TWI745363B - Resin composition - Google Patents

Abstract

The present invention provides a resin composition that can bring about low dielectric tangent, and excellent compatibility and melt viscosity of an insulating layer with plating adhesion and underlayer adhesion.

The resin composition of the present invention is a resin composition containing (A) epoxy resin, (B) hardener, (C) resin having a vinyl group, and (D) indencoumarone resin, wherein (D) The content of the component is 5 to 20% by mass when the resin component is 100% by mass.

Description

Resin composition

The present invention relates to a resin composition. More details are related to adhesive films, printed circuit boards, and semiconductor devices.

The manufacturing technology of the printed circuit board is a manufacturing method in which the insulating layer and the conductor layer are alternately overlapped on the inner substrate. The insulating layer is generally formed by curing the resin composition. For example, Patent Document 1 describes a resin composition containing a specific epoxy resin and a curing agent, and having low dielectric properties and high heat resistance.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2015-57465 A

In recent years, the miniaturization and high performance of electronic devices have progressed. Multilayer printed circuit boards have been multi-layered, requiring miniaturization and high-density wiring. In order to achieve finer and higher-density wiring, it is necessary to A resin composition with a low dielectric tangent, excellent plating adhesion and underlayer adhesion, compatibility of the insulating layer, and good melt viscosity is required, but the current situation has not yet reached all these characteristics.

The subject of the present invention is to provide a resin composition that can bring about a low dielectric tangent, and excellent compatibility and melt viscosity of the insulating layer for plating adhesion and underlayer adhesion.

As a result of careful examination of the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by using a resin having a vinyl group in combination with a specific amount of indocumarone resin and completed the present invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a hardener, (C) a resin having a vinyl group, and (D) an indencoumarone resin, wherein (D) ) The content of the component is 5 to 20% by mass when the resin component is 100% by mass.

[2] The resin composition of [1], wherein at least one of the component (C) has an aromatic ring.

[3] The resin composition of [1] or [2], wherein the content of component (C) is 5% by mass to 20% by mass when the resin component is 100% by mass.

[4] The resin composition of any one of [1] to [3], wherein at least one of the component (B) is an active ester hardener.

[5] The resin composition of any one of [1] to [4], which further comprises (E) Inorganic filler.

[6] The resin composition of [5], wherein the content of the component (E) is 50% by mass or more when the non-volatile content of the resin composition is 100% by mass.

[7] The resin composition of any one of [1] to [6], wherein the component (D) is a copolymer of indene, coumarone, and styrene.

[8] The resin composition of any one of [1] to [7], which is used for forming the insulating layer of a printed circuit board.

[9] An adhesive film having a support and a resin composition layer containing the resin composition of any one of [1] to [8] provided on the support.

[10] A printed circuit board comprising an insulating layer formed by a cured product of the resin composition of any one of [1] to [8].

[11] A semiconductor device comprising the printed circuit board of [10].

According to the present invention, it is possible to provide a resin composition with a low dielectric tangent and excellent compatibility and melt viscosity of the insulating layer with excellent plating adhesion and underlayer adhesion.

[The form of implementing the invention]

Hereinafter, the resin composition, adhesive film, printed circuit board, and semiconductor device of the present invention will be described in detail.

[Resin composition]

The resin composition of the present invention includes (A) epoxy resin, (B) hardener, (C) resin with vinyl group, and (D) indencoumarone resin, wherein the content of (D) component is the resin component When it is 100% by mass, it is 5% by mass to 20% by mass. In addition, in the present invention, the "resin component" refers to the non-volatile components constituting the resin composition, except for the following (E) inorganic filler. Hereinafter, each component contained in the resin composition of the present invention will be explained in detail.

<(A) Epoxy resin>

The resin composition of the present invention contains (A) epoxy resin. Examples of the epoxy resin include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentane Diene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, Naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, thread Aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, Naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. The epoxy resin can be used individually by 1 type or in combination of 2 or more types. (A) From the viewpoint of reducing the average linear thermal expansion rate, the component is preferably an epoxy resin containing an aromatic skeleton, and more preferably selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, and naphthalene epoxy resin. 1 type of resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin Above, it is more preferably a biphenyl type epoxy resin. Aromatic skeleton refers to a chemical structure generally defined as aromatic, including polycyclic aromatics and aromatic heterocycles.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it is preferable to include an epoxy resin having 3 or more epoxy groups in one molecule and being solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). The epoxy resin may contain only a solid epoxy resin, or an epoxy resin that has two or more epoxy groups per molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") With solid epoxy resin. By using a liquid epoxy resin and a solid epoxy resin as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition can also be improved.

The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and epoxy resin. Propylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, epoxypropylamine type epoxy resin, and epoxy resin with butyl Diene structure epoxy resin, more preferably epoxy propyl amine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin . Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, and "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. , "825", "Epikote828EL" (bisphenol A ring Oxygen resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine epoxy resin) Resin), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "EX-721" (ring Oxypropyl ester type epoxy resin), "CELLOXID2021P" (alicyclic epoxy resin with ester skeleton) made by DAICEL, "PB-3600" (epoxy resin with butadiene structure), new "ZX1658", "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., and "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. Resin) and so on. These can be used individually by 1 type or in combination of 2 or more types.

The solid epoxy resin is preferably a naphthalene type tetrafunctional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, and a bicarbonate type epoxy resin. Benzene type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, more preferably naphthalene type tetrafunctional epoxy resin, naphthalene Phenolic epoxy resin and biphenyl epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "HP4032H" manufactured by DIC Corporation. N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP -7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (Naphthylene ether epoxy Resin), Nippon Kayaku (Stock) "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (linked Benzene type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolak type epoxy resin), "ESN475V" (naphthol novolak type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bis-xylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500" manufactured by Mitsubishi Chemical Corporation, "YL7760" (Bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (茀-type epoxy resin), Mitsubishi Chemical Corporation (stock) "JER1010" (solid bisphenol A epoxy resin), "jER1031S" (tetraphenylethane epoxy resin), etc. These can be used individually by 1 type or in combination of 2 or more types.

The epoxy resin is a case where a liquid epoxy resin and a solid epoxy resin are used together, and their quantity ratio (liquid epoxy resin: solid epoxy resin) is expressed in terms of mass ratio, preferably 1:0.1~ 1:15 range. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in this range, it can be obtained i) when used in the form of adhesive film, it can bring moderate adhesion, ii) when used in the form of adhesive film In this case, sufficient flexibility can be obtained, and workability can be improved, and iii) a cured product with sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the ratio of the amount of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is expressed by mass ratio, and more preferably 1: 0.5~1: 10 range, and more Preferably, the range is 1:1~1:8.

The content of the epoxy resin in the resin composition, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, when the resin component is set to 100% by mass, it is preferably 5% by mass or more, and more preferably 10 Mass% or more, and more preferably 20 mass% or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention can be exhibited. It is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By being within this range, the crosslinking density of the cured product is sufficient and the surface roughness of the insulating layer is small. In addition, the epoxy equivalent can be measured in accordance with JIS K7236 and is the mass of the resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

<(B) Hardener>

The resin composition of the present invention contains (B) a curing agent. The curing agent is not particularly limited as long as it has the function of curing epoxy resin. Examples include phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate esters. Hardeners, carbodiimide hardeners, etc. The curing agent may be used singly or in combination of two or more kinds. (B) Ingredients are selected from One or more of phenolic hardeners, naphthol hardeners, active ester hardeners, carbodiimide hardeners, and cyanate ester hardeners are preferred, and active ester hardeners are more preferred.

The phenolic hardener and the naphthol hardener are preferably a phenol hardener having a novolak structure or a naphthol hardener having a novolak structure from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer, a phenol novolak hardener containing a triazine skeleton is preferred.

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-7851H", Nippon Kasei Co., Ltd. "NHN", "CBN", "GPH" under the pharmaceutical (stock) system, "SN170", "SN180", "SN190", "SN475", "SN485", "SN495" under the Nippon Steel & Sumitomo Metal Corporation system , "SN375", "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB- 9500" and so on.

From the viewpoint of obtaining an insulating layer excellent in adhesion to the conductor layer, an active ester-based curing agent is preferred. The active ester curing agent is not particularly limited. Generally, it is preferable to use phenol esters, Thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc., having two or more in one molecule. The ester-based compound with high reactivity. The active ester is hardened The agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred . 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. Phenol compounds or naphthol compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol series, 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, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol Novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol for one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of phenol novolac, and an active ester compound containing a phenol novolak of benzoate Active ester compounds are preferred, and among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. "Dicyclopentadiene-type diphenol structure" means a divalent structural unit formed by phenylene-dicyclopentyl-phenylene.

Commercially available active ester hardener, which contains dicyclopentane Active ester compounds with diene-type diphenol structure, including "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (DIC (Stock), the active ester compound containing naphthalene structure, including "EXB9416-70BK" (manufactured by DIC), the active ester compound containing the acetone of phenol novolak, including "DC808" (Mitsubishi Chemical (Stock), the active ester of phenol novolac benzoate, including "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), the active ester hardener of phenol novolac acetate, including "DC808 "(Mitsubishi Chemical Co., Ltd.), the active ester hardener of phenol novolac benzoate, including "YLH1026" (Mitsubishi Chemical Co., Ltd.) and "YLH1030" (Mitsubishi Chemical Co., Ltd.) , "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

The cyanate ester curing agent includes, for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'- Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis( 4-cyanate ester) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate ester-3,5-dimethylphenyl)methane, 1,3- Bis (4-cyanate phenyl-1-(methyl ethylene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyanate phenyl) ether, etc. 2 Functional cyanate ester resins, polyfunctional cyanate ester resins derived from phenol novolacs and cresol novolacs, and some of these cyanate ester resins are pre-triazineified Polymer and so on. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resin) manufactured by Lonza Japan, "BA230", and "BA230S75" (Prepolymer of bisphenol A dicyanate in which part or all of triazine has been triazine) and so on.

Specific examples of the carbodiimide hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The ratio of the amount of epoxy resin to hardener is expressed by the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], preferably in the range of 1:0.1~1:10, More preferably, it is 1:0.5~1:5, and even more preferably 1:1~1:3. Here, the reactive groups of the hardener refer to active hydroxyl groups, active ester groups, etc., which vary depending on the type of hardener. In addition, the total number of epoxy groups of epoxy resin refers to the total value of the solid content of each epoxy resin divided by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of hardener refers to For all the hardeners, the solid content of each hardener is divided by the total value of the equivalent of the reactive group. By setting the ratio of the amount of the epoxy resin to the hardening agent in this range, the heat resistance of the hardened product of the resin composition is further improved.

The content of the hardener in the resin composition is not particularly limited. When the resin component is 100% by mass, it is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less. In addition, the lower limit is not particularly limited, and is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more.

<(C) Resin with vinyl group>

The resin composition of the present invention contains (C) a resin having a vinyl group. By combining the component (C) and the component (D) described later, it is possible to obtain the compatibility and melt viscosity of the insulating layer with low dielectric tangent and excellent plating adhesion and underlayer adhesion. Good resin composition. (C) A component may be used individually by 1 type, and may use 2 or more types.

The component (C) is not particularly limited as long as it has a vinyl group. It preferably has an aromatic ring. Among them, the resin represented by the following formula (1) is preferable from the viewpoint of storage stability.

(In formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents a group represented by the following formula (2) or the following formula (3).)

【Chemical 2】-CH ₂ -OEO-CH _2- (2)

(In formula (2), E represents the following formula (E-1), (E-2) or (E-3).)

(In formula (3), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group with 6 or less carbon atoms or a phenyl group, and E represents the following formula (E-1), (E-2) or (E- 3). a and b indicate that at least one of them is not an integer of 0 to 100.)

(In formulas (E-1) to (E-3), R ¹⁵ to R ³⁴ each independently represent a hydrogen atom, an alkyl group with 6 or less carbon atoms, or a phenyl group. G represents a linear chain with 20 or less carbon atoms , Branched or cyclic divalent hydrocarbon group.)

In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom. The alkyl group having 1 to 4 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, and the like.

R ⁷ to R ^{14 in formula (3) and R 15} to R ^{34 in} formulas (E-1) to (E-3) each independently represent a hydrogen atom, an alkyl group with 6 or less carbon atoms, or a phenyl group. Examples of alkyl groups having 6 or less carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, and hexyl. R ⁷ to R ^{14 are} preferably a hydrogen atom or a methyl group.

a and b indicate that at least one of them is not an integer of 0 to 100. There is a condition that at least one of a and b is not 0, preferably an integer of 0-50, and more preferably an integer of 0-10.

G represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. The divalent hydrocarbon group includes an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms. Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propyl, and butyl. The alkenylene group having 2 to 20 carbon atoms includes an ethylene group, a propenylene group, and a butenylene group. The alkynylene group having 2 to 20 carbon atoms includes ethynylene, propynylene, butynylene, and the like.

The ethylene group in the ethylene group resin may have a substituent. In addition, the above-mentioned alkyl group, phenyl group, and divalent hydrocarbon group may have a substituent.

The substituent is not particularly limited, and examples thereof include halogen atoms, -OH, -OC _1-6 alkyl, -N(C _1-6 alkyl) ₂ , C _1-6 alkyl, C _6-10 aryl,- NH ₂ , -CN, -C(O)OC _1-6 alkyl, -COOH, -C(O)H, -NO ₂ and so on.

Here, the term “C _pq ”(p and q are positive integers and satisfy p<q.) means that the number of carbon atoms of the organic group described after this term is p~q. For example _{, the expression of "C 1-6} alkyl" means an alkyl group with 1 to 6 carbon atoms.

The above-mentioned substituent may further contain a substituent (hereinafter, it may be referred to as a "secondary substituent"). When the secondary substituent is not specifically described, the same one as the above-mentioned substituent can be used.

Although the specific example of (C)component is illustrated below, this invention is not limited to these.

(In the formula, R ¹ to R ⁶ , E, a, and b are the same as the symbols in formula (1) or formula (3), and the preferred range is also the same.)

(C) Commercial products can be used as components. Specific examples of commercial products include "OPE-2St 2200 (number average molecular weight 2200)" and "OPE-2St 1200 (number average molecular weight 2200) manufactured by Mitsubishi Gas Chemical Co., Ltd. "(Styrene modified polyphenylene ether resin), "YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Corporation, (bis-xylenol diallyl ether resin), etc.

(C) The number average molecular weight of the component, to prevent the resin varnish from drying From the viewpoint of volatilization during drying and preventing excessive increase of the melt viscosity of the resin composition, the range is preferably 100 to 10,000, and more preferably 200 to 3,000. In addition, the number average molecular weight in the present invention is measured by the gel permeation chromatography (GPC) method (in terms of polystyrene). The number average molecular weight by the GPC method, specifically, the measuring device uses Shimadzu Corporation LC-9A/RID-6A, and the column uses Showa Denko Corporation Shodex K-800P/K-804L/K- 804L, using chloroform as the mobile phase, and measuring at a column temperature of 40°C, which can be calculated using the calibration curve of standard polystyrene.

(C) For the details of the ingredients, please refer to the descriptions in paragraphs 0010 to 0022 of JP 2014-34580 A, which are included in this specification.

(C) The content of the component, from the viewpoint of obtaining a resin composition with good compatibility, when the resin component is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less or 15% by mass or less. The lower limit of the content of the component (C), from the viewpoint of achieving the desired effect in combination with the component (D) described later, when the resin component is set to 100% by mass, it is preferably 1% by mass or more, and more preferably 3% by mass or more, more preferably 5% by mass or more.

<(D) Indocumarone resin>

The resin composition of the present invention contains a specific amount of (D) indencoumarone resin. By containing the component (D) in a specific amount, a resin composition with improved compatibility and a good balance of physical properties can be obtained. (D) The coumarone skeleton contained in the component has good compatibility with epoxy resins or hardeners with high polarity, and the indene skeleton And the coumarone skeleton system has good compatibility with vinyl resin with low polarity. Therefore, it acts as a compatibilizer between a resin with a high polarity and a resin with a low polarity, thereby improving the compatibility of the entire resin composition.

(D) As a component, the copolymer of indene and coumarone, the copolymer of indene, coumarone, and styrene, etc. are mentioned, for example.

The content ratio of the coumarone component in the incoumarone resin is preferably 5 mol% or more, more preferably 8 mol% or more, and still more preferably 10 mol% or more. The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.

The content rate of the indene component in the incoumarone resin is preferably 30 mol% or more, more preferably 35 mol% or more, and still more preferably 40 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 75 mol% or less, and still more preferably 70 mol% or less.

In the case where the indene coumarone resin is a copolymer of indene, coumarone, and styrene, the content ratio of the styrene component is preferably 20 mol% or more, more preferably 25 mol% or more, and still more preferably 30 More than mol%. The upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less.

Specific examples of the incoumarone resin include "H-100", "V-120S", and "V-120" manufactured by Nico Chemical Co., Ltd.

(D) From the viewpoint of obtaining a resin composition with good compatibility, the content of the component is 5% by mass or more when the resin component is 100% by mass, preferably 8% by mass or more, and more preferably 10% by mass or more. (D) The upper limit of the content of the component, from the viewpoint of obtaining a resin composition with good melt viscosity In terms of obtaining an insulating layer with excellent underlayer adhesion, it is 20% by mass or less, preferably 18% by mass or less, and more preferably 16% by mass or less or 15% by mass or less.

<(E) Inorganic filler>

The resin composition of the present invention may further contain (E) an inorganic filler. The material of the inorganic filler is not particularly limited, and examples include silica, alumina, glass, vermilionite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore , Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly preferred. In addition, the silica is preferably spherical silica. The inorganic filler may be used singly or in combination of two or more kinds.

The average particle size of the inorganic filler is preferably 5μm or less, more preferably 2.5μm or less, still more preferably 2μm or less, and more preferably 1.5 Below μm. The lower limit of the average particle size is not particularly limited, and is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more, 0.5 μm or more, or 1 μm or more. Commercial products of inorganic fillers having such an average particle size include, for example, "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS, "YC100C" and "YA050C" manufactured by Admatechs. ", "YA050C-MJE", "YA010C", "UFP-30" manufactured by Denka Co., Ltd., "SilFile NSS-3N" manufactured by Tokuyama, "SilFile NSS-4N", "SilFile NSS-5N", (Stock) ) Admatechs "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc.

The average particle size of the inorganic filler can be diffracted by laser based on Mie scattering theory. Scattering method to measure. Specifically, a laser diffraction scattering type particle size distribution measuring device can be used to produce the particle size distribution of the inorganic filler on a volume basis, and the median particle size can be used as the average particle size for measurement. The measurement sample is preferably one that disperses the inorganic filler in water by ultrasonic waves. The laser diffraction scattering type particle size distribution measuring device can use the "LA-500" manufactured by Horiba Manufacturing Co., Ltd., etc.

The inorganic filler is preferably an aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, alkoxysilane compound, and organosilazane compound from the viewpoint of improving moisture resistance and dispersibility. , One or more surface treatment agents such as titanate coupling agent. Commercial products of surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-Glycoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl-3) manufactured by Shin-Etsu Chemical Co., Ltd. -Aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-103" (phenyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Base silane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy Type silane coupling agent) and so on.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg/m ² or more. In addition, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the sheet form from rising, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m ² or less .

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to an inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant liquid and drying the solid content, use a carbon analyzer to measure the amount of carbon per unit surface area of the inorganic filler. The carbon analyzer can use "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc.

The content of the inorganic filler in the resin composition, from the viewpoint of obtaining an insulating layer with a low thermal expansion rate, when the non-volatile content in the resin composition is 100% by mass, it is preferably 50% by mass or more, more preferably 55 Mass% or more, more preferably 60% by mass or more, or 65% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, or 80% by mass or less from the viewpoint of the mechanical strength of the insulating layer, particularly stretching.

<(F) Hardening accelerator>

The resin composition of the present invention may contain (F) a hardening accelerator. Examples of hardening accelerators include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, organic peroxide hardening accelerators, etc., preferably phosphorus It is a hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a metal hardening accelerator, and more preferably an amine hardening accelerator, an imidazole hardening accelerator, or a metal hardening accelerator. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus-based hardening accelerators include, for example, triphenyl phosphine, phosphonium borate chloride compound, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium decanoate, (4- (Methyl phenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., preferably triphenyl phosphine, tetrabutyl phosphonium Decanoate.

Amine-based hardening accelerators include, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-s (dimethylamino) Methyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo(5, 4,0)-Undecene.

The imidazole-based hardening accelerators include, for example, 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-cyano Ethyl-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-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resin, preferably It is 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As an imidazole-based hardening accelerator, commercially available products may also be used, and examples include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine-based hardening accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-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-(o-tolyl) biguanide, etc., preferably Dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt acetone (II) and cobalt acetone (III), organic copper complexes such as copper acetone (II), and Organic zinc complexes such as zinc acetone (II), organic iron complexes such as iron acetone (III), organic nickel complexes such as nickel acetone (II), manganese acetone (II) ) And other organic manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc decalinate, cobalt decalinate, tin stearate, and zinc stearate.

Organic peroxide-based curing accelerators, for example, dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide Oxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide (cumene hydroperoxide), tert-butyl hydroperoxide Wait. The organic peroxide-based hardening accelerator can be a commercially available product, and examples include "Percumyl D" manufactured by NOF Corporation.

The content of the hardening accelerator in the resin composition is not particularly limited, but when the resin component is 100% by mass, it is preferably 0.01% by mass to 3% by mass.

<(G) Thermoplastic resin>

The resin composition of the present invention may contain (G) thermoplastic resin. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, and polyamides. The imide resin, polyetherimine resin, polyether resin, polyetherether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, preferably phenoxy resin. The thermoplastic resin may be used alone or in combination of two or more kinds.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight of thermoplastic resin converted to polystyrene is measured by gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin can be measured using Shimadzu LC-9A/RID-6A as a measuring device, and Shodex K- manufactured by Showa Denko Co., Ltd. as a pipe column. 800P/K-804L/K-804L, use chloroform etc. as the mobile phase, measure at a column temperature of 40°C, and calculate using a standard polystyrene calibration curve.

Examples of the phenoxy resin include those having a skeleton selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, sulphur skeleton, dicyclopentadiene skeleton, A phenoxy resin with one or more skeletons of the group consisting of norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing bisphenol A skeleton), and "YX8100" (benzene containing bisphenol S skeleton) Oxy resin), and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), other examples include "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd. , "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482", etc.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of polyvinyl acetal resins include "electrochemical butyraldehyde 4000-2", "electrochemical butyraldehyde 5000-A", "electrochemical butyraldehyde 6000-C", and "electrochemical butyraldehyde 4000-2" manufactured by the Electrochemical Industry Co., Ltd. Electrochemical Butyraldehyde 6000-EP", S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of polyimide resins include "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical Co., Ltd. Specific examples of polyimide resins include linear polyimide obtained by reacting bifunctional hydroxyl-terminated polybutadiene, diisocyanate compound and tetrabasic acid anhydride (LINEAR POLYIMIDE) (Japanese Patent Application Publication No. 2006-37083) The modification of polyimide described in), polyimide containing polysiloxane skeleton (polyimide described in Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386), etc. Polyimide.

Specific examples of polyimide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. In addition, specific examples of polyimide resins include Japanese Modified polyamides such as "KS9100" and "KS9300" (polysiloxane-based polyimide imide) manufactured by Tachihwa Chemical Co., Ltd.

Specific examples of polyether resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., etc.

Specific examples of the polymer resin include polymer "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Among them, the thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin. Therefore, in a more suitable embodiment, the thermoplastic resin contains one or more types selected from the group consisting of phenoxy resins and polyvinyl acetal resins.

When the resin composition of the present invention contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% to 15% by mass, more preferably 0.6% to 12% by mass when the resin component is 100% by mass, It is more preferably 0.7% by mass to 10% by mass.

<(H) Flame Retardant>

The resin composition of the present invention may further contain (H) a flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, silica flame retardants, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

Commercial products can also be used as flame retardants, such as "HCA-HQ" manufactured by Sankoh Co., Ltd., "PX-200" manufactured by Dahachi Chemical Industry Co., Ltd., etc.

When the resin composition of the present invention contains a flame retardant, the content of the flame retardant is not particularly limited. When the resin content is 100% by mass, it is preferably 0.5% to 20% by mass, more preferably 0.5% to 15% by mass. %, and more preferably 0.5% by mass to 10% by mass.

<(I) Organic Filling Material>

The resin composition of the present invention may also contain (I) an organic filler. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed circuit board can be used, and examples thereof include rubber particles, polyamide particles, and silica particles.

Commercially available rubber particles can also be used, and examples include "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3816N" manufactured by Aica Industrial Co., Ltd., and the like.

When the resin composition of the present invention contains an organic filler, the content of the organic filler is when the resin component is 100% by mass, preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and More preferably, it is 0.3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

<(J) Other additives>

The resin composition of the present invention may further contain other additives when necessary. The other additives may include, for example, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, as well as thickeners, defoamers, and smoothing agents. Resin additives such as adhesives, adhesion-imparting agents, and coloring agents.

The resin composition of the present invention can provide an insulating layer with low dielectric tangent, excellent plating adhesion and underlayer adhesion, and good compatibility and melt viscosity. Therefore, the resin composition of the present invention is suitable for use as a resin composition for forming an insulating layer of a printed circuit board (resin composition for an insulating layer of a printed circuit board), and is more suitable for use as a resin for forming an interlayer insulating layer of a printed circuit board The composition (resin composition for the interlayer insulating layer of a printed circuit board) is used. In addition, the resin composition of the present invention can provide an insulating layer with a good part embedding property, so it can also be applied to the case where the printed circuit board is a circuit board with a built-in part.

[Next film]

The adhesive film of the present invention has a support and a resin composition layer containing the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, since the present invention can reduce the plating depth, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

As the support, for example, a film made of plastic material, metal foil, release paper, etc., preferably a film made of plastic material, metal foil.

When a film made of a plastic material is used as a support, the plastic material can be, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN") and other polyesters, polycarbonate (hereinafter sometimes referred to as "PC"), polymethyl methacrylate (PMMA), etc. Acrylic acid, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. Copper foil can also be a foil made of a single metal of copper, or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The support may be subjected to matte treatment, corona treatment, and antistatic treatment to the surface to be joined with the resin composition layer.

In addition, as the support, a support with a mold release layer having a mold release layer on the surface to be bonded to the resin composition layer can also be used. The mold release agent used in the mold release layer of the support with the mold release layer includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Release agent. Commercial products can be used for the support with a release layer. Examples include PET films with a release layer mainly composed of alkyd resin-based release agents, namely "SK-1" and "Lintec" made by Lintec. "AL-5", "AL-7", Toray's "LumirrorT6AM", etc.

Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In the case of using a support with a release layer, the thickness of the entire support with a release layer is preferably within the above-mentioned range.

The film is then prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and it can be manufactured by coating this resin varnish on a support using a die coater or the like, and drying it to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol Acetates such as acetate, cellosolve and carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide ( Amine-based solvents such as DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be performed by conventional methods such as heating and blowing hot air. Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less for drying. It varies with the boiling point of the organic solvent in the resin varnish, but for example, when a resin varnish containing 30% to 60% by mass of organic solvent is used, the resin can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes Composition layer.

In the adhesive film, a protective film conforming to the support may be further laminated on the surface that is not bonded to the support of the resin composition layer (that is, the surface on the opposite side to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent the adhesion or scars of dust on the surface of the resin composition layer. The film can then be wound into a roll for storage. When the next film has a protective film, it can be used by peeling off the protective film.

The lowest melt viscosity of the resin composition layer (or resin composition) in the film, from the viewpoint of maintaining the thickness of the resin composition layer even if it is thin, is preferably 1000 poise or more, more preferably 1500 poise or more, and even more preferably 2000 poise above. The upper limit of the minimum melt viscosity is preferably 12,000 poise or less, more preferably 10,000 poise or less, and still more preferably 8,000 poise or less and 5000 poise or less from the viewpoint of obtaining good circuit embedding.

The lowest melt viscosity of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity decreases with the temperature increase in the initial stage, and then, when the temperature exceeds a certain level, the melt viscosity increases along with the temperature increase. The minimum melt viscosity refers to the minimum melt viscosity. The minimum melt viscosity of the resin composition layer can be measured using a dynamic viscoelastic method, for example, it can be measured according to the method described in the below-mentioned <Measurement of the minimum melt viscosity of the resin composition layer>.

The resin composition layer (or resin composition) in the adhesive film of the present invention exhibits excellent compatibility. That is, the resin composition layer (or resin composition) in the adhesive film of the present invention does not precipitate coarse particles of 50 μm or more. Compatibility can be measured by the method described in the below-mentioned "Evaluation of Compatibility".

The insulating layer formed using the adhesive film (or resin composition) of the present invention exhibits a low dielectric tangent. From the viewpoint of preventing heat generation at high frequencies and reducing signal delay and signal noise, the dielectric tangent is preferably 0.010 or less. It is more preferably 0.009 or less, still more preferably 0.008 or less, 0.007 or less, 0.006 or less, or 0.005 or less. The lower the lower limit of the dielectric tangent, the better, but it can usually be 0.001 or more. The dielectric tangent can be measured by the method described in the below-mentioned "Evaluation of Dielectric Tangent".

The insulating layer formed using the adhesive film (or resin composition) of the present invention exhibits good plating adhesion. That is, it brings about an insulating layer showing good plating peel strength. The plating peel strength is preferably 1.5 kgf/cm or less, more preferably 1 kgf/cm or less, and still more preferably 0.5 kgf/cm or less. The upper limit may be 0.1 kgf/cm or more. The evaluation of the plating peel strength can be measured by the method described in [Measurement of Plating Adhesion] described later.

The insulating layer formed using the adhesive film (or resin composition) of the present invention exhibits good adhesion to the underlayer. That is, it brings about an insulating layer showing good peel strength of the bottom layer. The peel strength of the bottom layer is preferably 1.5 kgf/cm or less, more preferably 1 kgf/cm or less, and still more preferably 0.5 kgf/cm or less. The upper limit may be 0.1 kgf/cm or more. The evaluation of the adhesion of the bottom layer can be measured by the method described in [Measurement of the adhesion of the bottom layer] described later.

The resin composition of the present invention can be used to form a prepreg. A prepreg can be formed by impregnating a sheet-like fibrous substrate with the resin composition of the present invention. Therefore, in one embodiment, the prepreg of the present invention includes a sheet-like fibrous base material and the resin composition of the present invention in which the sheet-like fibrous base material is impregnated.

The sheet-like fibrous substrate used for the prepreg is not particularly limited, and those commonly used as substrates for prepregs such as glass cloth, aromatic polyamide nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like can be used. From the viewpoint of thinning of the printed circuit board, the thickness of the sheet-like fiber substrate is preferably 900 μm or less Below, it is more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, since the present invention can reduce the plating depth, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, but it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

The prepreg can be manufactured by a conventional method such as a hot melt method and a solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the adhesive film described above.

[A printed circuit board]

The printed circuit board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

In detail, the printed circuit board of the present invention can be manufactured by a method including the following steps (I) and (II) using the adhesive film described above.

(I) A step of bonding the resin composition layer of the adhesive film to the inner substrate on the inner layer substrate to laminate the adhesive film, and (II) the step of thermosetting the resin composition layer to form an insulating layer.

The "inner substrate" used in step (I) mainly refers to substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc., or the A circuit substrate with a pattern-processed conductor layer (circuit) formed on one or both sides of the substrate. Also, when manufacturing printed circuit boards, in addition, insulating layers and/or conductors should be formed The inner layer circuit substrate of the intermediate product of the layer is also included in the "inner layer substrate" of the present invention. When the printed circuit board is a circuit board with a built-in part, it is sufficient to use an inner-layer substrate with a built-in part.

The lamination of the inner substrate and the adhesive film can be performed, for example, by heating and compressing the adhesive film to the inner substrate from the support side. The member for heat-compressing the adhesive film to the inner substrate (hereinafter also referred to as "heat-compression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller). In addition, instead of pressing the heating and pressing member directly on the adhesive film, it is better to press the adhesive film to fully follow the surface irregularities of the inner substrate through an elastic material such as heat-resistant rubber.

The lamination of the inner substrate and the adhesive film can be implemented by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to In the range of 1.47MPa, the heating and crimping time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under a reduced pressure condition of a pressure of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressure laminator manufactured by Meiji Seisakusho Co., Ltd., and a vacuum coater manufactured by Nikko-Materials Co., Ltd., and the like.

After lamination, under normal pressure (under atmospheric pressure), for example, the heating and pressing member is pressed from the support side, and the subsequent film after lamination is smoothed. The suppression conditions of the smoothing treatment can be the same as the above The heating and pressing conditions of the lamination are the same. The smoothing treatment can be performed by a commercially available laminator. In addition, lamination and smoothing can also be performed continuously using the above-mentioned commercially available vacuum laminator.

The support can be removed between step (I) and step (II), and can also be removed after step (II).

In step (II), the resin composition layer is thermally cured to form an insulating layer.

The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally used when forming the insulating layer of a printed circuit board can be used.

For example, the thermal curing conditions of the resin composition layer also vary depending on the type of resin composition, etc., but the curing temperature can be in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170 ℃~200℃), the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin composition layer may be prepared at a temperature of 50°C or higher but not 120°C (preferably 60°C or higher and 110°C or lower, more preferably 70°C or higher and 100°C or lower). Heating for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed circuit board, at least any one of (III) a step of opening a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further implemented. These steps (III) to (V) can be in accordance with the technical field used in the manufacture of printed circuit boards. It can be implemented in various ways known to the common knowledgeable person. In addition, when the support is removed after step (II), the removal of the support can be between step (II) and step (III), step (III) and step (IV), or step (IV) Implemented between step (V).

In other embodiments, the printed circuit board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as in the case of using an adhesive film.

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be implemented in accordance with the composition of the resin composition used in the formation of the insulating layer, for example, using a drill, a laser, and a plasma. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board.

Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and a known order and conditions generally used when forming the insulating layer of a printed circuit board can be adopted. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid can be carried out in order to roughen the insulating layer. The swelling liquid is not particularly limited, and an alkali solution, a surfactant solution, etc. may be mentioned, and an alkali solution is preferred, and the alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is more It is better to immerse the hardened body in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited, and, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment by 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°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Commercially available oxidants include, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. In addition, the neutralization liquid is preferably an acidic aqueous solution, and commercially available products include "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., for example. The treatment with the neutralization solution can be carried out by immersing the treated surface roughened with an oxidizing agent in a neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object roughened with an oxidizing agent in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after roughening is preferably 280nm or less, more preferably 250nm or less, and still more preferably 200nm or less, 140nm or less, 130nm or less, 120nm or less, 110nm or less, 100nm or less, 95nm or less, or 90nm or less. The lower limit of the Ra value is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured with a non-contact surface roughness meter. Specific examples of non-contact surface roughness meters include "WYKO" manufactured by Veeco Instruments NT3300".

Step (V) is a step of forming a conductor layer.

The conductor material used in the conductor layer is not particularly limited. In a more suitable embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium . The conductor layer may be a single metal layer or an alloy layer. The alloy layer may be formed of, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy).的层。 The layer. Among them, in terms of the versatility, cost, and ease of patterning of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or nickel. Chrome alloy, copper. Nickel alloy, copper. The alloy layer of titanium alloy is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or nickel. The alloy layer of chromium alloy is more preferably a single metal layer of copper.

The conductor layer can be a single-layer structure, a single metal layer made of different types of metals or alloys, or a multiple-layer structure in which two or more alloy layers are laminated. When the conductor layer is a multi-layer structure, the layer adjacent to the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or nickel. Alloy layer of chromium alloy.

Although the thickness of the conductor layer varies depending on the desired printed circuit board design, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductive layer can be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method and a full-additive method to form a conductor layer having a desired wiring pattern. The following shows an example of forming the conductor layer by the semi-additive method.

First, a shield layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating protection layer, a mask pattern corresponding to the desired wiring pattern is formed so that a part of the plating protection layer is exposed. After the metal layer is formed by electroplating on the exposed plating protection layer, the mask pattern is removed. Then, by removing the unnecessary plating protection layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

[Semiconductor device]

The semiconductor device of the present invention includes a printed circuit board. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

Semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, televisions, etc.) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes, etc.).

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) due to the conduction of the printed circuit board. "Condition" refers to "the place where electrical signals are transmitted on the printed circuit board". The place can be a surface or a place where it is buried. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The method of mounting a semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively function. Specifically, a wire bonding mounting method, a flip chip mounting method, and Bumpless build-up layer (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method Methods etc. Here, "the mounting method with bumpless build-up (BBUL)" refers to "the mounting method in which the semiconductor chip is directly embedded in the recess of the printed circuit board and the semiconductor chip is connected to the wiring on the printed circuit board" .

[Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. In addition, in the following description, "parts" and "%" indicate "parts by mass" and "% by mass", unless otherwise specified.

[Example 1]

40 parts of biphenyl type epoxy resin (epoxy equivalent 269, "NC3000" manufactured by Nippon Kayaku Co., Ltd.) was heated and dissolved in 25 parts of solvent naphtha under stirring, and then cooled to room temperature. 330 parts of inorganic fillers ("SO-C2" manufactured by Admatechs, average particle size 0.5μm, carbon content per unit surface 0.38mg/m ² ) were mixed, and kneaded and dispersed with 3 rolls. Then, 92.3 parts of an active ester curing agent ("HPC-8000-65T" made by DIC Co., Ltd., a toluene solution with an active group equivalent of about 223 and a non-volatile content of 65% by mass), and a vinyl resin (Mitsubishi Gas Chemical (Stock) 25 parts of OPE-2St 2200 non-volatile toluene solution of 60% by mass), 15 parts of nincoumarone resin (Nippon Chemical Co., Ltd. "H-100"), as a hardening accelerator 2 parts of a 5 mass% MEK solution of 4-dimethylaminopyridine (DMAP) was uniformly dispersed with a rotary mixer to produce a resin varnish 1.

Use a die coater to uniformly coat the resin varnish 1 on the mold release surface of a polyethylene terephthalate film (Lintec (stock) "AL-5", thickness 38μm)) with alkyd resin-based mold release treatment Above, the thickness of the resin composition layer after drying was set to 40 μm, and dried at 80 to 110° C. (average 95° C.) for 5 minutes to produce an adhesive film 1.

[Example 2]

In Example 1, the resin with vinyl (manufactured by Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" with a non-volatile content of 60% by mass in toluene solution) was changed to a resin with vinyl (manufactured by Mitsubishi Gas Chemical Co., Ltd.) "OPE-2St 1200" a toluene solution with a non-volatile content of 60% by mass). Except for the above matters, the resin varnish 2 and the adhesive film 2 were produced in the same manner as in Example 1.

[Example 3]

In Example 1, indencoumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed to indencoumarone resin ("V-120S" manufactured by Nitto Chemical Co., Ltd.). Except for the above matters, the resin varnish 3 and the adhesive film 3 were produced in the same manner as in Example 1.

[Example 4]

In Example 1, indencoumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed to indencoumarone resin ("V-120" manufactured by Nitto Chemical Co., Ltd.). Except for the above matters, the resin varnish 4 and the adhesive film 4 were produced in the same manner as in Example 1.

[Example 5]

In Example 1, (1) 25 parts of resin with vinyl group (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" non-volatile toluene solution with 60% by mass) was changed to resin with vinyl group (Mitsubishi Gas Chemical Co., Ltd.) 8.3 parts of "OPE-2St 2200" non-volatile toluene solution with 60% by mass produced by Mitsubishi Gas Chemical Co., Ltd.) and vinyl resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St" with 60% by mass non-volatile toluene Solution) 16.7 parts, and (2) The blending amount of indencoumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 8 parts.

Except for the above matters, the resin varnish 5 and the adhesive film 5 were produced in the same manner as in Example 1.

[Example 6]

In Example 1, (1) The compounding amount of the resin with vinyl (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" non-volatile toluene solution of 60% by mass) was changed from 25 parts to 16.7 parts, ( 2) The blending amount of indencoumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 25 parts.

Except for the above matters, the resin varnish 6 and the adhesive film 6 were produced in the same manner as in Example 1.

[Comparative Example 1]

In Example 1, (1) The compounding amount of the resin with vinyl (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" non-volatile toluene solution of 60% by mass) was changed from 25 parts to 50 parts, ( 2) The compounding amount of the indencoumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 2 parts.

Except for the above matters, the resin varnish 7 and the adhesive film 7 were produced in the same manner as in Example 1.

[Comparative Example 2]

In Example 1, (1) The compounding amount of resin with vinyl group (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 2200" non-volatile content 60% by mass toluene solution) was changed from 25 parts to 8.3 parts, ( 2) The blending amount of indencoumarone resin ("H-100" manufactured by Nitto Chemical Co., Ltd.) was changed from 15 parts to 34 parts.

Except for the above matters, a resin varnish 8 and an adhesive film 8 were produced in the same manner as in Example 1.

[Evaluation] <Evaluation of Dielectric Tangent>

The adhesive films produced in the Examples and Comparative Examples were thermally cured at 190°C for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. Harden The product was cut into a length of 80 mm and a width of 2 mm, and used as an evaluation sample. For this evaluation sample, the dielectric tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity perturbation method using HP8362B device manufactured by Agilent Technologies (Agilent Technologies).

<Measurement of the lowest melt viscosity of the resin composition layer>

Using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM), the melt viscosity of the resin composition layer of the adhesive film produced in the Examples and Comparative Examples was measured. For 1g of the sample resin composition, use a parallel plate with a diameter of 18mm. From the starting temperature of 60°C to 200°C, the temperature rises at a temperature rise rate of 5°C/min. The measurement temperature interval is 2.5°C, the number of vibrations is 1Hz, and the deformation is 1deg. Dynamic viscoelasticity rate, calculate the lowest melt viscosity (poise).

<Evaluation of Compatibility>

Using a microscope ("DIGITAL MICROSCOPE KH-8700" manufactured by Hirox Co., Ltd.), the resin composition layer side of the adhesive film produced in the Examples and Comparative Examples was observed to confirm the presence or absence of coarse particles, and the evaluation was based on the following criteria.

-Judgment criteria for compatibility-

○: No coarse particles of 50 μm or more precipitated out of the resin composition layer of the adhesive film.

×: Coarse particles of 50 μm or more are deposited on the resin composition layer of the film.

[Measurement of plating adhesion] <Preparation of Evaluation Board> (1) Bottom layer treatment of inner circuit board

The glass cloth base epoxy resin double-sided copper laminate (copper foil thickness of 18μm, substrate thickness of 0.4mm, panasonic (stock) "R1515A") on both sides of the glass cloth substrate with inner circuit formed is immersed in MEC (stock) In "CZ8101", the copper surface is roughened by etching 1μm.

(2) Adhesive film lamination treatment

Using a batch-type vacuum pressure laminator (Meiji Co., Ltd. "MVLP-500"), the resin composition layer and the inner circuit board are bonded together, and the adhesive films produced in the examples and comparative examples are laminated Processed on both sides of the inner circuit board. The lamination process was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer

From the adhesive film after the lamination process, the PET film of the support is peeled off. Then, after preliminary heating at 80°C for 30 minutes, the resin composition layer was thermally cured at 170°C for 30 minutes to form a cured product (insulating layer) on both sides of the inner layer circuit board.

(4) Coarse treatment of hardened material

The inner layer circuit board with the hardened material formed on both sides is placed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether) at 60°C Impregnation For 10 minutes, then immerse in a roughening solution (Atotech Japan Co., Ltd. "Concentrate Compact P", potassium permanganate concentration of about 6% by mass, sodium hydroxide concentration of about 4% by mass aqueous solution), and then immerse at 80 ℃ for 20 Finally, it was immersed in a neutralization solution ("Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., aqueous hydroxylamine sulfate solution) at 40°C for 5 minutes. Then, it was dried at 80°C for 30 minutes.

(5) Formation of conductor layer

According to the semi-additive method, a conductive layer is formed on the roughened surface of the hardened object.

That is, the roughened substrate is _{immersed in an electroless plating solution containing PdCl 2} at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Then, it is heated at 150° C. for 30 minutes, and an annealing treatment is performed to form an etching resist, and a pattern is formed by etching. Then, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. The annealing treatment was performed at 200°C for 60 minutes to obtain an evaluation substrate.

<Measurement of the peel strength (plating adhesion) between the surface of the hardened product and the conductor layer>

On the conductor layer of the evaluation substrate, apply a cut with a width of 10mm and a length of 100mm, peel off this end, and hold it with a clamp. At room temperature (25°C), measure at a speed of 50mm/min, and pull it in the vertical direction. The load at 35mm (kgf/cm) is used to determine the peel strength. The measurement system uses a tensile testing machine (Autocom type testing machine "AC-50C-SL" manufactured by TSE (Stock)).

[Measurement of Bottom Adhesion] (1) Bottom treatment of copper foil

The glossy surface of 3EC-III (electric field copper foil, 35μm) manufactured by Mitsui Metals Mines Co., Ltd. is immersed in MECetchBOND CZ-8101 manufactured by MEC (stock), and the copper surface is roughened (Ra value = 1μm) to prevent Rust treatment (CL8300). This copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130°C for 30 minutes.

(2) Laminating and insulating layer formation of copper foil

The same operation as "(2) Adhesive film lamination process" of the above-mentioned [Measurement of plating adhesion] was performed to prepare a substrate from which the PET film of the support was peeled off. Laminate the treated surface of the 3EC-III CZ copper foil on the resin composition layer under the same conditions as the above-mentioned [Measurement of plating adhesion] "(2) Adhesive film lamination treatment". Then, the resin composition layer was cured under curing conditions of 190°C for 90 minutes to form an insulating layer, and a sample was produced.

(3) Measurement of copper foil tensile peel strength (adhesion to the bottom layer)

Cut the produced sample into small pieces of 150×30 mm. The small piece of copper foil is cut with a cutting knife on the part with a width of 10mm and a length of 100mm. One end of the copper foil is peeled off, and it is held by a clamp ((share) TSE, Autocom type testing machine "AC-50C-SL") , Using the Instron universal testing machine, at room temperature, in accordance with JIS C6481, measured at a speed of 50mm/min, the load when peeling 35mm in the vertical direction, as the "underlying adhesion".

In the table, the content of the (A) component, the content of the (B) component, the content of the (C) component, and the content of the (D) component indicate the content when the resin component is 100% by mass.

It can be seen from the table that the quantified (D) component and the (C) component of Examples 1 to 6 have high compatibility, excellent dielectric tangent and melt viscosity, as well as plating adhesion and underlayer adhesion. Excellent.

In addition, it was found that the lowest melt viscosity of Comparative Example 2 in which the content of the component (D) was large became low, and the adhesion of the primer layer was inferior to those of Examples 1 to 6.

In addition, Comparative Example 1 with a small content of the component (D) had poor compatibility, so crystals precipitated in the film, and the lowest melt viscosity could not be measured. In addition, due to poor compatibility, an insulating layer could not be formed, and the dielectric tangent, plating adhesion, and underlayer adhesion could not be measured.

Claims (11)

A resin composition comprising (A) epoxy resin, (B) hardener, (C) resin having a vinyl group, and (D) indencoumarone resin, wherein (D) component When the content of the resin component is 100% by mass, it is 5 mass% to 20% by mass. When the content of component (C) is 100% by mass resin component, it is 1% by mass to 30% by mass. The component (C) is as follows The resin represented by formula (1),

(In formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and A represents a group represented by the following formula (2) or the following formula (3)) -CH ₂ -OEO-CH _2- (2) (In formula (2), E represents the following formula (E-1), (E-2) or (E-3))

(In formula (3), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group with less than 6 carbon atoms or a phenyl group, and E represents the following formula (E-1), (E-2) or (E- 3), a and b mean at least one of them is not an integer from 0 to 100)

(In formulas (E-1)~(E-3), R ¹⁵ ~ R ³⁴ each independently represent a hydrogen atom, an alkyl group with less than 6 carbon atoms, or a phenyl group, and G represents a linear chain with less than 20 carbon atoms , Branched or cyclic divalent hydrocarbon group). The resin composition of claim 1, wherein at least one of component (C) has an aromatic ring. Such as the resin composition of claim 1, wherein the content of component (C) is 5% to 20% by mass when the resin component is 100% by mass. The resin composition of claim 1, wherein at least one of the component (B) is an active ester hardener. The resin composition of claim 1, which further contains (E) an inorganic filler. For the resin composition of claim 5, the content of component (E) is 50% by mass or more when the non-volatile content of the resin composition is 100% by mass. The resin composition of claim 1, wherein component (D) is a copolymer of indene, coumarone, and styrene. Such as the resin composition of claim 1, which is used for forming an insulating layer of a printed circuit board. An adhesive film having a support and a resin composition layer containing the resin composition of any one of claims 1 to 8 arranged on the support. A printed circuit board comprising an insulating layer formed by a hardened product of the resin composition of any one of claims 1 to 8. A semiconductor device provided with a printed circuit of claim 10 plate.