4000HK”) 5 parts, naphthylene 33 parts of ether type epoxy resin (epoxy equivalent 260, "HP6000" manufactured by DIC Corporation), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type tetrafunctional epoxy resin (Epoxy equivalent 162, "HP4700" manufactured by DIC Co., Ltd.) 5 parts, phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts "YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., and 75 parts MEK. , 25 parts of cyclohexanone were dissolved by heating while stirring. To, active ester curing agent (active group equivalent 223, toluene solution having a solid content of 65%, "HPC8000-65T" manufactured by DIC Corporation) 20 parts, triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50) % 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate ( Sinocera's "HBT-030F") 400 parts, ether type nonionic surfactant ("ADE-15A" manufactured "LB-1520", polyoxyalkylene lauryl ether) 4 parts are mixed and uniformly dispersed by a high speed rotating mixer. Then, a varnish was prepared, and then the crocodile was placed on polyethylene terephthalate (thickness: 38 μm). The resin composition was applied by a die coater so that the thickness of the resin composition after drying was 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%). A 15 μm-thick polypropylene film was attached to the surface of the resin composition layer and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm. It was

[Example 3]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 13 parts of a naphthalene type curing agent (phenol equivalent 215, “SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), a triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P") 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F"). ) 400 parts and 4 parts of an ether type nonionic surfactant ("LB-1520" manufactured by ADEKA Corporation, polyoxyalkylene lauryl ether) were mixed and uniformly dispersed by a high speed rotation mixer to prepare a varnish. Next, on the polyethylene terephthalate (thickness 38 μm), the resin composition after drying the varnish was prepared. It was applied with a die coater to a thickness of 10 μm and 40 μm, and dried for 6 minutes at 80 to 120 ° C. (average 100 ° C.) (residual solvent amount: about 2%). A 15 μm polypropylene film was attached and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Example 4]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, ether type nonionic surfactant (ADEKA Corporation "LB-1520", polyoxyalkylene lauryl ether) 4 parts, silane coupling agent (N-phenyl-). 3-aminopropyltrimethoxysilane, "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a varnish.Next, the thickness of the resin composition after drying the varnish was 10 μm and 40 μm on polyethylene terephthalate (thickness 38 μm). Was coated with a die coater as described above and dried for 6 minutes at 80 to 120 ° C. (average of 100 ° C.) (residual solvent amount: about 2%), while a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer. The roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Example 5]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 540 parts, ether type nonionic surfactant ("ADEKA Co., Ltd." LB-1520 ", polyoxyalkylene lauryl ether) 5.4 parts are mixed and mixed with a high speed rotating mixer. A varnish was prepared by uniformly dispersing the varnish on polyethylene terephthalate (thickness: 38 μm). Was coated with a die coater so that the thickness of the resin composition after drying was 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%). Next, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm, from which a sheet-shaped adhesive film of 507 mm × 336 mm size was formed. Got

[Example 6]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera “HBT-030F”) 240 parts, spherical silica (average particle size 0.5 μm, specific surface area 6.8 m ² / g, Admatex Co., Ltd. “SO-C2” (aminosilane coupling agent treatment) 120 parts, ether type nonionic surfactant ("LB-1520" manufactured by ADEKA Corporation, polyoxya) (Kylene lauryl ether) 2.4 parts were mixed and evenly dispersed with a high-speed rotary mixer to prepare a varnish.Next, the thickness of the resin composition after drying the varnish on polyethylene terephthalate (thickness 38 μm) Of 10 μm or 40 μm by a die coater, and dried for 6 minutes at 80 to 120 ° C. (average of 100 ° C.) (residual solvent amount: about 2%). The film was wound into a roll while adhering the polypropylene film of 1. to the sheet.

[Example 7]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera's "HBT-030F") 400 parts, styrene-maleic acid-based surfactant (NOF CORPORATION), trade name Marialim AKM-0531, allyl alcohol-maleic anhydride-styrene copolymer and polyoxy. Grafted product with alkyl ether: weight average molecular weight: 15,000) 4 parts, A varnish was prepared by uniformly dispersing the varnish on a polyethylene terephthalate (thickness: 38 μm) with a die coater so that the resin composition after drying had a thickness of 10 μm and 40 μm. And dried for 6 minutes at 80 to 120 ° C. (100 ° C. on average) (residual solvent amount about 2%), and then wound in a roll shape while adhering a polypropylene film having a thickness of 15 μm to the surface of the resin composition layer. The roll-shaped adhesive film was slit into a width of 507 mm, and a sheet-shaped adhesive film having a size of 507 mm × 336 mm was obtained from this slit.

[Example 8]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, polyethylene glycol (Tokyo Kasei Kogyo Co., Ltd. "Polyethylene Glycol 600", number average molecular weight: 600) 4 parts are mixed and uniformly dispersed by a high speed rotating mixer. Then, a varnish was prepared.Next, polyethylene terephthalate (thickness: 38 μm The varnish was applied onto the above with a die coater so that the thickness of the dried resin composition would be 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%. Then, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound into a roll, the roll-shaped adhesive film was slit into a width of 507 mm, and a sheet-shaped adhesive having a size of 507 mm × 336 mm was bonded from the slit. I got a film.

[Comparative Example 1]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, phenylsilane type silane coupling agent (phenyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM103""4 parts) are mixed and uniformly dispersed by a high-speed rotating mixer. Then, a varnish was prepared. The resin composition was applied by a die coater so that the thickness of the resin composition after drying was 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%). A polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm. It was

[Comparative Example 2]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, epoxysilane type silane coupling agent (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM403") 4 parts are mixed and rotated at high speed. A varnish was prepared by uniformly dispersing with a mixer, and then polyethylene terephthalate (thickness 3 varnish was coated on the above with a die coater so that the thickness of the resin composition after drying was 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (the amount of residual solvent was about 10 μm). Then, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm, and a sheet having a size of 507 mm × 336 mm was formed from the slit. The adhesive film of was obtained.

[Comparative Example 3]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, phenylaminosilane type silane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM573") 4 parts are mixed, A varnish was prepared by uniformly dispersing with a high-speed rotating mixer. The varnish was applied onto a sheet (thickness 38 μm) by a die coater so that the thickness of the dried resin composition would be 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes. (Amount of residual solvent is about 2%.) Then, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound up in a roll shape.The roll-shaped adhesive film was slit into a width of 507 mm, and 507 mm × A 336 mm-sized sheet-shaped adhesive film was obtained.

[Comparative Example 4]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, aminosilane type silane coupling agent (3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM903""4parts" are mixed, and the mixture is homogenized with a high-speed rotary mixer. To prepare a varnish, which was then placed on polyethylene terephthalate (thickness: 38 μm). Was coated with a die coater so that the thickness of the resin composition after drying was 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%). Next, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm, from which a sheet-shaped adhesive film of 507 mm × 336 mm size was formed. Got

[Comparative Example 5]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera “HBT-030F”) 400 parts, 4 parts titanate coupling agent (Ajinomoto Fine-Techno Co., Ltd. “Planeact KR-46B”) 4 parts were mixed and uniformly dispersed with a high-speed rotary mixer, and varnish. Next, a resin set after drying the varnish on polyethylene terephthalate (thickness 38 μm) was prepared. The composition was applied with a die coater to a thickness of 10 μm or 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount: about 2%). Then, a polypropylene film having a thickness of 15 μm was stuck to the roll and wound up in a roll shape, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Comparative Example 6]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera "HBT-030F") 400 parts, 4 parts of anionic polymer dispersant having a phosphonic acid group (Big Chemie Co., Ltd. "BYK W-9010") are mixed and uniformly dispersed by a high-speed rotating mixer. Then, a varnish was produced on a polyethylene terephthalate (thickness: 38 μm). The composition was applied with a die coater to a thickness of 10 μm or 40 μm and dried for 6 minutes at 80 to 120 ° C. (average 100 ° C.) (residual solvent amount: about 2%). Then, a polypropylene film having a thickness of 15 μm was stuck to the roll and wound up in a roll shape, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Comparative Example 7]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera's "HBT-030F") 400 parts and 4 parts of a carboxylic acid group-containing anionic polymer dispersant (Kao Corporation's "Homogenol L-18") are mixed and uniformly dispersed by a high-speed rotating mixer. Then, a varnish was prepared, and the resin composition after the varnish was dried on polyethylene terephthalate (thickness 38 μm). Was coated with a die coater to a thickness of 10 μm or 40 μm and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%). A 15 μm-thick polypropylene film was laminated and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Comparative Example 8]
Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation) 20 parts, bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 5 parts, biphenylaralkyl 35 parts of epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthalene type 4 functional epoxy 5 parts of resin (epoxy equivalent 162, “HP4700” manufactured by DIC Corporation), phenoxy resin (MEK / cyclohexanone = 1/1 solution having a solid content of 30%, 15 parts of “YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK75) And 25 parts of cyclohexanone were dissolved by heating while stirring There, 20 parts of active ester curing agent (active group equivalent 223, toluene solution of solid content 65%, "HPC8000-65T" manufactured by DIC Corporation), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid content 50% 2-methoxypropanol solution, DIC Corporation "LA3018-50P" 20 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% MEK solution) 4 parts, barium titanate (Sinocera's "HBT-030F") 400 parts, cationic surfactant (NOF Corporation's "Nissan cation VB-F", alkyl trimethyl ammonium chloride solution) 5 parts are mixed and uniformly mixed with a high-speed rotating mixer. A varnish was prepared by dispersing the crocodile into polyethylene terephthalate (thickness: 38 μm). Was applied by a die coater so that the thickness of the dried resin composition would be 10 μm and 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount about 2%). A 15 μm-thick polypropylene film was attached to the surface of the composition layer and wound into a roll, and the roll-shaped adhesive film was slit into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm. .

  Table 1 below shows the compositions of the resin compositions of Examples 1-8 and Comparative Examples 1-8. Correspondence between the epoxy resin, the curing agent and the dispersant in Table 1 and the material type of the product name (abbreviation thereof) is as follows.

Epoxy resin
828US: Liquid bisphenol A type epoxy resin
YX4000HK: Bixylenol type epoxy resin
NC3000: Biphenyl aralkyl type epoxy resin
HP6000: Naphthylene ether type epoxy resin
ESN-475V: Naphthol type epoxy resin
HP4700: Naphthalene type tetrafunctional epoxy resin

Curing agent
HPC8000-65T: Active ester curing agent
SN485: Naphthalene type curing agent
LA3018-50P: Triazine skeleton-containing cresol novolac type curing agent dispersant
LB-1520: Nonionic surfactant (ether type)
AKM-0531: Nonionic surfactant (styrene-maleic acid copolymer type)
KBM-103: Phenylsilane type silane coupling agent
KBM-403: Epoxy silane type silane coupling agent
KBN-573: Phenylaminosilane type silane coupling agent
KBM-903: Aminosilane type silane coupling agent
KR-46B: Titanate type coupling agent
W-9010: Polymer dispersant having phosphonic acid group (anionic dispersant)
L-18: Polymer dispersant having a carboxylic acid group (anionic dispersant)
VB-F: Cationic surfactant

Table 2 below shows the test (evaluation) results of Examples 1-8 and Comparative Examples 1-8. Table 2 in "10 ^ 11", such as "10 ^ 9" represents ^{"10 11",} "10 ^9", etc. (* 1).

  In general, in order to improve the dispersibility of an inorganic filler typified by silica in an epoxy resin, the inorganic filler may be treated with a silane-based or titanium-based coupling agent. However, when the dielectric powder (barium titanate) was treated with the coupling agent, a varnish in which the dielectric powder was dispersed in a good dispersion state could not be prepared (Comparative Examples 1 to 4). Further, even if a varnish in which the dielectric powder (barium titanate) is dispersed in a good dispersion state can be prepared, the dielectric powder settles during the storage of the varnish, and the dielectric powder and the resin component are separated. However, a varnish excellent in dispersion stability could not be obtained (Comparative Example 4).

  On the other hand, when the dielectric powder is treated with a nonionic surfactant, a varnish in which the dielectric powder is dispersed in a good dispersion state can be prepared, and further, the dielectric powder and the resin component may be separated during storage. It was possible to obtain a varnish having excellent dispersion stability of the dielectric powder. In addition, a resin composition layer is formed by coating and drying a varnish obtained by treating a dielectric powder with a nonionic surfactant, and the insulating layer obtained by thermosetting the resin composition layer has a high temperature and a high temperature. The insulating layer has high insulation reliability and maintains its high electric resistance even in a humid environment. When the dielectric powder is treated with an anionic or cationic dispersant (surfactant), it is not possible to obtain a varnish having excellent dispersion stability of the dielectric powder, or an insulating layer with high insulation reliability. It was not possible to obtain a varnish capable of forming (Comparative Examples 5 to 8).

Claims (13)

(A) Epoxy resin,
(B) Dielectric powder,
(C) one general formula (3):

(In the formula, A ¹ represents an alkylene group, R ² represents hydrogen, an alkyl group, or an aryl group, and n represents an integer of 1 to 100.)
A polymer compound having a side chain having an oxyalkylene group or a polyoxyalkylene group , which is a compound having a segment represented by, and one or more selected from the group consisting of polyethylene glycol, and (D) curing the resin composition you containing agent. The resin composition according to claim 1, wherein A ¹ is each independently an ethylene group or a propylene group. R ² is a methyl group or an ethyl group, resin composition according to claim 1 or 2. The number average molecular weight of the polyethylene glycol is 150～30,000 resin composition according to any one of claims 1-3. (B) The dielectric powder is one or two selected from the group consisting of barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, zirconium titanate, zinc titanate and titanium dioxide. including more, the resin composition according to any one of claims 1-4. (B) a dielectric powder, barium titanate, resin composition according to any one of claims 1-5. (B) Dielectric powder, (C) a polymer compound having a side chain having an oxyalkylene group or a polyoxyalkylene group, which is a compound having a segment represented by the general formula (3), and a group consisting of polyethylene glycol The resin composition according to any one of claims 1 to 6, which is treated with one kind or two or more kinds selected from the following. The curing agent (D) comprises one or more selected from the group consisting of a phenolic curing agent, a cyanate ester curing agent and an active ester curing agent, according to any one of claims 1 to 8. The resin composition described. A capacitor forming resin composition of the multilayer printed wiring board, the resin composition according to any one of claims 1-8. A fingerprint sensor for the resin composition, the resin composition according to any one of claims 1-8. Claim 1-8 or 1 resin composition according to the resin composition according to paragraph varnish. Sheet laminate material formed by using the resin composition according to any one of claims 1-8. Sandwiched claim 1-8 or insulating layer comprising a cured product of the resin composition according to item 1 has two conductive layers of forming a capacitor, a multilayer printed wiring board with a built-in capacitor.