JP2017075221A - Method for producing resin composition, adhesive film and coreless substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of forming an insulation layer having excellent workability during the polishing and grinding step and excellent adhesion reliability.SOLUTION: There is provided a resin composition which comprises (a) an epoxy resin, (B) a curing agent and (C) an inorganic filler, wherein the Vickers hardness of (HV1) of a resin composition cured by heating at 180°C for 30 minutes satisfies the expression (i): 40<HV1<220, the relation between HV1 and the Vickers hardness of (HV2) of a resin composition cured by heating at 180°C for 90 minutes satisfies the expression (ii): 1<HV2/HV1<1.5 and a resin composition cured by heating at 180°C for 90 minutes has a glass transition temperature of 140°C or more.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and an adhesive film useful for a method for producing a coreless substrate, and a method for producing a coreless substrate.

  With the development of the electronics industry, the demand for higher functionality, lighter, thinner, and smaller electronic components has been increasing rapidly. As a result, printed circuit boards on which such electronic components are mounted are also required to have higher density wiring and thinner plates. It has been. In particular, in order to meet the demand for thinner printed circuit boards, a coreless board that can reduce the overall thickness by removing the core layer and shorten the signal processing time has attracted attention (for example, Patent Document 1).

Special table 2015-5186651 gazette

The coreless substrate can be manufactured, for example, by a method including the following steps (1) to (3):
(1) A circuit precursor and a resin composition layer are in contact with a core layer on which a circuit precursor is formed and an adhesive film having a support and a resin composition layer bonded to the support. And then the resin composition layer is thermally cured after peeling the adhesive film support, or the adhesive film support is peeled off after curing the resin composition layer and cured. Forming an insulating layer as a layer;
(2) A step of polishing and cutting the surface of the insulating layer, and (3) A step of installing a solder ball in contact with the circuit precursor after removing the core layer.

  As an example of the core layer used in the step (1), a schematic view of the core layer having a circuit precursor formed on one side is shown in FIG. FIG. 2 shows a schematic view of the core layer obtained in the above step (1), on which the insulating layer and the circuit precursor are formed. FIG. 3 shows a schematic diagram of the core layer obtained by the step (2), on which the insulating layer and the circuit precursor that have been polished and cut are formed. FIG. 4 shows a schematic view of a coreless substrate having a circuit precursor, an insulating layer, and solder balls obtained in the above step (3).

  Moreover, the schematic of the core layer in which the circuit precursor was formed in both surfaces as an example of the core layer used at the said process (1) is shown in FIG. As such a core layer, for example, a copper clad laminate (CCL) having a peelable copper foil can be used. When CCL having a circuit precursor formed on both sides is used as the core layer, the removal of the core layer in the above step (3) is performed by removing the central copper foil and the resin layer (or prepreg layer) via the release layer. This can be done by peeling off and then removing the remaining copper foil by etching.

  Further, a circuit precursor is formed by plating or the like on the insulating layer and the core layer on which the circuit precursor is ground and cut obtained in the step (2), and the steps (1) and (2) are further performed. After the repetition, the above-mentioned step (3) is performed to remove the core layer, and a solder ball is installed, whereby a multi-layer coreless substrate as shown in FIG. 6 can be manufactured. FIG. 6 shows a coreless substrate having a two-layer structure, but a coreless substrate having a structure of three or more layers can also be manufactured.

  An object of this invention is to provide the resin composition which can form the insulating layer especially suitable for using for the said coreless board | substrate. Specifically, the present invention provides a resin composition that exhibits excellent workability and excellent adhesion reliability during the polishing and cutting process of (2) above, and can form an insulating layer that does not wear the grindstone. The purpose is to do. Furthermore, when forming a conductor layer on this insulating layer, this invention aims at providing the resin composition which can form the conductor layer which has high peel strength. Here, being excellent in adhesion reliability in the polishing cutting process means that the insulating layer is not chipped or cracked by the stress generated in the polishing cutting process, and the insulating layer is not peeled off from the core layer.

  As a result of extensive studies by the present inventors, it has been found that the above object can be achieved by adjusting the Vickers hardness and glass transition temperature of the cured resin composition to be in a specific range. The present invention based on this finding is as follows.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And the glass transition temperature of the resin composition cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher.
[2] The resin composition according to [1], wherein the peel strength between the resin composition cured by heating at 180 ° C. for 30 minutes and the conductor layer formed on the surface thereof is 0.3 kgf / cm or more. object.
[3] The resin composition according to [1] or [2], wherein the epoxy resin as the component (A) includes a biphenyl type epoxy resin.
[4] The resin composition according to any one of [1] to [3], wherein the epoxy resin as the component (A) includes an aminophenol type epoxy resin.
[5] The resin composition according to any one of [1] to [4], further including (E) a polymer resin having an elastic modulus at 23 ° C. of 5 to 200 MPa.
[6] The resin composition according to [5], wherein the polymer resin as the component (E) has a glass transition temperature of 30 ° C. or lower.
[7] The polymer resin as the component (E) is a resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure [5] ] Or the resin composition as described in [6].
[8] The polymer resin as the component (E) is a polyimide resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure. The resin composition according to any one of 5] to [7].
[9] The structure represented by the formula (1-a) and the structure represented by the formula (1-b) of the polymer resin as the component (E):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure, and R2 represents a tetravalent organic group. R3 represents a divalent organic group. ]
The resin composition according to any one of [5] to [8], which is a polyimide resin having
[10] A structure in which the polymer resin as the component (E) is represented by the formula (abc):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure, and R2 represents a tetravalent organic group. R3 represents a divalent organic group, and n and m represent integers. ]
The resin composition according to any one of [5] to [9], which is a polyimide resin having
[11] The resin composition according to any one of [5] to [10], wherein the polymer resin as the component (E) has a number average molecular weight of 5,000 to 25,000.
[12] An adhesive film having a support and a resin composition layer composed of the resin composition according to any one of [1] to [11] bonded to the support.
[13] (1) A core layer having a circuit precursor formed thereon, and an adhesive film having a support and a resin composition layer bonded to the support, the circuit precursor and the resin composition layer. And then the resin composition layer is thermally cured after peeling the adhesive film support, or the adhesive film support is peeled and cured after the resin composition layer is thermally cured. Forming an insulating layer which is a resin composition layer;
(2) An adhesive film used in a method of manufacturing a coreless substrate, comprising: a step of polishing and cutting the surface of an insulating layer; and (3) a step of installing a solder ball in contact with a circuit precursor after removing the core layer. And
The resin composition layer includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And a glass transition temperature of a resin composition layer cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher.
[14] (1) A core layer having a circuit precursor formed thereon, and an adhesive film having a support and a resin composition layer bonded to the support, the circuit precursor and the resin composition layer. And then the resin composition layer is thermally cured after peeling the adhesive film support, or the adhesive film support is peeled and cured after the resin composition layer is thermally cured. Forming an insulating layer which is a resin composition layer;
(2) a step of polishing and cutting the surface of the insulating layer, and (3) a method of manufacturing a coreless substrate, including a step of installing a solder ball that contacts the circuit precursor after removing the core layer,
The resin composition layer includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And the glass transition temperature of the resin composition layer cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher.

  From the resin composition of the present invention, an insulating layer having excellent workability and excellent adhesion reliability during the polishing cutting process can be formed.

It is the schematic of the core layer in which the circuit precursor was formed in the single side | surface. It is the schematic of the core layer in which the insulating layer and the circuit precursor were formed on it. It is the schematic of the core layer in which the insulating layer and circuit precursor which were grind | polished and cut were formed on it. It is the schematic of the coreless board | substrate which has a circuit precursor, an insulating layer, and a solder ball. It is the schematic of the core layer in which the circuit precursor was formed in both surfaces. It is the schematic of the coreless board | substrate of a multilayer (2 layer) structure.

(I) Resin Composition The resin composition of the present invention has a Vickers hardness (HV1) of a resin composition cured by heating at 180 ° C. for 30 minutes, the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And the glass transition temperature of the resin composition cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher. Hereinafter, (A) epoxy resin and the like will be described in order.

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as the component (A). Only one type of epoxy resin may be used, or two or more types may be used in combination. The number average molecular weight of the epoxy resin is preferably 100 to 5,000, more preferably 200 to 3,000.

  The content of the epoxy resin as the component (A) is from 100% by mass of the solid content of the resin composition, preferably 3 to 50% by mass, from the viewpoint of imparting chemical resistance to the resin composition after thermosetting. More preferably, it is 3.5-40 mass%.

  In the present invention, the epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule and having an epoxy equivalent of 50 g / eq or more and less than 5,000 g / eq. The epoxy equivalent of the epoxy resin is more preferably 50 to 3000 g / eq, further preferably 80 to 2000 g / eq, still more preferably 110 to 1000 g / eq, and particularly preferably 150 to 300 g / eq. Here, the epoxy equivalent is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236.

  Examples of the epoxy resin include biphenyl type epoxy resin, aminophenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert- Butyl-catechol type epoxy resin, naphthalene type epoxy resin (for example, “EXA-731-G4S” manufactured by DIC Corporation), naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type Epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having polybutadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy Fat, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, and halogenated epoxy resins.

  From the viewpoint of imparting low hygroscopicity to the resin composition, the epoxy resin preferably contains a biphenyl type epoxy resin. Biphenyl type epoxy resin may use only 1 type and may use 2 or more types. Specific examples of the biphenyl type epoxy resin include “NC-3000H”, “NC-3000L”, “NC-3000”, “NC-3100” manufactured by Nippon Kayaku Co., Ltd., “ YX-4000 "," YX-4000H ", etc. are mentioned.

  When a biphenyl type epoxy resin is used, the content thereof is preferably 10 to 80% by mass, more preferably 15 to 70% by mass in 100% by mass of the epoxy resin.

  From the viewpoint of imparting heat resistance to the resin composition, the epoxy resin preferably contains an aminophenol type epoxy resin. Only 1 type may be used for an aminophenol type epoxy resin, and 2 or more types may be used for it. Specific examples of the aminophenol type epoxy resin include “630LSD” and “630” manufactured by Mitsubishi Chemical Corporation, “EP-3950S” and “EP-3950L” manufactured by ADEKA Corporation.

  When using an aminophenol type epoxy resin, the content thereof is preferably 2 to 80% by mass, more preferably 3 to 70% by mass in 100% by mass of the epoxy resin.

  From the viewpoint of imparting flowability to the resin composition, the epoxy resin preferably contains a liquid epoxy resin. Here, the liquid epoxy resin means an epoxy resin that is liquid at 25 ° C. A liquid epoxy resin may use only 1 type and may use 2 or more types.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, and alicyclic epoxy resins having an ester skeleton. And epoxy resins having a butadiene structure are preferable, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ( Bisphenol A type epoxy resin and bisphenol F type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (ester structure) manufactured by Daicel Corporation Alicyclic Epoxy with Resin), "PB-3600" (epoxy resin having a butadiene structure) and the like.

  When using a liquid epoxy resin, the content thereof is preferably 10 to 90% by mass, more preferably 20 to 80% by mass in 100% by mass of the epoxy resin.

<(B) Curing agent>
The resin composition of this invention contains a hardening | curing agent as a component (B). In the present invention, the curing agent is not particularly limited as long as it has a reactive group that reacts with the epoxy resin and has a function of curing the epoxy resin. The reactive group may be protected. Examples of the curing agent include amine-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phenol-based curing agents (for example, phenol novolac resins), naphthol-based curing agents, benzoxazine-based curing agents, carbodiimide-based curing agents, Examples include cyanate ester-based curing agents, active ester-based curing agents, acid anhydride-based curing agents, and epoxy adducts or microencapsulated ones thereof. Only one type of curing agent may be used, or two or more types may be used in combination.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent and a nitrogen-containing naphthol-based curing agent are preferable, and a triazine skeleton-containing phenol-based curing agent and a triazine skeleton-containing naphthol-based curing agent are more preferable. preferable. Of these, a triazine skeleton-containing phenol novolak resin and a triazine skeleton-containing naphthol novolak resin are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052," "LA-7054," "LA-3018," "LA-1356," "TD2090" manufactured by DIC Corporation ".

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, Bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl diester. Cyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, , 3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bifunctional cyanate resins such as bis (4-cyanatephenyl) ether, phenol novolac and cresol novolac From Guide is the polyfunctional cyanate resin, these cyanate resins prepolymers and the like obtained by partly triazine of. These may be used alone or in combination of two or more. Examples of commercially available cyanate ester curing agents include dicyclopentadiene structure-containing cyanate ester resins (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000), “primerset ( “Primaset BA200” (manufactured by Lonza), “Primaset BA230S” (manufactured by Lonza), “Primaset LECY” (Lonza), which is a bisphenol H-type cyanate ester resin. ), “Arocy L10” (manufactured by Bantico), “Primaset PT30” (manufactured by Lonza), “Arocy XU371” (Bante), a novolac-type cyanate ester resin Manufactured by co Ltd.), a dicyclopentadiene type cyanate ester resin "Aroshi (Arocy) XP71787.02L" (Vantico Inc.), and the like. Only one type of cyanate ester curing agent may be used, or two or more types may be used in combination.

  Although it does not specifically limit as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are generally in 1 molecule. A compound having two or more is preferably used. The active ester 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester 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.

  Specifically, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolak, and an active ester compound containing a benzoylated product of a phenol novolak are preferred. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferred.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (DIC Corporation) as active ester compounds containing a dicyclopentadienyl diphenol structure. Manufactured product), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoylated compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  As the curing agent, a phenol curing agent, a naphthol curing agent, a cyanate ester curing agent and an active ester curing agent are preferable, a phenol curing agent and a naphthol curing agent are preferable, and a phenol curing agent is more preferable. From the viewpoint of imparting sufficient heat resistance to the resin composition, the content of the curing agent is preferably 10 to 90 parts by mass, more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin as the component (A). It is 85 mass parts, More preferably, it is 20-80 mass parts.

<(C) Inorganic filler>
The resin composition of the present invention contains an inorganic filler as the component (C). Only one type of inorganic filler may be used, or two or more types may be used in combination.

  Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica and alumina are preferable, and silica is more preferable.

  As commercially available alumina, for example, “DAW-3”, “DAW-1”, “DAW-7”, “DAW-45”, “ASFP-20” manufactured by Denka Co., Ltd., Admatechs Co., Ltd. “AO-802”, “AO-809”, “AO-820” manufactured by Showa Denko KK, “CB-P02”, “CB-P05”, “CB-P07”, “CB-P10” , “CB-P15”, “CB-P40”, “CB-A20S”, “CB-A30S”, “CB-A40S”, and the like.

  Examples of the silica include amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica. From the viewpoint of enhancing the filling property, fused silica and spherical silica are preferable, and spherical fused silica is more preferable. Examples of commercially available spherical fused silica include “SO-C1”, “SO-C2”, and “SO-C5” manufactured by Admatechs Co., Ltd.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, even more preferably 1 μm or less, and even more preferably 0.8 μm or less from the viewpoint of insulation reliability. Particularly preferred is 0.6 μm or less. On the other hand, from the viewpoint of preventing the viscosity of the resin composition from increasing and handling properties from decreasing, the average particle size is preferably 0.01 μm or more, more preferably 0.03 μm or more, and 0.05 μm or more. More preferably, 0.07 μm or more is even more preferable, and 0.1 μm or more is even 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 prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  The content of the inorganic filler is preferably from 40 to 93% by mass, more preferably from 50 to 92% by mass, and still more preferably from 100% by mass of the solid content of the resin composition from the viewpoint of improving the coefficient of thermal expansion and tack. It is 60-90 mass%.

  As the inorganic filler, it is preferable to use an inorganic filler surface-treated with one or more surface treatment agents. Examples of the surface treatment agent include amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, and sulfides. Examples include silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents. By the surface treatment, the dispersibility and moisture resistance of the inorganic filler can be improved.

  Specific surface treatment agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-methylamino. Aminosilane coupling agents such as propyltrimethoxysilane, N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; 3-glycidyloxy Propyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane; mercapto such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Silane coupling agents; styrylsilane coupling agents such as p-styryltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryl Acrylate silane coupling agents such as oxypropyltriethoxysilane and 3-methacryloxypropyldiethoxysilane; 3-isocyanatopropyltrimethoxy Isocyanate silane coupling agents such as run; sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxy Silane coupling agents such as silane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane; hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyl Disilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3 Organosilazane compounds such as 1,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane; tetra-n- Butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxytitanium bis (triethanolaminate), dihydroxytitanium bislactate, dihydroxybis (ammonium lactate) G) Titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl Bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl Phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryliso And titanate coupling agents such as theaeroyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-amidoethyl / aminoethyl) titanate . Of these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred, and aminosilane coupling agents are more preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like.

  The surface treatment method of the inorganic filler with the surface treatment agent is not particularly limited, and examples thereof include a dry method and a wet method. As a dry method, for example, an inorganic filler is charged in a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, followed by further stirring, classification with a sieve, and then surface treatment by heating. And a method of dehydrating and condensing the agent and the inorganic filler. As a wet method, for example, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, classification is performed by filtration, drying and sieving, and then the surface treatment agent and the inorganic solvent are heated. The method of dehydrating and condensing with a filler is mentioned.

<(D) Curing accelerator>
The resin composition of this invention can contain a hardening accelerator as a component (D). A hardening accelerator is a compound which has a function which accelerates | stimulates reaction of (A) epoxy resin and (B) hardening | curing agent, or (A) reaction between epoxy resins. A hardening accelerator may use only 1 type and may use 2 or more types together. Although it does not specifically limit as a hardening accelerator, For example, an imidazole type hardening accelerator, an amine type hardening accelerator, a guanidine type hardening accelerator, a phosphonium type hardening accelerator etc. are mentioned.

  Examples of the imidazole curing accelerator include 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 trimellitate, 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-dihydroxymethylimidazole, 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, 2-phenyl-imidazoline, etc. imidazole compounds of and imidazole compounds and adducts such as with epoxy resin. A commercial item may be used for an imidazole series hardening accelerator. Examples of commercially available imidazole-based curing accelerators include “2P4MZ” manufactured by Shikoku Kasei Co., Ltd.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. And amine compounds such as [5.4.0] -undecene (hereinafter abbreviated as DBU).

  Examples of the guanidine curing accelerator include 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-phenyl biguanide, 1- ( - tolyl) biguanide, and the like.

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

  When using a curing accelerator, the content thereof is preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin as the component (A) from the viewpoint of storage stability of the resin composition. Preferably it is 0.3-4 mass parts, More preferably, it is 0.4-3 mass parts.

<(E) Polymer resin having an elastic modulus of 5 to 200 MPa at 23 ° C.>
The resin composition of the present invention may further contain a polymer resin having an elastic modulus at 23 ° C. of 5 to 200 MPa as the component (E). Only 1 type may be used for the polymeric resin which is a component (E), and 2 or more types may be used together.

  The elastic modulus at 23 ° C. of the polymer resin as the component (E) is as follows. First, a polymer resin film is produced according to Japanese Industrial Standard (JIS K7127), It is the value measured by conducting a tensile test of the film using a testing machine (manufactured by A & D Co., Ltd.). From the viewpoint of imparting sufficient flexibility to the resin composition, the elastic modulus is preferably 7 to 180 MPa, more preferably 10 to 150 MPa.

  From the viewpoint of imparting sufficient heat resistance, the number average molecular weight of the polymer resin as the component (E) is preferably 5,000 to 25,000, more preferably 7,000 to 22,000, and still more preferably. 9,000 to 20,000. Here, the number average molecular weight of the polymer resin is a value measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight determined by the GPC method is 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. 804 L can be measured using chloroform as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

  From the viewpoint of imparting sufficient flexibility to the resin composition, the glass transition temperature of the polymer resin as the component (E) is preferably 30 ° C. or lower, more preferably −15 ° C. to 29 ° C., still more preferably − 10 ° C to 20 ° C. Here, the glass transition temperature of the polymer resin can be read from a tan δ peak temperature obtained by dynamic viscoelasticity measurement or thermomechanical analysis by a tensile load method using a thermomechanical analyzer.

  When using the polymer resin as the component (E), the content thereof is preferably 100% by mass in the solid content of the resin composition from the viewpoint of securing the adhesion between the resin composition and the adherend. It is 2-40 mass%, More preferably, it is 3-30 mass%, More preferably, it is 4-20 mass%.

  The polymer resin as component (E) is preferably a resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure. Both the polybutadiene structure and the polyisoprene structure may be hydrogenated. The polymer resin is more preferably a polyimide resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure, and more preferably a polybutadiene structure, A polyimide resin having an isoprene structure or a polycarbonate structure, particularly preferably a polyimide resin having a polybutadiene structure or a polycarbonate structure.

  When using a polyimide resin as a component (E), the acid value is preferably 3 to 30 mgKOH / g, and more preferably 5 to 20 mKOH / g.

  Examples of the polybutadiene structure include a polybutadiene structure represented by the formula (ia) or the formula (ib), or a hydrogenated polybutadiene structure represented by the formula (ic) or the formula (id). Can be mentioned.

[In the formulas (ia) to (id), n1 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  Examples of the polyisoprene structure include a polyisoprene structure represented by the formula (ii-a) or a hydrogenated polyisoprene structure represented by the formula (ii-b).

[In formulas (ii-a) and (ii-b), n2 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  Examples of the polycarbonate structure include those represented by the formula (iii).

[In formula (iii), R4 and R5 each independently represent an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and n3 is an integer of 5 to 30 (preferably 10 to 20). Integer). ]

  Examples of the (meth) acrylate structure include those represented by the formula (iv).

[In Formula (iv), R6 represents a hydrogen atom or a methyl group, and R7 represents an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms. ]

  Examples of the polysiloxane structure include those represented by the formula (v).

(Wherein R8 and R9 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms, and R10 to R14 each independently represent a carbon number. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group; a, b and c each independently represent an integer of 0 or more, and b + c ≧ 1 and a + b + c ≧ 60 In the formula, a hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.)

  Specific examples of the resin having a polysiloxane structure include those described in International Publication No. 2010/053185.

  Examples of the polyimide resin having a polybutadiene structure, a polyisoprene structure, or a polycarbonate structure include a structure represented by the formula (1-a) and a structure represented by the formula (1-b):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure (preferably a divalent organic group having a polybutadiene structure). Group or a divalent organic group having a polycarbonate structure), R2 represents a tetravalent organic group, and R3 represents a divalent organic group. ]
(Hereinafter sometimes abbreviated as “polyimide resin (1-a) (1-b)”).

  Among the polyimide resins (1-a) (1-b), a structure represented by the formula (abc):

[Wherein, R1 to R3 have the same meanings as described above, and n and m represent integers. ]
A polyimide resin (hereinafter sometimes abbreviated as “polyimide resin (abc)”) is preferred. n is an integer of, for example, 1 to 100, preferably an integer of 1 to 10, and m is an integer of, for example, 1 to 100, preferably an integer of 1 to 10. Hereinafter, the polyimide resin (1-a) (1-b) and the polyimide resin (abc) may be collectively referred to as “polyimide resin (E)”.

  The divalent organic group having a polybutadiene structure is, for example, a residue excluding the hydroxy group of a bifunctional hydroxy group-terminated polybutadiene used as a raw material. Examples of such groups include the following.

[In the formulas (ia) to (id), n1 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  The divalent organic group having a polyisoprene structure is, for example, a residue excluding the hydroxy group of a bifunctional hydroxy group-terminated polyisoprene used as a raw material. Examples of such groups include the following.

[In formulas (ii-a) and (ii-b), n2 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  The divalent organic group having a polycarbonate structure is, for example, a residue excluding the hydroxy group of polycarbonate diol used as a raw material. Examples of such groups include the following.

[In formula (iii), R4 and R5 each independently represent an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and n3 is an integer of 5 to 30 (preferably 10 to 20). Integer). ]

  The tetravalent organic group is, for example, a residue excluding a carboxy group or an acid anhydride group of a polybasic acid or its anhydride used as a raw material. Examples of such tetravalent organic groups include the following groups.

[Wherein, A is an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , or C (CCl ₃ ) ₂ Represents. In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like. ]

  The divalent organic group which is R3 is, for example, a residue excluding the isocyanate group of the diisocyanate compound. Examples of the diisocyanate compound include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; fats such as isophorone diisocyanate. And cyclic diisocyanates. Among these, aromatic diisocyanates and alicyclic diisocyanates are preferable, and toluene-2,4-diisocyanate and isophorone diisocyanate are more preferable.

  A polyimide resin having a polybutadiene structure, a polyisoprene structure or a polycarbonate structure can be produced, for example, as follows. First, a bifunctional hydroxy group-terminated polybutadiene, a bifunctional hydroxy group-terminated polyisoprene or a polycarbonate diol, and a diisocyanate compound are converted into a bifunctional hydroxy group-terminated polybutadiene, a bifunctional hydroxy group-terminated polyisoprene, or a hydroxy group 1 of a polycarbonate diol. The amount of the isocyanate group of the diisocyanate compound with respect to mol is reacted at a ratio exceeding 1 mol, and the formula (ab):

[Wherein R 1, R 3 and n are as defined above. ]
The diisocyanate reaction product represented by the formula (hereinafter sometimes abbreviated as “diisocyanate reaction product (ab)”) is produced.

  The number average molecular weight of the bifunctional hydroxy group-terminated polybutadiene used as a raw material is preferably 800 to 10,000, more preferably 1,000 to 6,000, from the viewpoint of good compatibility with other raw materials. It is. The method for measuring the number average molecular weight of the bifunctional hydroxy group-terminated polybutadiene is the same as the method for measuring the number average molecular weight of the polymer resin (GPC method). The preferred number average molecular weight of the residue excluding the hydroxy group of the bifunctional hydroxy group-terminated polybutadiene as R1 is the same as described above.

  Commercially available products can be used as the bifunctional hydroxy group-terminated polybutadiene. Examples of such commercial products include G-3000, G-1000, GI-3000, GI-1000 manufactured by Nippon Soda Co., Ltd., R-45EPI manufactured by Idemitsu Petrochemical Co., Ltd., and the like.

  The number average molecular weight of the bifunctional hydroxy group-terminated polyisoprene used as a raw material is preferably 800 to 10,000, more preferably 1,000 to 6, from the viewpoint of good compatibility with other raw materials. 000. The method for measuring the number average molecular weight of the bifunctional hydroxy group-terminated polyisoprene is the same as the method for measuring the number average molecular weight of the polymer resin (GPC method). The preferred number average molecular weight of the residue excluding the hydroxy group of the bifunctional hydroxy group-terminated polyisoprene as R1 is the same as described above.

  Commercially available products can be used as the bifunctional hydroxy group-terminated polyisoprene.

  The number average molecular weight of the polycarbonate diol used as the raw material is preferably 500 to 5,000, more preferably 1,000 to 3,000, from the viewpoint of good compatibility with other raw materials. In addition, the measuring method of the number average molecular weight of polycarbonate diol is the same as the measuring method (GPC method) of the above-mentioned polymer resin. Moreover, the preferable number average molecular weight of the residue except the hydroxyl group of polycarbonate diol which is said R1 is also the same as the above.

  A commercially available product can be used as the polycarbonate diol. Examples of such commercially available products include C-1015N and C-2015N manufactured by Kuraray Co., Ltd., T-6002, T-4672, T-5562 manufactured by Asahi Kasei Chemicals Corporation, and CD205 manufactured by Daicel Corporation. CD205PL, CD205HL, CD210, CD210PL, Nippon Polyurethane Industry Co., Ltd. Nippon Run 981, 980R, and the like.

  Examples of the diisocyanate compound used as a raw material include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate. And alicyclic diisocyanates such as Among these, aromatic diisocyanates and alicyclic diisocyanates are preferable, and toluene-2,4-diisocyanate and isophorone diisocyanate are more preferable.

  Bifunctional hydroxy group-terminated polybutadiene, difunctional hydroxy group-terminated polyisoprene or polycarbonate diol, in an amount such that the molar ratio of hydroxy group: isocyanate group of diisocyanate compound is 1: 1.5 to 1: 2.5. It is preferable to react.

  The reaction between the bifunctional hydroxy group-terminated polybutadiene and the difunctional hydroxy group-terminated polyisoprene or polycarbonate diol and the diisocyanate compound is usually carried out in an organic solvent at a temperature of 80 ° C. or lower for 1 to 8 hours. In this reaction, a catalyst may be used if necessary.

  Examples of the organic solvent include N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′-diethylacetamide, dimethyl sulfoxide, diethyl sulfoxide, N-methyl- Examples include polar solvents such as 2-pyrrolidone, tetramethylurea, γ-butyrolactone, cyclohexanone, diglyme, triglyme, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These polar solvents may use only 1 type and may use 2 or more types together. Further, if necessary, nonpolar solvents such as aromatic hydrocarbons may be appropriately mixed and used.

  Examples of the catalyst include organometallic catalysts such as dibutyltin dilaurate, dimethyltin dichloride, cobalt naphthenate, and zinc naphthenate.

  Next, a polybasic acid or an anhydride thereof is reacted with the obtained diisocyanate reactant (ab).

  Examples of the polybasic acid or its anhydride used as a raw material include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3- Tetrabasic acids such as methyl-cyclohexene-1,2-dicarboxylic acid, 3,3′-4,4′-diphenylsulfonetetracarboxylic acid and their anhydrides, tribasic acids such as trimellitic acid, cyclohexanetricarboxylic acid, and These anhydrides, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphth (1,2-C) furan-1,3-dione Etc. Among these, tetrabasic acid anhydrides are preferable, tetrabasic acid dianhydrides are more preferable, and benzophenone tetracarboxylic dianhydride is more preferable.

In order to prevent the isocyanate group from remaining in the polyimide resin (E) as much as possible, the molar amount of the isocyanate group contained in the diisocyanate compound is X, bifunctional hydroxy group-terminated polybutadiene, bifunctional hydroxy group-terminated polyisoprene or polycarbonate diol. When the molar amount of the hydroxy group contained in W is W, the molar amount of the carboxy group contained in the polybasic acid or its anhydride is Y ₁ and the molar amount of the acid anhydride group is Y ₂ , 0.5Y ₁ + Y ₂ > It is preferable to carry out the reaction in an amount satisfying the relationship of X−W ≧ (0.5Y ₁ + Y ₂ ) / 5.

  The reaction between the diisocyanate reactant (ab) and the polybasic acid or anhydride thereof is usually performed at a temperature of 120 to 180 ° C. for 2 to 24 hours. In this reaction, a catalyst may be used if necessary. Further, the reaction may be carried out after further adding the above-mentioned organic solvent.

  Examples of the catalyst include amines such as tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, N, N′-dimethylpiperidine, α-methylbenzyldimethylamine, N-methylmorpholine, and triethylenediamine. It is done. Of these, triethylenediamine is preferred.

  In the reaction described above, it is preferable to confirm the disappearance of the isocyanate group by FT-IR or the like so as not to leave the isocyanate group (—NCO) in the polyimide resin (E) as much as possible. The end of the polyimide resin (E) thus obtained is represented by formula (1-c) or formula (1-d):

[In each formula, R2 is as defined above. ]
Can be expressed as

In the production of the polyimide resin (E), after reacting the diisocyanate reactant (ab) with a polybasic acid or its anhydride, the resulting reactant is further reacted with a diisocyanate compound to obtain a higher molecular weight. The polyimide resin can be manufactured. In this case, the reaction ratio of the isocyanate compound is not particularly limited, but the molar amount of the isocyanate group contained in the diisocyanate compound is X, the hydroxy group contained in the bifunctional hydroxy group-terminated polybutadiene, difunctional hydroxy group-terminated polyisoprene or polycarbonate diol. the molar amount of isocyanate group contained a molar amount of base is W, the molar amount of carboxyl groups contained in the polybasic acid or its anhydride molar amount of Y ₁ and acid anhydride groups in Y _2, a diisocyanate compound is further reacted Is Z, it is preferable to carry out the reaction in an amount satisfying the relationship of (0.5Y ₁ + Y ₂ ) − (X−W)> Z ≧ 0.

  The above reaction with a further diisocyanate compound is usually carried out at a temperature of 120 to 180 ° C. for 2 to 24 hours.

  When the polyisocyanate or the anhydride thereof is reacted with the diisocyanate reactant (ab), a modifier such as a polyfunctional phenol compound can be added as appropriate.

<Other ingredients>
The resin composition of the present invention may contain other components in addition to the components (A) to (E) described above.

  The resin composition of the present invention may further contain a thermoplastic resin. When using a thermoplastic resin, the content thereof is preferably 100 to 40% by mass, more preferably 0.7 to 30% by mass, and even more preferably 1 to 100% by mass of the solid content of the resin composition. 25% by mass.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 1,000,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  As a thermoplastic resin, an acrylate copolymer and a phenoxy resin are preferable, and a phenoxy resin is more preferable.

  Specific examples of the acrylic ester copolymer include “Taisan Resin SG-P3”, “Taisan Resin SG-600LB”, “Taisan Resin SG-280”, and “Taisan Resin SG-790” manufactured by Nagase ChemteX Corporation. ”,“ Taisan Resin SG-K2 ”,“ SN-50 ”,“ AS-3000E ”,“ ME-2000 ”manufactured by Negami Kogyo Co., Ltd., and the like.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YL6954BH30", "YX7553", "YL6794" manufactured by Mitsubishi Chemical Corporation, “YL7213”, “YL7290” and “YL7482” may be mentioned.

  The epoxy equivalent of the phenoxy resin is preferably 6,000 to 30,000 g / eq, more preferably 7,000 to 20,000 g / eq, and still more preferably 9,000 to 15,000 g / eq. The weight average molecular weight in terms of polystyrene of the phenoxy resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 10,000 to 100,000, and still more preferably in the range of 20,000 to 60,000.

  The resin composition of the present invention may further contain a bismaleimide resin, a bisallylnadiimide resin, a vinyl benzyl ether resin, a benzoxazine resin, a polymer of bismaleimide and a diamine, and the like.

  Examples of the bismaleimide resin include “BMI-S” (Mitsui Chemical Co., Ltd.), which is 4,4′-phenylmethane bismaleimide, and “BMI-M-20” (Mitsui Chemicals, Inc.), which is polyphenylmethane maleimide. Etc.). Bismaleimide resin may use only 1 type and may use 2 or more types together.

  Examples of the bisallylnadiimide resin include “BANI-M” (manufactured by Maruzen Petrochemical Co., Ltd.), which is diphenylmethane-4,4′-bisallylnadicimide. A bisallyl nadiimide resin may use only 1 type and may use 2 or more types together.

  Examples of the vinyl benzyl ether resin include V-1000X (manufactured by Showa Polymer Co., Ltd.), US Pat. No. 4,116,936, US Pat. No. 4,170,711, US Pat. No. 4,278,708, and JP-A-9-31006. No. 1, JP-A No. 2001-181383, JP-A No. 2001-253992, JP-A No. 2003-277440, JP-A No. 2003-283076, WO 02/083610, and the like. . Only 1 type may be used for a vinyl benzyl ether resin, and it may use 2 or more types together.

  Examples of the benzoxazine resin include “Ba type benzoxazine” and “Bm type benzoxazine” manufactured by Shikoku Kasei Co., Ltd. Only one type of benzoxazine resin may be used, or two or more types may be used in combination.

  Examples of the polymer of a bismaleimide compound and a diamine compound that are thermosetting resins include “Techmite E2020” manufactured by Printec Co., Ltd. As the polymer of the bismaleimide compound and the diamine compound, only one type may be used, or two or more types may be used in combination.

  The resin composition of the present invention further comprises organic fillers such as silicone powder, nylon powder, fluorine powder, rubber particles; thickeners such as Orben and Benton; silicone-based, fluorine-based, polymer-based antifoaming agents or Leveling agents; adhesion-imparting agents such as thiazole-based silane coupling agents and triazole-based silane coupling agents; coloring agents such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, and carbon black; organophosphorous flame retardants , Organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, flame retardants such as metal hydroxides, and the like.

<Vickers hardness (HV1) of resin composition cured by heating at 180 ° C. for 30 minutes>
In the resin composition of the present invention, HV1 has the formula (i):
40 <HV1 <220 (i)
One of the characteristics is to satisfy. The Vickers hardness can be measured using a Vickers hardness meter (for example, manufactured by Mitutoyo Corporation) in accordance with Japanese Industrial Standard (JIS Z 2244).

  By satisfying 40 <HV1, problems such as clogging of the grindstone can be prevented in the polishing and cutting process, and the polishing and cutting process can be performed smoothly. Moreover, by satisfying HV1 <220, the wear of the grindstone can be suppressed and the life of the grindstone can be extended. HV1 is preferably 41 or more, more preferably 45 or more, preferably 219 or less, more preferably 210 or less.

  The amount of (A) epoxy resin, (B) curing agent, and (C) inorganic filler to be blended in the resin composition is appropriately adjusted, or (A) type of epoxy tree, (C) type of inorganic filler HV1 can satisfy the formula (i) by appropriately selecting. For example, HV1 can be increased by increasing the amount of the (C) inorganic filler blended in the resin composition, and HV1 can be decreased by reducing the amount of the (C) inorganic filler. it can.

<Relationship between Vickers Hardness (HV1) of Resin Composition Cured by Heating at 180 ° C. for 30 Minutes and Vickers Hardness (HV2) of Resin Composition Cured by Heating at 180 ° C. for 90 Minutes>
In the resin composition of the present invention, the relationship between HV1 and HV2 is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
One of the characteristics is to satisfy.

  By satisfying 1 <HV2 / HV1, good adhesion between the cured resin composition and the core layer can be achieved. Moreover, by satisfy | filling HV2 / HV1 <1.5, workability | operativity and grindstone abrasion resistance at the time of the grinding | polishing cutting process of the hardened | cured resin composition can be ensured stably irrespective of hardening time. HV2 / HV1 is preferably 1.05 or more, more preferably 1.1 or more, preferably 1.45 or less, more preferably 1.4 or less.

    HV2 / HV1 satisfies the formula (ii) by selecting the type and amount of the (A) epoxy resin and / or (B) curing agent to be blended in the resin composition and appropriately adjusting the reactivity of both. Can be.

<Glass Transition Temperature of Resin Composition Cured by Heating at 180 ° C. for 90 Minutes>
One characteristic of the resin composition of the present invention is that the glass transition temperature is 140 ° C. or higher. When the glass transition temperature is 140 ° C. or higher, problems such as clogging of the grindstone can be prevented in the polishing and cutting process, and the polishing and cutting process can be performed smoothly. The glass transition temperature is preferably 150 ° C. or higher. On the other hand, the upper limit of the glass transition temperature is not particularly limited, but the glass transition temperature is, for example, 300 ° C. or less, preferably 200 ° C. or less, more preferably 180 or less. This glass transition temperature can be measured by the method described in the Examples.

<Peel strength between the resin composition cured by heating at 180 ° C. for 30 minutes and the conductor layer formed on the surface>
The peel strength between the resin composition cured by heating at 180 ° C. for 30 minutes and the conductor layer formed on the surface thereof was “(7) formed on the cured resin composition layer and the surface thereof in the following examples. It can be measured by the method described in “Peel Strength Between Conducted Layers”. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, further preferably 0.4 kgf / cm or more, and particularly preferably 0.5 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but the peel strength is, for example, 2 kgf / cm or less, preferably 1.2 kgf / cm or less.

<Manufacture of resin composition>
The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. Can be manufactured.

(II) Adhesive film The present invention provides an adhesive film having a support and a resin composition layer comprising the resin composition of the present invention bonded to the support. The description of the resin composition is as described above.

The present invention is also an adhesive film used in a method of manufacturing a coreless substrate described later,
The resin composition layer includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And an adhesive film in which the glass transition temperature of the resin composition layer cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher is also provided.

  Description of (A) epoxy resin etc. which a resin composition layer contains, and description of HV1, HV2 and the said glass transition temperature of a resin composition layer are the same as the description in the above-mentioned resin composition. Hereafter, the support body of an adhesive film, etc. are demonstrated in order.

<Support>
Examples of the support used for the adhesive film include a plastic film, a release paper, a copper foil, a metal foil such as an aluminum foil, and the like. Among these, a plastic film is preferable. Examples of the plastic film include polyolefin (eg, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (eg, polyethylene terephthalate), polyethylene naphthalate, etc.), polycarbonate, polyimide, etc., among these, A polyester film is preferable, and a polyethylene terephthalate film is more preferable.

  The thickness of the support is preferably 3 to 100 μm, more preferably 10 to 75 μm, from the viewpoint of securing good handling properties.

<Formation of resin composition layer>
The resin composition layer may be formed by a method known to those skilled in the art. For example, a varnish in which the resin composition of the present invention is dissolved in an organic solvent is prepared, and the varnish is applied and dried on a support. Can be formed. The organic solvent can be dried by, for example, hot air blowing.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol. Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc .; Aromatic mixed solvents such as solvent naphtha. You may use an organic solvent 1 type or in combination of 2 or more types.

  The drying conditions are not particularly limited, but the drying temperature is, for example, 30 to 150 ° C., preferably 50 to 140 ° C., and the drying time is, for example, 1 to 10 minutes, preferably 2 to 8 minutes.

  The thickness (thickness after drying) of the resin composition layer is preferably 3 to 700 μm, more preferably 4 to 650 μm, and still more preferably 5 to 600 μm.

(III) Manufacturing method of coreless substrate
(1) A circuit precursor and a resin composition layer are in contact with a core layer on which a circuit precursor is formed and an adhesive film having a support and a resin composition layer bonded to the support. And then the resin composition layer is thermally cured after peeling the adhesive film support, or the adhesive film support is peeled off after curing the resin composition layer and cured. Forming an insulating layer as a layer;
(2) a step of polishing and cutting the surface of the insulating layer, and (3) a method of manufacturing a coreless substrate, including a step of installing a solder ball that contacts the circuit precursor after removing the core layer,
The resin composition layer includes (A) an epoxy resin, (B) a curing agent, and ((C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And a glass transition temperature of the resin composition layer cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher.

  Description of (A) epoxy resin etc. which a resin composition layer contains, and description of HV1, HV2 and the said glass transition temperature of a resin composition layer are the same as the description in the above-mentioned resin composition. Hereinafter, process (1) etc. are demonstrated in order.

<Step (1)>
In step (1), laminating can be performed on one or both sides of the core layer. Examples of the core layer include a metal plate, a glass plate, a resin (for example, engineering plastic) layer, a prepreg layer (for example, a resin layer including glass cloth), or a metal on one or both sides of the glass plate, the resin layer, or the prepreg layer. A layer-formed one (for example, a copper clad laminate (CCL) having a peelable copper foil) or the like is used. The thickness of the core layer is, for example, 30 to 800 μm.

  The circuit precursor can be formed by a general method using a photoresist. That is, the core layer is covered with a photoresist, and the photoresist is exposed and developed using a mask to create a pattern. A trace layer is formed by adhering the produced pattern with a conductive material such as copper. Thereafter, metal pillars are formed on the trace layer by a similar process using a similar photoresist. For example, the metal pillar has a width of 30 to 90 μm and a height of 10 to 200 μm. The thermosetting of the resin composition can be performed, for example, in an oven or the like. For example, the temperature of thermosetting is 130-220 ° C., and the time is 15-120 minutes. Thermal curing can be carried out in the air or under an inert gas.

<Step (2)>
In step (2), polishing cutting is performed on the insulating layer (cured resin composition layer) formed in step (1). The polishing cutting can be performed by polishing using, for example, belt polishing, buff polishing, a surface grinder, or the like. Various counts of abrasive grains can be used depending on the state of the surface of the insulating layer after the target polishing and cutting.

<Step (3)>
The removal of the core layer in step (3) can be performed by chemical etching or mechanically. The installation of the solder ball after the removal of the core layer can be performed by a general method.

  If necessary, the formation of the conductor layer and the insulating layer in steps (1) and (2) may be repeated to form a multilayer wiring layer. Alternatively, after step (2), (a) drilling the insulating layer, (b) roughening the insulating layer, and (c) forming the conductor layer one or more times. Also good.

  Through the step (b) (step of drilling in the insulating layer), holes such as via holes and through holes can be formed in the insulating layer. Step (A) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the circuit board.

  The procedure and conditions for the roughening treatment in the step (b) are not particularly limited, and known procedures and conditions that are usually used in forming the insulating layer of the circuit board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  The arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 280 nm or less, even more preferably 260 nm or less, still more preferably 240 nm or less, still more preferably 220 nm or less, particularly preferably. 200 nm or less. Although the minimum of Ra is not specifically limited, Ra is 1 nm or more, for example, Preferably it is 3 nm or more, More preferably, it is 5 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  The formation of the conductor layer in the step (c) can be performed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. However, the present invention is not limited by the following synthesis examples and the like, and can be applied to the above and the following purposes. It is of course possible to carry out the invention with appropriate modifications, and these are all included in the technical scope of the present invention. Note that “%” and “parts” described below mean “% by mass” and “parts by mass” unless otherwise specified.

  The “equivalent” described below means the number of grams (g / eq) of a compound containing 1 gram equivalent of a functional group. In other words, the “equivalent” described below means a value obtained by dividing the molecular weight of a compound having a functional group that is the target of equivalent by the number of functional groups that the compound has, that is, the molecular weight per functional group. To do.

Synthesis example 1
(1) Production of polymer resin E varnish Bifunctional hydroxy group-terminated polybutadiene (number average molecular weight: 5,047 (GPC method), hydroxyl equivalent: 1798 g / eq, solid content 100%, Nippon Soda Co., Ltd.) 50 g of “G-3000”), 23.5 g of an aromatic hydrocarbon mixed solvent (“Ipsol 150” manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed. When the mixture became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08 g / eq) was added, and the reaction was carried out for about 3 hours. It was. The reaction was then cooled to room temperature before it was mixed with 8.96 g benzophenone tetracarboxylic dianhydride (anhydride equivalent: 161.1 g / eq), 0.07 g triethylenediamine, and diethylene glycol monoethyl ether acetate. 40.4 g of “Ethyl Diglycol Acetate” manufactured by Daicel Chemical Industries, Ltd. was added, the temperature was raised to 130 ° C. while stirring, and the reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. Upon confirming the disappearance of the NCO peak, the reaction was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a filter cloth having an opening of 100 μm to obtain a varnish of polymer resin E having an imide skeleton, urethane skeleton and polybutadiene skeleton. Got.
Viscosity of polymer resin E varnish: 7.5 Pa · s (25 ° C., E-type viscometer)
Solid content of polymer resin E varnish: 50%
Acid value of polymer resin E: 16.9 mgKOH / g
Number average molecular weight of polymer resin E: 13,723
Glass transition temperature of polymer resin E: −10 ° C.
Content ratio of polybutadiene structure portion of polymer resin E: 50 / (50 + 4.8 + 8.96) × 100 = 78.4%
Elastic modulus of polymer resin E at 23 ° C .: 20 MPa

(2) Measurement of elastic modulus at 23 ° C. The elastic modulus at 23 ° C. of the obtained polymer resin E was measured as follows. The polymer resin E varnish obtained was diluted with diethylene glycol monoethyl ether acetate so that the solid content was 40%. Subsequently, the diluted polymer resin E varnish was applied on a polyethylene terephthalate film (thickness 38 μm) with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried in an oven. The organic solvent was removed to obtain a polymer resin film. Based on the Japanese Industrial Standard (JIS K7127), the film was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.), and its elastic modulus at 23 ° C. was measured.

Example 1
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), acrylic ester copolymer ("Taisan Resin SG-P3" manufactured by Nagase ChemteX Corporation), solid content 15% Methyl ethyl ketone solution, weight average molecular weight of acrylate copolymer: 850,000) 1,000 parts, Crezo Surface with 12 parts of Lunovolak resin (“KA-1163” manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 118 g / eq), inorganic filler {phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) 950 parts of treated spherical fused silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)} and 20 parts of methyl ethyl ketone are mixed and dispersed uniformly with a high-speed rotary mixer. A composition varnish was prepared. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. It was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 2
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolak resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) 950 parts of spherical fused silica surface-treated with “KBM573” (manufactured by Admatechs Co., Ltd., “SO-C2”, average particle size: 0.5 μm)} and 20 parts of methyl ethyl ketone were mixed with a high-speed rotating mixer. The resin composition varnish was prepared by uniformly dispersing. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 3
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolak resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) 950 parts of alumina ("DAW-3" manufactured by Denka Co., Ltd., average particle size: 3 μm)} and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer. A resin composition varnish was prepared. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 4
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 42 parts, naphthalene type 10 parts of epoxy resin (DIC Corporation “EXA-731-G4S”, epoxy equivalent: 186 g / eq), biphenyl type epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent: 288 g / eq ) 8 parts, aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq), curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 Part, phenoxy resin solution ("YX-6654" manufactured by Mitsubishi Chemical Corporation), methyl ethyl ketone and cyclohexanone Methyl ethyl ketone of mixed solution, solid content: 30%, phenoxy resin weight average molecular weight: 38,000 20 parts, naphthol-based curing agent (“SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent: 215 g / eq) 30 parts of a solution (solid content: 50%), 30 parts of methyl ethyl ketone, and an inorganic filler {phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) “SO-C2” manufactured by Admatechs, average particle size: 0.5 μm)} was mixed and uniformly dispersed by a high-speed rotary mixer to prepare a resin composition varnish. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 5
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolak resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) 950 parts of spherical fused silica surface-treated with “KBM573” (manufactured by Admatex Co., Ltd., “SO-C5”, average particle size: 1.5 μm)} and 20 parts of methyl ethyl ketone were mixed with a high-speed rotating mixer. The resin composition varnish was prepared by uniformly dispersing. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 6
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 42 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), naphthalene type epoxy resin (“EXA-7311-G4S” manufactured by DIC Corporation), epoxy equivalent: 186 g / eq ) 10 parts, aminophenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90-105 g / eq), curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 Part, phenoxy resin solution ("YX-6654" manufactured by Mitsubishi Chemical Corporation), methyl ethyl ketone and cyclohexanone Methyl ethyl ketone of mixed solution, solid content: 30%, phenoxy resin weight average molecular weight: 38,000 20 parts, naphthol-based curing agent (“SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent: 215 g / eq) 30 parts of a solution (solid content: 50%), 30 parts of methyl ethyl ketone, and an inorganic filler {phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) alumina (manufactured by Denka Corporation) 500 parts of “DAW-3”, average particle size: 3 μm) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin composition varnish. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 7
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolak resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) Spherical fused silica surface-treated with “KBM573” (manufactured by Admatex Co., Ltd., “SO-C5”, average particle size: 1.5 μm)} 780 parts and 20 parts of methyl ethyl ketone are mixed and uniformly mixed with a high-speed rotary mixer To obtain a resin composition varnish. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 8
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 42 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), naphthalene type epoxy resin (“EXA-7311-G4S” manufactured by DIC Corporation), epoxy equivalent: 186 g / eq ) 12 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), phenoxy resin solution (“YX-6554” manufactured by Mitsubishi Chemical Co., Ltd.), mixed solution of methyl ethyl ketone and cyclohexanone, solid content : 30%, weight average molecular weight: 38,000) 20 parts, naphthol-based curing agent (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) SN-485 ", hydroxyl equivalent: 215 g / eq) of methyl ethyl ketone solution (solid content: 50%) 30 parts, inorganic filler {phenylaminosilane coupling agent (" KBM573 "manufactured by Shin-Etsu Chemical Co., Ltd.)) 500 parts of spherical fused silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)} and 20 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition A product varnish was prepared. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Example 9
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 35 parts of 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio, epoxy equivalent: 169 g / eq), naphthalene type Epoxy resin (DIC Corporation “EXA-731-G4S”, epoxy equivalent: 186 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq) ) 5 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolak resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical) 950 parts of spherical fused silica surface-treated with "KBM573" (manufactured by Co., Ltd.) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size: 0.5 µm)} and 20 parts of methyl ethyl ketone are mixed together. A resin composition varnish was prepared by uniformly dispersing with a rotary mixer. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Comparative Example 1
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolak resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) Spherical fused silica surface-treated with “KBM573” (manufactured by Admatex Co., Ltd., “SO-C2”, average particle size: 0.5 μm)} 650 parts and 20 parts of methyl ethyl ketone are mixed and uniformly mixed with a high-speed rotary mixer To obtain a resin composition varnish. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Comparative Example 2
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 42 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), naphthalene type epoxy resin (“EXA-7311-G4S” manufactured by DIC Corporation), epoxy equivalent: 186 g / eq ) 10 parts, aminophenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90-105 g / eq), curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 Part, phenoxy resin solution ("YX-6654" manufactured by Mitsubishi Chemical Corporation), methyl ethyl ketone and cyclohexanone Mixed solution, solid content: 30%, weight average molecular weight: 38,000 20 parts, naphthol-based curing agent (“SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent: 215 g / eq) in methyl ethyl ketone solution (solid Min: 50%) 30 parts of inorganic filler {Phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) Spherical fused silica (“SO-C2” manufactured by Admatechs Co., Ltd.) , Average particle size: 0.5 μm)} 1030 parts and 35 parts of methyl ethyl ketone were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin composition varnish. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Comparative Example 3
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 30 parts, biphenyl type Epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 8 parts of aminophenol type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 90-105 g / eq ) 5 parts, curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 0.2 part, polymer resin E varnish 300 parts, cresol novolac resin (“KA-1163” manufactured by DIC Corporation), phenol Hydroxyl group equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) Spherical fused silica surface-treated with “KBM573” manufactured by Co., Ltd. (“SO-C5” manufactured by Admatechs Co., Ltd., average particle size: 1.5 μm)} 780 parts and 20 parts of methyl ethyl ketone are mixed, and a high-speed rotating mixer Were uniformly dispersed to prepare a resin composition varnish. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Comparative Example 4
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 33 parts of 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), naphthalene type Epoxy resin (DIC Corporation “EXA-731-G4S”, epoxy equivalent: 186 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq) ) 2 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolac resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical) 950 parts of spherical fused silica surface-treated with "KBM573" (manufactured by Co., Ltd.) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size: 0.5 µm)} and 20 parts of methyl ethyl ketone are mixed together. A resin composition varnish was prepared by uniformly dispersing with a rotary mixer. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

Comparative Example 5
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 33 parts of 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), naphthalene type Epoxy resin (DIC Corporation “EXA-731-G4S”, epoxy equivalent: 186 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq) ) 2 parts, 1 part of curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of polymer resin E varnish, cresol novolac resin (“KA-1163” manufactured by DIC Corporation), phenolic hydroxyl group Equivalent: 118 g / eq) 12 parts, inorganic filler {phenylaminosilane coupling agent (Shin-Etsu Chemical) Spherical fused silica surface-treated with “KBM573” (manufactured by Co., Ltd.) (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)} 1020 parts and 20 parts of methyl ethyl ketone are mixed together. A resin composition varnish was prepared by uniformly dispersing with a rotary mixer. Next, on the polyethylene terephthalate film (thickness 38 μm), the obtained resin composition varnish was applied with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and 80 to 120 ° C. The film was dried at (average 100 ° C.) for 10 minutes to obtain an adhesive film.

  The characteristics of the resin composition layers of the adhesive films obtained in the above examples and comparative examples were evaluated as follows. The composition of the resin composition layer (amount in solid content excluding the solvent) and the evaluation results are shown in Table 1 below.

(1) Glass transition temperature of resin composition layer cured by heating at 180 ° C. for 90 minutes Using an oven, the resin composition layer was cured by heating the adhesive film at 180 ° C. for 90 minutes. Next, the cured resin composition layer was peeled from the polyethylene terephthalate film, and then cut into a width of 5 mm and a length of 15 mm to prepare a test piece. Using a dynamic viscoelasticity measuring device (“EXSTAR6000” manufactured by SII Nanotechnology Co., Ltd.), the obtained specimen was subjected to thermomechanical analysis by a tensile load method. Specifically, after mounting the test piece on the apparatus, thermomechanical analysis was performed twice continuously under the conditions of a load of 200 mN, a temperature increase rate of 2 ° C./min, and a measurement temperature range of 25 to 270 ° C. After the first measurement was completed, the temperature was lowered to the initial measurement temperature by air cooling, and then the second measurement was performed. From the point at which the slope of the dimensional change signal in the second thermomechanical analysis changes, the glass transition temperature (° C.) of the test piece was calculated. The results are shown in the column of “Glass transition temperature (° C.)” in Table 1 below.

(2) Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes and Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes
Using an oven, the cured resin composition was cured by heating the adhesive film at 180 ° C. for 30 or 90 minutes. Next, the cured resin composition layer was peeled off from the polyethylene terephthalate film, and then cut into a width of 30 mm and a length of 30 mm to prepare a test piece. Using a Vickers hardness meter (manufactured by Mitutoyo Corporation), the Vickers hardness of the obtained test piece was measured. The result of the Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes is cured by heating at 180 ° C. for 90 minutes in the column of “Vickers hardness (HV1)” in Table 1 below. The result of the Vickers hardness (HV2) of the resin composition layer is described in the column of “Vickers hardness (HV2)”. The results of “HV2 / HV1” are also shown in Table 1 below.

(3) Elastic modulus at 23 ° C. of the resin composition layer cured by heating at 180 ° C. for 90 minutes Using an oven, the resin composition layer was cured by heating the adhesive film at 180 ° C. for 90 minutes. Thereafter, the cured resin composition layer was peeled off from the polyethylene terephthalate film. In accordance with Japanese Industrial Standard (JIS K7127), a tensile test of the cured resin composition layer is performed using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.), and its elastic modulus at 23 ° C. is measured. did. The results are shown in the column of “elastic modulus (GPa)” in Table 1 below.

(4) Clogging of grinding stone, etc. A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic Corporation “R5715ES”) having a size of 500 mm × 300 mm. It was immersed in a metal surface treatment solution (“CZ8100” manufactured by MEC Co., Ltd.), and the copper surface on both sides of the laminated plate was roughened.
The adhesive film (thickness of the resin composition layer after drying: 100 μm) was laminated on one side of a laminate using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
Then, heat curing was performed at 180 ° C. for 30 minutes, and the cured resin composition layer was polished and cut with a surface grinder (polishing cutting conditions: grinding wheel peripheral speed 500 m / min, table speed 13 m / min, once The cutting amount was 3 μm, the total cutting thickness was 50 μm, the grinding wheel count # 1000), the clogging of the grinding stone, and the like were evaluated according to the following criteria. The results are listed in the column of “Whetstone clogging” in Table 1 below.
○: There is no clogging of the grindstone, and the appearance of the resin composition surface after polishing and cutting is uniform.
Δ: Clogging of the grindstone occurred, and some spots were formed on the resin composition surface after grinding and polishing cutting.
X: Clogging of the grindstone occurred, and spots were formed on the entire surface of the resin composition after polishing and cutting.

(5) Grinding wheel wear, etc. Glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic Corporation “R5715ES”) of 500 mm × 300 mm in size It was immersed in a surface treatment solution (“CZ8100” manufactured by MEC Co., Ltd.) to perform a roughening treatment on the copper surfaces on both sides of the laminate.
The adhesive film (thickness of the resin composition layer after drying: 100 μm) was laminated on one side of a laminate using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
Then, heat curing was performed at 180 ° C. for 30 minutes, and the cured resin composition layer was polished and cut with a surface grinder (polishing cutting conditions: grinding wheel peripheral speed 500 m / min, table speed 13 m / min, once The incision amount of 3 μm, the grinding wheel count # 1000), the wear of the grinding wheel and the like were evaluated according to the following criteria. The results are shown in the column of “Wearing of the grinding wheel” in Table 1 below.
○: There is little abrasion of a grindstone, and there is almost no change in the efficiency of polishing cutting.
Δ: Grinding wheel wear occurs, and polishing cutting efficiency is slightly deteriorated.
X: Grinding wheel wear occurs, and the efficiency of polishing and cutting rapidly deteriorates.

(6) Adhesion reliability at the time of polishing cutting process 500 mm × 300 mm glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, “R5715ES” manufactured by Panasonic Corporation) ”) Was immersed in a metal surface treatment solution (“ CZ8100 ”manufactured by MEC Co., Ltd.) to roughen the copper surfaces on both sides of the laminate.
The adhesive film (thickness of the resin composition layer after drying: 100 μm) was laminated on one side of a laminate using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
Then, heat curing was performed at 180 ° C. for 30 minutes, and the cured resin composition layer was polished and cut with a surface grinder (polishing cutting conditions: grinding wheel peripheral speed 500 m / min, table speed 13 m / min, once The total cutting thickness was 50 μm and the grinding stone count was # 1000), and the adhesion reliability during the polishing cutting process was evaluated according to the following criteria. The results are listed in the column “Reliability of adhesion” in Table 1 below.
○: The insulating layer and the core layer are peeled off, and no cracks are observed on the surface of the insulating layer.
Δ: Although there is no peeling between the insulating layer and the core layer, cracks on the surface of the insulating layer are observed.
X: Peeling between the insulating layer and the core layer is observed.

(7) Peel strength between the cured resin composition layer and the conductor layer formed on the surface thereof A glass cloth base epoxy resin double-sided copper clad laminate having a size of 500 mm × 300 mm (copper foil thickness: 18 μm, substrate A thickness of 0.3 mm, “R5715ES” manufactured by Panasonic Corporation was dipped in a metal surface treatment solution (“CZ8100” manufactured by MEC Co., Ltd.), and the copper surfaces on both sides of the laminated plate were roughened.
The adhesive film (thickness of the resin composition layer after drying: 100 μm) was laminated on one side of a laminate using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
Thereafter, heat curing was performed at 180 ° C. for 30 minutes, and the cured resin composition layer was polished and cut with a surface grinder (Polishing cutting conditions: grinding wheel peripheral speed 500 m / min, table speed 13 m / min, one cut) 3 μm in volume, total cutting thickness 50 um, grinding wheel count # 1000).
After polishing and cutting, the laminate with an insulating layer (cured resin composition layer) is immersed in a swelling dip / seculigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 5 minutes. Next, as a roughening solution, it is immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, It was immersed for 5 minutes at 40 ° C. in the reduction Shoryushin securigant P of Atotech Japan Co., Ltd. The laminated board after the roughening treatment was used as an evaluation board A.
In order to form a circuit on the surface of the insulating layer, the evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. Next, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 180 ° C. for 60 minutes. The laminated board after plating was used as an evaluation board B.
The conductor layer of the evaluation board B is cut into a portion having a width of 10 mm and a length of 100 mm, and one end thereof is peeled off and grasped by a gripping tool (TSE Corporation, Autocom type testing machine AC-50C-SL). The load when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured as peel strength (kgf / cm). The results are shown in the column of “Peel Strength (kgf / cm)” in Table 1 below.

  The resin composition of this invention can form the insulating layer which has the outstanding workability | operativity at the time of an abrasive cutting process, and the outstanding contact | adherence reliability. Therefore, the resin composition of the present invention is useful for producing a coreless substrate.

DESCRIPTION OF SYMBOLS 1 Core layer 2 Circuit precursor 3 Insulating layer 4 Solder ball 5 Coreless board | substrate 6 Resin layer (or prepreg layer)
7 Copper foil 8 Release layer

Claims (14)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And the glass transition temperature of the resin composition cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher.   2. The resin composition according to claim 1, wherein the peel strength between the resin composition cured by heating at 180 ° C. for 30 minutes and the conductor layer formed on the surface thereof is 0.3 kgf / cm or more.   The resin composition according to claim 1 or 2, wherein the epoxy resin as the component (A) contains a biphenyl type epoxy resin.   The resin composition as described in any one of Claims 1-3 in which the epoxy resin which is a component (A) contains an aminophenol type epoxy resin.   Furthermore, (E) The resin composition as described in any one of Claims 1-4 containing the polymeric resin whose elasticity modulus in 23 degreeC is 5-200 Mpa.   The resin composition according to claim 5, wherein the polymer resin as the component (E) has a glass transition temperature of 30 ° C. or lower.   The polymer resin as the component (E) is a resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure. The resin composition as described.   The polymer resin as the component (E) is a polyimide resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure. The resin composition as described in any one of these. The polymer resin as the component (E) is a structure represented by the formula (1-a) and a structure represented by the formula (1-b):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure, and R2 represents a tetravalent organic group. R3 represents a divalent organic group. ]
The resin composition according to any one of claims 5 to 8, which is a polyimide resin having A structure in which the polymer resin as the component (E) is represented by the formula (abc):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure, and R2 represents a tetravalent organic group. R3 represents a divalent organic group, and n and m represent integers. ]
The resin composition according to any one of claims 5 to 9, which is a polyimide resin having   The resin composition according to any one of claims 5 to 10, wherein the polymer resin as the component (E) has a number average molecular weight of 5,000 to 25,000.   The adhesive film which has a resin composition layer which consists of a resin composition as described in any one of Claims 1-11 currently joined to the support body and this support body. (1) A circuit precursor and a resin composition layer are in contact with a core layer on which a circuit precursor is formed and an adhesive film having a support and a resin composition layer bonded to the support. And then the resin composition layer is thermally cured after peeling the adhesive film support, or the adhesive film support is peeled off after curing the resin composition layer and cured. Forming an insulating layer as a layer;
(2) An adhesive film used in a method of manufacturing a coreless substrate, comprising: a step of polishing and cutting the surface of an insulating layer; and (3) a step of installing a solder ball in contact with a circuit precursor after removing the core layer. And
The resin composition layer includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And a glass transition temperature of a resin composition layer cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher. (1) A circuit precursor and a resin composition layer are in contact with a core layer on which a circuit precursor is formed and an adhesive film having a support and a resin composition layer bonded to the support. And then the resin composition layer is thermally cured after peeling the adhesive film support, or the adhesive film support is peeled off after curing the resin composition layer and cured. Forming an insulating layer as a layer;
(2) a step of polishing and cutting the surface of the insulating layer, and (3) a method of manufacturing a coreless substrate, including a step of installing a solder ball that contacts the circuit precursor after removing the core layer,
The resin composition layer includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The Vickers hardness (HV1) of the resin composition layer cured by heating at 180 ° C. for 30 minutes has the formula (i):
40 <HV1 <220 (i)
The filling,
The relationship between HV1 and the Vickers hardness (HV2) of the resin composition layer cured by heating at 180 ° C. for 90 minutes is represented by the formula (ii):
1 <HV2 / HV1 <1.5 (ii)
And the glass transition temperature of the resin composition layer cured by heating at 180 ° C. for 90 minutes is 140 ° C. or higher.