CN106256862B

CN106256862B - Resin composition

Info

Publication number: CN106256862B
Application number: CN201610423902.5A
Authority: CN
Inventors: 藤岛祥平; 中村茂雄
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2015-06-22
Filing date: 2016-06-16
Publication date: 2020-11-03
Anticipated expiration: 2036-06-16
Also published as: KR20160150587A; TWI701288B; TW201710366A; JP6648425B2; CN106256862A; KR102535432B1; JP2017008204A

Abstract

The invention provides a resin composition which can form an insulating layer excellent in any of circuit embeddability, dielectric loss tangent and elongation at break when a printed wiring board is manufactured, and an adhesive film, a printed wiring board and a semiconductor device using the resin composition. The resin composition comprises (A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. And further relates to an adhesive film, a printed wiring board, and a semiconductor device.

Background

As a technique for manufacturing a printed wiring board, a manufacturing method using a stack (build) method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method using the stack method, the resin composition is usually cured to form the insulating layer.

For example, patent document 1 discloses a resin composition containing a hydroxyl group-containing organosilicon compound (a), a cyanate ester compound (B) and/or a phenol resin (C), and an inorganic filler (D).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2014-84327.

Disclosure of Invention

Problems to be solved by the invention

It is disclosed that the resin composition of patent document 1 maintains high flame retardancy by curing, has high heat resistance, has a low coefficient of thermal expansion in the plane direction, and has excellent drilling processability. However, it is not sufficient to satisfy various characteristics important in the production of a printed wiring board with good balance.

The invention provides a resin composition which can form an insulating layer excellent in any of circuit embeddability, dielectric loss tangent and elongation at break when a printed wiring board is manufactured, and an adhesive film, a printed wiring board and a semiconductor device using the resin composition.

Means for solving the problems

The present inventors have made extensive studies on the above problems, and as a result, have found that the above problems can be solved by using (a) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent in combination, and have completed the present invention.

That is, the present invention includes the following:

[1] a resin composition containing (a) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent;

[2] the resin composition according to [1], wherein the content of the component (B) is 1 to 30% by mass, based on 100% by mass of nonvolatile components in the resin composition;

[3] the resin composition according to [1] or [2], wherein the content of the component (C) is 0.01 to 5% by mass, based on 100% by mass of nonvolatile components in the resin composition;

[4] the resin composition according to any one of [1] to [3], which comprises (D) an inorganic filler;

[5] the resin composition according to [4], wherein the content of the component (D) is 50% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass;

[6] the resin composition according to [4] or [5], wherein the component (D) has an average particle diameter of 0.01 to 3 μm;

[7] the resin composition according to any one of [4] to [6], wherein the component (D) is silica;

[8] the resin composition according to any one of [1] to [7], which comprises (E) a thermoplastic resin;

[9] an adhesive film comprising a support and, provided on the support, a resin composition layer containing the resin composition according to any one of [1] to [8 ];

[10] the adhesive film according to [9], wherein the resin composition layer has a minimum melt viscosity of 3000 poise or less;

[11] the adhesive film according to [9] or [10], wherein the elongation at break of the cured resin composition layer is 1.5% or more;

[12] a printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [8 ];

[13] a semiconductor device comprising the printed wiring board according to [12 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a resin composition which can form an insulating layer excellent in any of circuit embeddability, dielectric loss tangent and elongation at break in the production of a printed wiring board, and an adhesive film, a printed wiring board and a semiconductor device each using the resin composition.

Detailed Description

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

[ resin composition ]

The resin composition of the present invention is characterized by containing (A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

(A) epoxy resin

The resin composition of the present invention contains (a) an epoxy resin (hereinafter also referred to as component (a)).

Examples of the epoxy resin include: bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol novolac (naphthol novolac) type epoxy resin, phenol novolac (phenol novolac) type epoxy resin, t-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol novolac-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresolnovolac (cresol novolac) type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-containing epoxy resin, cyclohexane dimethanol-type epoxy resin, naphthylene ether (naphthylene ether) -type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, naphthalene-type epoxy resin, and mixtures thereof, And a bismethylphenol (ビキシレノール) type epoxy resin. The epoxy resins may be used alone or in combination of two or more.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. It is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule, based on 100% by mass of the nonvolatile components of the epoxy resin. Among them, it preferably contains: an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ℃ (hereinafter referred to as "liquid epoxy resin"), and an epoxy resin having three or more epoxy groups in one molecule and being solid at a temperature of 20 ℃ (hereinafter referred to as "solid epoxy resin"). By using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

As the liquid epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, and epoxy resin having a butadiene structure are preferable; more preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, and naphthalene type epoxy resins. Specific examples of the liquid epoxy resin include: "HP 4032", "HP 4032D", "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC, 828US ", jER828 EL" (bisphenol a type epoxy resin), jER807 "(bisphenol F type epoxy resin), jER 152" (phenol novolac type epoxy resin), "ZX 1059" (a mixture of bisphenol a type epoxy resin and bisphenol F type epoxy resin) manufactured by mitsubishi chemical corporation, "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX corporation, "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by university road, and "PB-3600" (epoxy resin having a butadiene structure). These may be used alone or in combination of two or more.

As the solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol a type epoxy resin, tetraphenylethane type epoxy resin are preferable; more preferred are naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, and biphenyl type epoxy resins. Specific examples of the solid epoxy resin include: "HP 4032H" (naphthalene epoxy resin), "HP-4700", "HP-4710" (naphthalene 4-functional epoxy resin), "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP-7200 HH", "EXA 7311-G3", "EXA 7311-G4", "EXA 7311-G4S", "HP 6000" (naphthylene ether epoxy resin), "EPPN-502H" (trisphenol epoxy resin), "NC 7000L" (naphthol novolac epoxy resin), "NC 3000H", "NC 633000", "NC 3000L", "NC 3100" (biphenyl epoxy resin), and "ESN 475V" (ESN phenol epoxy resin), "ESN 485" (naphthol novolac epoxy resin) manufactured by Nippon Metal chemical Co., Ltd, "YX 4000H" (biphenyl type epoxy resin), "YL 6121" (biphenyl type epoxy resin), "YX 4000 HK" (bismethylphenol type epoxy resin), "YX 8800" (anthracene type epoxy resin), "PG-100" (PG-500) manufactured by osaka gas chemistry (osaka ガスケミカル) (inc.), "YL 7800" (fluorene type epoxy resin) manufactured by mitsubishi chemical, and "jER 1010" (solid bisphenol a type epoxy resin), "jER 1031S" (tetraphenylethane type epoxy resin), "YL 7760" (bisphenol AF type epoxy resin) manufactured by mitsubishi chemical.

In the case of using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1-1: and 6. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the following effects can be obtained: i) the adhesive film can provide adequate adhesiveness when used in the form of an adhesive film, ii) can provide sufficient flexibility and improved handling properties when used in the form of an adhesive film, and iii) can provide a cured product having sufficient breaking strength. From the viewpoint of the effects of the above i) to iii), the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin), more preferably 1: 0.3-1: 5, more preferably 1: 0.6-1: 4 in the above range.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention can be obtained, and is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100 mass%, unless otherwise specified.

The epoxy resin preferably has an epoxy equivalent of 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and even more preferably 110 to 1000. When the amount is within this range, the crosslinking density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

< (B) an active ester compound

The resin composition of the present invention contains (B) an active ester compound (hereinafter also referred to as component (B)).

The active ester compound is an active ester compound having one or more active ester groups in one molecule. The active ester compound is preferably an active ester compound having two or more active ester groups in one molecule, and for example, active ester compounds having two or more highly reactive ester groups in one molecule, such as phenol esters (phenoesters), thiophenol esters (thiophenol esters), N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester compounds may be used alone or in combination of two or more.

From the viewpoint of improving heat resistance, an active ester compound obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound is more preferable; more preferably an aromatic compound having two or more active ester groups in one molecule, which is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group; more preferably, the aromatic compound is obtained by reacting a carboxylic acid compound having at least two or more carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group, that is, an aromatic compound having two or more active ester groups in one molecule. The active ester compound may be linear or branched. Furthermore, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be improved; when the compound is a compound having an aromatic ring, the heat resistance can be improved.

Examples of the carboxylic acid compound include: aliphatic carboxylic acids having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms), and aromatic carboxylic acids having 7 to 20 carbon atoms (preferably 7 to 10 carbon atoms). Examples of the aliphatic carboxylic acid include: acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid, and the like. Examples of the aromatic carboxylic acid include: benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable, from the viewpoint of heat resistance.

The thiocarboxylic acid compound is not particularly limited, and examples thereof include: thioacetic acid, thiobenzoic acid, and the like.

Examples of the phenol compound include: a phenol compound having 6 to 40 carbon atoms (preferably 6 to 30 carbon atoms, more preferably 6 to 23 carbon atoms, and further preferably 6 to 22 carbon atoms) includes, as suitable examples: hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol (benzzenetriol), dicyclopentadiene type diphenol, and the like. As the phenol compound, a phenol novolac (phenomenovolak) or a phosphorus atom-containing oligomer having a phenolic hydroxyl group as described in Japanese patent laid-open publication No. 2013-40270 can be used.

Examples of the naphthol compound include: the naphthol compound having 10 to 40 carbon atoms (preferably 10 to 30 carbon atoms, more preferably 10 to 20 carbon atoms) includes, as suitable examples: alpha-naphthol, beta-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, and the like. As the naphthol compound, naphthol phenol resin can also be used.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol, phenol-novolac resin, phosphorus atom-containing oligomer having phenolic hydroxyl group; more preferably catechol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriphenol, dicyclopentadiene type diphenol, phenol-phenol resin, phosphorus atom-containing oligomer having phenolic hydroxyl group; further preferred are 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol-novolac resins, phosphorus atom-containing oligomers having phenolic hydroxyl groups; still more preferably 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phenol novolac resin, phosphorus atom-containing oligomer having phenolic hydroxyl group; particularly more preferred are 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phosphorus atom-containing oligomer having a phenolic hydroxyl group; dicyclopentadiene type diphenols are particularly preferred.

The thiol compound is not particularly limited, and examples thereof include: benzenedithiol, triazinedithiol, and the like.

Suitable examples of the active ester compound include: an active ester compound having a dicyclopentadiene type diphenol structure, an active ester compound having a naphthalene structure, an active ester compound having an acetylate of a phenol-novolac resin, an active ester compound having a benzoyl of a phenol-novolac resin, an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group; among them, an active ester compound having a dicyclopentadiene type diphenol structure, an active ester compound having a naphthalene structure, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. In the present invention, the "dicyclopentadiene type diphenol structure" represents a 2-valent structural unit containing phenylene-dicyclopentylene (ジシクロペンチレン) -phenylene.

As the active ester compound, the active ester compounds disclosed in japanese patent application laid-open nos. 2004-277460 and 2013-40270 can be used, and commercially available active ester compounds can also be used. Examples of commercially available active ester compounds include "EXB 9451", "EXB 9460S", "HPC-8000-65T", "HPC-8000L-65M" (an active ester compound having a dicyclopentadiene type diphenol structure), "EXB 9416-70 BK" (an active ester compound having a naphthalene structure) manufactured by DIC, and "DC 808" (an active ester compound having an acetylate of a phenol novolac resin) manufactured by Mitsubishi chemical, and "YLH 1026" (an active ester compound having a benzoylate of a phenol novolac resin) manufactured by Mitsubishi chemical, and "EXB 9050L-62M" (an active ester compound having a phosphorus atom) manufactured by DIC.

The content of the active ester compound in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and further preferably 4% by mass or more, 5% by mass or more, 6% by mass or more, or 7% by mass or more. The upper limit of the content of the active ester compound is not particularly limited, and is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, or 10% by mass or less.

When the number of epoxy groups of the epoxy resin (a) is 1, the number of reaction groups of the active ester compound (B) is preferably 0.1 to 2, more preferably 0.2 to 1.5, and even more preferably 0.3 to 1, from the viewpoint of obtaining an insulating layer having good mechanical strength. Here, the "number of epoxy groups of the epoxy resin" refers to a value obtained by summing up values obtained by dividing the mass of the solid content of each epoxy resin present in the resin composition by the epoxy equivalent weight, with respect to all the epoxy resins. The "reactive group" refers to a functional group capable of reacting with an epoxy group, and the "number of reactive groups of the active ester compound" refers to a total value obtained by dividing the mass of the solid content of the active ester compound present in the resin composition by the equivalent of the reactive group.

< (C) triphenylimidazole which may have a substituent

The resin composition of the present invention contains (C) triphenylimidazole which may have a substituent (hereinafter also referred to as component (C)) as a curing accelerator.

The inventors of the present invention found that: by using the component (B) and the component (C) in combination in the resin composition, an insulating layer excellent in any of circuit embeddability, dielectric loss tangent and elongation at break can be formed in the production of a printed wiring board. This is considered to be because the phenyl group in the component (C) is a rigid substituent, so that the curing reaction between the component (a) and the component (B) becomes slow, and the melt viscosity in the semi-cured state (B stage) of the resin composition layer described below is likely to decrease. In the case where the content of the inorganic filler is increased, the melt viscosity is increased and the circuit embeddability is liable to be lowered, but in the present invention, the use of the component (C) can maintain the melt viscosity at a low level, and thus a good circuit embeddability can be achieved.

In the present specification, "triphenylimidazole which may have a substituent" means both triphenylimidazole whose hydrogen atom is not substituted by a substituent and triphenylimidazole whose hydrogen atom is partially or entirely substituted by a substituent. When triphenylimidazole has a substituent, the hydrogen atom at the 1-position of imidazole may be substituted with a substituent, and the hydrogen atom of phenyl group may be substituted with a substituent.

The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -O-C_1-6Alkyl, -N (C)_1-6Alkyl radical)₂、C_1-6Alkyl radical, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-6Alkyl, -COOH, -C (O) H, -NO₂And the like.

Here, "C_p-qThe term "(p and q are positive integers, and p < q.) indicates that the organic group described immediately after the term has p to q carbon atoms. E.g. "C_1-6The expression "alkyl" denotes an alkyl group having 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). As the secondary substituent, the same groups as those described above may be used unless otherwise specified.

Among them, the component (C) is preferably triphenylimidazole in which a hydrogen atom at the 1-position of imidazole or a hydrogen atom of phenyl group is not substituted by a substituent, and more preferably 2,4, 5-triphenylimidazole.

(C) The content of the component (b) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.05% by mass or more, or 0.1% by mass or more. (C) The upper limit of the content of the component (b) is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0.3% by mass or less.

When the content of the component (B) is B (mass%) and the content of the component (C) is C (mass%) when the nonvolatile component of the resin composition is 100 mass%, C/B is preferably 0.001 to 0.2, more preferably 0.005 to 0.1, and still more preferably 0.01 to 0.05.

(D) inorganic filler

The resin composition of the present invention preferably contains (D) an inorganic filler (hereinafter also referred to as component (D)) in addition to components (a) to (C).

The material of the inorganic filler is not particularly limited, and examples thereof include: silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, zirconium phosphate, zirconium phosphotungstate phosphate, and the like. Of which silicon dioxide is particularly suitable. In addition, as the silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is not particularly limited, and is preferably 3 μm or less, more preferably 2 μm or less, and still more preferably 1 μm or less, from the viewpoint of obtaining an insulating layer having a small surface roughness or from the viewpoint of improving the formability of fine wiring. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. Examples of commercially available inorganic fillers having such an average particle diameter include "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admatech, and "UFP-30" manufactured by Electrical chemical industry, and "シルフィル NSS-3N", "シルフィル NSS-4N", "シルフィル NSS-5N" manufactured by Deshan (Tokuyama), and "SO-C2" and "SO-C1" manufactured by Admatech.

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 is measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter is set as an average particle diameter. The measurement sample may preferably be one obtained by dispersing an inorganic filler in water using ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, there can be used "LA-500" manufactured by horiba, Ltd.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably treated with 1 or more surface-treating agents such as an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent. Examples of commercially available products of surface processing agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical Co., Ltd., "KBM 103" (phenyltrimethoxysilane) manufactured by shin-chemical Co., Ltd., "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by shin-chemical Co., Ltd.,.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, more preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet from increasing, it is preferably 1mg/m²Less than, more preferably 0.8mg/m²The concentration is preferably 0.5mg/m or less²The following.

The amount of carbon per unit surface area of the inorganic filler material can be determined by: the inorganic filler after the surface treatment is subjected to a cleaning treatment using a solvent such as Methyl Ethyl Ketone (MEK), and then measured. Specifically, MEK can be added to the inorganic filler after surface treatment with the surface treatment agent in a sufficient amount as a solvent, and ultrasonic cleaning can be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid content was dried, and then the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, there can be used "EMIA-320V" manufactured by horiba, Ltd.

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, from the viewpoint of obtaining an insulating layer having a low thermal expansion coefficient. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less, or 80% by mass or less, from the viewpoint of the mechanical strength of the insulating layer.

< (E) thermoplastic resin

The resin composition of the present invention preferably contains (E) a thermoplastic resin (hereinafter also referred to as component (E)) in addition to components (a) to (C).

Examples of the thermoplastic resin include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins, and phenoxy resins are preferable. The thermoplastic resin can be used alone in 1 kind, or can also be used in 2 or more combinations.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 8000 to 70000, more preferably 10000 to 60000, and still more preferably 20000 to 60000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by a Gel Permeation Chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin was obtained by measuring the weight average molecular weight of the resin using LC-9A/RID-6A manufactured by Shimadzu corporation as a measuring apparatus, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. K-800P/K-804L/K-804L as a column, chloroform or the like as a mobile phase, and at a column temperature of 40 ℃ and calculating the weight average molecular weight of the resin using a standard curve of standard polystyrene.

Examples of the phenoxy resin include: a phenoxy resin having one or more types of skeletons selected from a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol aldehyde (novolak) skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include: "1256" and "4250" (both phenoxy resins having a bisphenol a skeleton), "YX 8100" (phenoxy resin having a bisphenol S skeleton), and "YX 6954" (phenoxy resin having a bisphenol acetophenone skeleton), manufactured by mitsubishi chemical corporation, and others are: "FX 280" and "FX 293" manufactured by shin-Fe-sho chemical Co., Ltd, "YX 6954BH 30", "YX 7553BH 30", "YL 7769BH 30", "YL 6794", "YL 7213", "YL 7290", "YL 7891BH 30", and "YL 7482" manufactured by Mitsubishi chemical Co., Ltd.

Examples of the polyvinyl acetal resin include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "changed ブチラール 4000-2", "changed ブチラール 5000-a", "changed ブチラール 6000-C", "changed ブチラール 6000-EP", エスレック BH series, BX series, KS series, BL series, BM series, and the like, which are manufactured by electrochemical industries.

Specific examples of the polyimide resin include "リカコート SN 20" and "リカコート PN 20" manufactured by Nippon chemical and chemical Co., Ltd. Specific examples of the polyimide resin include modified polyimides such as linear polyimides obtained by reacting 2-functional hydroxyl-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in Japanese patent laid-open Nos. 2006-37083), polyimides containing a polysiloxane skeleton (polyimides described in Japanese patent laid-open Nos. 2002-12667 and 2000-319386).

Specific examples of the polyamideimide resin include "バイロマックス HR11 NN" and "バイロマックス HR16 NN" manufactured by Toyo Boseki Kabushiki Kaisha. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS 9100" and "KS 9300" (polyamide-imide having a polysiloxane skeleton) manufactured by hitachi chemical industry.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by sumitomo chemical corporation.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by ソルベイアドバンストポリマーズ (ltd.).

Specific examples of polyphenylene ether resins include an oligophenylene ether-styrene resin "OPE-2 St 1200" manufactured by Mitsubishi ガス chemical corporation.

Among them, the thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin. Therefore, in a suitable embodiment, the component (E) contains one or more selected from phenoxy resins and polyvinyl acetal resins.

The content of the thermoplastic resin in the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass.

< other additives >

The resin composition of the present invention may contain other additives as needed. Examples of the other additives include a curing agent other than the component (B), a curing accelerator other than the component (C), a flame retardant, and an organic filler.

Curing agent other than component (B)

The resin composition of the present invention may further contain a curing agent (hereinafter, also referred to as component (F)) other than component (B).

The component (F) is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include phenol (phenol) curing agents, naphthol curing agents, cyanate curing agents, benzoxazine curing agents, carbodiimide curing agents, and the like. These curing agents may be used singly, or 2 or more kinds may be used in combination.

Among these, in combination with the components (a) to (C), the component (F) is preferably a phenol-based curing agent or a naphthol-based curing agent in view of obtaining an insulating layer exhibiting good elongation at break.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a phenol-aldehyde (ノボラック) structure or a naphthol-based curing agent having a phenol-aldehyde structure is preferable from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of obtaining an insulating layer excellent in peel strength with the conductor layer, a nitrogen-containing phenol curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenol curing agent and a triazine skeleton-containing naphthol curing agent are more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and peel strength with the conductor layer, a phenol resin containing a triazine skeleton and a naphthol phenol resin containing a triazine skeleton are preferable. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Minghe Kaisha, "NHN", "CBN", "GPH" manufactured by Nippon Kaisha, "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", and "LA-7052", "LA-7054", "LA-3018", "LA-1356", "209TD 0" manufactured by DIC Kaisha.

The cyanate-based curing agent is not particularly limited, and examples thereof include: phenolic (novolak type (phenol novolak type, alkylphenol novolak type, etc.)) cyanate-based curing agents, dicyclopentadiene-type cyanate-based curing agents, bisphenol-type (bisphenol a type, bisphenol F type, bisphenol S type, etc.) cyanate-based curing agents, prepolymers in which a part of these is triazinized, and the like. Specific examples thereof include: 2-functional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate ester, oligo (3-methylene-1, 5-phenylene cyanate ester), 4 '-methylenebis (2, 6-dimethylphenyl cyanate ester), 4' -ethylenediphenyl dicyanate ester, hexafluorobisphenol A dicyanate ester, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate ester-phenyl) sulfide, and bis (4-cyanate ester-phenyl) ether, polyfunctional cyanate ester resins derived from phenol novolac, cresol novolac (cresol novolac), and the like, prepolymers in which a part of these cyanate ester resins is triazinized, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both phenol novolac-type polyfunctional cyanate ester resins) manufactured by Lonza Japan, and "BA 230" (a prepolymer in which a part or all of bisphenol a dicyanate is triazinized to form a trimer).

Specific examples of the benzoxazine-based curing agent include: "HFB 2006M" manufactured by Showa Polymer Co., Ltd, "P-d" and "F-a" manufactured by four national chemical industries, Ltd.

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

When the component (F) is used, the content of the curing agent in the resin composition is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and further preferably 0.7% by mass or more, or 1% by mass or more. The upper limit of the content is preferably 10% by mass or less, more preferably 8% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less.

Curing accelerator other than component (C) -

The resin composition of the present invention may further contain a curing accelerator (hereinafter also referred to as component (G)) other than component (C).

Examples of the component (G) include: phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators and the like, preferably phosphorus-based curing accelerators, amine-based curing accelerators and imidazole-based curing accelerators other than the component (C), more preferably amine-based curing accelerators and imidazole-based curing accelerators other than the component (C). The curing accelerator may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Examples of the phosphorus-based curing accelerator include: triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutylphosphonium decanoate being preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5,4,0) -undecene, and preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo (5,4,0) -undecene.

Examples of the imidazole-based curing accelerator other than component (C) include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-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-ethyl-4-methylimidazole, 2-cyanoethyl-2-phenylimidazole, 2-aminobutylimidazole, 2-butylimidazole, 2, 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, and mixtures thereof, Imidazole compounds such as 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 and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

Examples of the guanidine-based 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] deca-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like, preferably dicyandiamide, 1,5, 7-triazabicyclo [4.4.0] deca-5-ene.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The content of the component (G) in the resin composition is not particularly limited, and is preferably used in a range of 0.05 to 3% by mass.

Flame retardants-

The resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, an organic silicon flame retardant, and a metal hydroxide. The flame retardant may be used alone in 1 kind or in combination of 2 or more kinds.

As the flame retardant, commercially available products can be used, and examples thereof include "HCA-HQ" manufactured by Sanyo Co., Ltd., and "PX-200" manufactured by Daihuai chemical industry Co., Ltd.

The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and still more preferably 1.5 to 10 mass%.

Organic filling materials

The resin composition may further contain an organic filler (hereinafter also referred to as component (H)) in order to improve the elongation. As the component (H), any organic filler that can be used when forming an insulating layer of a printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

As the rubber particles, commercially available products can be used, and examples thereof include "EXL-2655" manufactured by Dow Chemical Co., Ltd., and "AC 3816N" manufactured by AICA industries, Ltd.

The content of the component (H) in the resin composition is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, even more preferably 0.3 to 5% by mass, or 0.5 to 3% by mass.

The resin composition may further contain other additives as needed, and examples of the other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additives such as organic fillers, tackifiers, defoaming agents, leveling agents, adhesion imparting agents, and colorants.

The glass transition temperature (Tg) of a cured product of the resin composition of the present invention is preferably 130 ℃ or higher, more preferably 150 ℃ or higher, and further preferably 155 ℃ or higher, or 160 ℃ or higher. The upper limit is preferably 200 ℃ or lower, more preferably 190 ℃ or lower, and still more preferably 180 ℃ or lower. The glass transition temperature (Tg) of a cured product of the resin composition can be measured by thermomechanical analysis using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku, ltd.) by a tensile load method (JIS K7197).

The elongation at break of the cured product of the resin composition of the present invention is preferably 1.5% or more, preferably 1.6% or more, more preferably 1.7% or more, and further preferably 1.8% or more, 1.9% or more, or 2.0% or more. The higher the upper limit of the elongation at break, the more preferable, and usually 5% or less. The elongation at break of the cured product of the resin composition can be measured by the method described in < measurement of elongation at break > below.

The dielectric loss tangent of a cured product of the resin composition of the present invention is preferably 0.02 or less, more preferably 0.01 or less, and further preferably 0.009 or less or 0.008 or less. The lower limit of the dielectric loss tangent is more preferable, and it may be usually 0.001 or more. The dielectric loss tangent of a cured product of the resin composition can be measured by the method described in < measurement of dielectric loss tangent > below.

The resin composition of the present invention can form an insulating layer excellent in any of circuit embeddability, dielectric loss tangent and elongation at break when used for manufacturing a printed wiring board. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for an interlayer insulating layer of a printed wiring board). The resin composition of the present invention can be suitably used as a solder resist.

[ adhesive film ]

The adhesive film of the present invention is characterized by comprising: and a resin composition layer comprising the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, further more preferably 50 μm or less or 40 μm or less, from the viewpoint of thinning of the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

From the viewpoint of obtaining good circuit embeddability, the minimum melt viscosity of the resin composition layer is preferably 3000 poise (300Pa seeds) or less, more preferably 2500 poise (250Pa seeds) or less, and further preferably 2000 poise (200Pa seeds) or less, 1500 poise (150Pa seeds) or less, or 1000 poise (100Pa seeds) or less. The lower limit of the minimum melt viscosity is preferably 100 poise (10Pa seeds) or more, more preferably 200 poise (20Pa seeds) or more, and still more preferably 250 poise (25Pa seeds) or more.

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 rise rate to melt the resin, the melt viscosity decreases with an increase in temperature in the initial stage, and then increases with an increase in temperature beyond a certain level. The lowest melt viscosity means the melt viscosity of the minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, and can be measured, for example, by the method described in < measurement of minimum melt viscosity > below.

Examples of the support include: the film, metal foil, and release paper made of a plastic material are preferably a film and metal foil made of a plastic material.

When a film made of a plastic material is used as the support, examples of the plastic material include: polyesters such as polyethylene terephthalate (hereinafter sometimes referred to simply as "PET"), polyethylene naphthalate (hereinafter sometimes referred to simply as "PEN"), acrylic-based polycarbonates (hereinafter sometimes referred to simply as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.

When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

The surface of the support to which the resin composition layer is bonded may be subjected to matting (マット) treatment or corona treatment.

In addition, as the support, a support with a release layer having a release layer on a surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include at least one selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support with a release layer, commercially available products can be used, and examples thereof include a PET film having a release layer containing an alkyd resin-based release agent as a main component, "SK-1", "AL-5", "AL-7" manufactured by Linekec corporation, and "Miller (ルミラー) T6 AM" manufactured by Toray corporation.

The thickness of the support is not particularly limited, but is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably within the above range.

The adhesive film can be produced, for example, by the following method: a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support using a die coater or the like, and then dried to form a resin composition layer.

Examples of the organic solvent include: ketones such as acetone, Methyl Ethyl Ketone (MEK) 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, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone, and the like. The organic solvent may be used alone or in combination of two or more.

The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the organic solvent is dried so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. The boiling point of the organic solvent in the resin varnish varies, but when a resin varnish containing 30 to 60 mass% of the organic solvent is used, for example, the resin varnish is dried at 50 to 150 ℃ for 3 to 10 minutes to form a resin composition layer.

In the adhesive film, a protective film corresponding to the support may be further laminated on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite 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, adhesion of dust or the like to the surface of the resin composition layer or scratch can be prevented. The adhesive film may be stored in a roll form. When the adhesive film has a protective film, the protective film may be peeled off.

The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[ printed Wiring Board ]

The printed wiring board of the present invention is characterized by containing an insulating layer formed by a cured product of the resin composition of the present invention.

For example, the printed wiring board of the present invention can be produced by a method comprising the steps (I) and (II) described below using the above adhesive film,

(I) laminating an adhesive film on the inner substrate so that the resin composition layer of the adhesive film is bonded to the inner substrate;

(II) a step of forming an insulating layer by thermally curing the resin composition layer.

The "inner layer substrate" used in the step (I) is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate, or a circuit substrate having a conductor layer (circuit) patterned on one surface or both surfaces of the substrate. In addition, in the case of manufacturing a printed wiring board, an inner layer circuit board, which is an intermediate product in which an insulating layer and/or a conductor layer is further formed, is also included in the "inner layer board" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-pressure bonding the adhesive film to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the adhesive film to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate or the like) and a metal roll (SUS roll). It is preferable that the pressure-bonding member is not directly pressed against the adhesive film, but is pressed through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the adhesive film may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressure bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and pressure bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and pressure bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7hPa or less.

The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko-Materials, Inc.

After lamination, the heat-pressure bonding member is pressed at normal pressure (atmospheric pressure), for example, from the support side, whereby the laminated adhesive film can be smoothed. The pressing conditions for the smoothing treatment may be the same as the heating and pressure bonding conditions for the laminate. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using the above-mentioned commercially available vacuum laminator.

The support may be removed between step (I) and step (II) or may be removed after step (II).

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

The conditions for heat curing of the resin composition layer are not particularly limited, and the conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing conditions of the resin composition layer differ depending on the kind of the resin composition and the like, but may be the following conditions: the curing temperature is in the range of 120 to 240 ℃ (preferably in the range of 150 to 220 ℃, more preferably in the range of 170 to 200 ℃) and the curing time is in the range of 5 to 120 minutes (preferably 10 to 100 minutes, more preferably 15 to 90 minutes).

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature of 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 110 ℃ or less, more preferably 70 ℃ or more and 100 ℃ or less) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

In the production of the printed wiring board, (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 performed. These steps (III) to (V) can be carried out according to various methods known to those skilled in the art used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

The step (III) is a step of opening the insulating layer, whereby holes such as a via hole (via hole) and a through hole (via hole) can be formed in the insulating layer. Step (III) can be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer, or the like. The size and shape of the hole may be determined as appropriate according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The roughening treatment step and conditions are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the roughening treatment may be performed on the insulating layer by performing an expansion treatment using an expansion liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid in this order. The swelling liquid is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and the alkali solution is preferably an alkali solution, and a sodium hydroxide solution and a potassium hydroxide solution are more preferably used as the alkali solution. Examples of commercially available swelling liquids include: "spinning Dip securigant P" and "spinning Diprechrigant SBU" manufactured by ATOTECH JAPAN (LTD), and the like. The expansion treatment using the expansion liquid is not particularly limited, and for example, the expansion treatment can be performed by immersing the insulating layer in the expansion liquid at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, the cured body is preferably immersed in the swelling solution at 40 to 80 ℃ for 5 to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using 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 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution securigant P" manufactured by ato ech JAPAN (ltd.). Further, as the neutralizing Solution, an acidic aqueous Solution is preferable, and as a commercially available product, for example, "Reduction Solution securigrant P (リダクションソリューション seed セキュリガント P)" manufactured by ato ech JAPAN (ltd.) can be mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to dip the object subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400nm or less, more preferably 350nm or less, and further preferably 300nm or less, 250nm or less, 200nm or less, 150nm or less, or 100nm or less. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. Specific examples of the non-contact type surface roughness meter include "WYKO NT 3300" manufactured by VeecoInstruments Inc.

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

The conductor material used for the conductor layer is not particularly limited. In a preferred 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, and examples of the alloy layer include layers formed of an alloy of two or more metals selected from the above-mentioned metals (e.g., a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.

The conductor layer may have a single-layer structure, or may have a multilayer structure in which two or more single metal layers or alloy layers containing different types of metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally from 3 μm to 35 μm, preferably from 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed using plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method (フルアディティブ method). An example of forming a conductor layer by the semi-additive method is described below.

First, plating seed layers are formed on the surfaces of the insulating layers by electroless plating (めっきシード body regions). Next, a mask pattern is formed on the plating seed layer so as to expose a part of the plating seed layer in accordance with a desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electroplating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

[ semiconductor device ]

The semiconductor device of the present invention is characterized by containing the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, airplanes, and the like).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conduction portion of a printed wiring board. The "conductive portion" refers to a "portion that conducts an electrical signal in the printed wiring board", and the position thereof may be either a surface or a buried portion. The semiconductor chip is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting the semiconductor chip in the production of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, and specific examples thereof include: wire bonding mounting methods, flip chip mounting methods, mounting methods using a built-in non-rugged layer (バルプなしビルドアップ body frame, BBUL), mounting methods using an Anisotropic Conductive Film (ACF), mounting methods using a non-conductive film (NCF), and the like. Here, the "mounting method using a base band non-convex layer (BBUL)" is a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In the following description, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise stated.

First, various measurement methods and evaluation methods will be described.

< measurement of minimum melt viscosity >

The melt viscosity of the resin composition layer in the adhesive films prepared in examples and comparative examples was measured. The melt viscosity was measured under the measurement conditions of 60 ℃ to 200 ℃ from the initial temperature, a temperature rise rate of 5 ℃/min, a measurement temperature interval of 2.5 ℃ and a vibration of 1 Hz/deg.C using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM Co., Ltd.) with a resin amount of 1G and a parallel plate diameter of 18 mm.

< determination of elongation at Break >

The adhesive films prepared in examples and comparative examples were heated at 200 ℃ for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The resulting cured product was referred to as "cured product for evaluation". The cured product for evaluation was subjected to a tensile test using a Tensilon Universal tester ("RTC-1250A" manufactured by Orientec corporation) in accordance with Japanese Industrial Standard (JIS K7127), and the elongation at break was measured.

< measurement of glass transition temperature >

The cured product for evaluation was cut into a test piece having a width of about 5mm and a length of about 15mm, and subjected to thermomechanical analysis by a tensile load method using a thermomechanical analyzer ("Thermo Plus TMA 8310" manufactured by Rigaku corporation). Specifically, after the test piece was mounted on the thermomechanical analyzer, the measurement was performed twice continuously under the measurement conditions of a load of 1g and a temperature rise rate of 5 ℃/min. Then, in the second measurement, the glass transition temperature (Tg;. deg.C) was calculated.

< determination of dielectric loss tangent >

The cured product for evaluation was cut into test pieces having a width of 2mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured by the resonance cavity method at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using a dielectric constant measuring apparatus ("HP 8362B" manufactured by Agilent Technologies Co., Ltd.). Two test pieces were measured, and the average value was calculated.

< example 1 >

30 parts of bisphenol A epoxy resin ("828 US" manufactured by Mitsubishi chemical corporation, epoxy equivalent of about 180) and 30 parts of biphenyl epoxy resin ("NC 3000H" manufactured by Nippon Kabushiki Kaisha, epoxy equivalent of about 269) were dissolved in 55 parts of solvent oil with stirring and heated, and then cooled to room temperature. To the mixed solution, 260 parts of spherical silica (average particle size 0.5 μm, SO-C2, manufactured by Admatech, Ltd.) surface-treated with an aminosilane-based coupling agent ("KBM 573", manufactured by shin-Etsu chemical Co., Ltd.) was added, and the mixture was kneaded with 3 rolls to be uniformly dispersed. To this roll dispersion, 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC corporation, having an active group equivalent of about 223, and a toluene solution having a nonvolatile content of 65 mass%), 20 parts of a phenoxy resin ("YX 6954BH 30" manufactured by mitsubishi chemical corporation, a 1: 1 solution of 30 mass% methyl ethyl ketone (hereinafter, abbreviated as "MEK") and cyclohexanone, 24 parts of a curing accelerator ("2, 4, 5-triphenylimidazole" manufactured by tokyo chemical industry, and a 1: 1 solution of MEK and cyclohexanone having a solid content of 2.5 mass%) and MEK10 parts were mixed, and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish.

As a support, a PET film (AL-5 manufactured by Linekaceae, Ltd., thickness: 38 μm) having an alkyd resin-based release layer was prepared. The resin varnish was uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer was 40 μm, and the resin composition layer was dried at 80 to 120 ℃ (average 100 ℃) for 5 minutes to prepare an adhesive film.

< example 2 >

A resin varnish and an adhesive film were produced in the same manner as in example 1, except that 14 parts of a triazine skeleton-containing phenol curing agent ("LA-3018-50P" manufactured by DIC corporation, 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a solid content of 50%) was further mixed with the roll dispersion in example 1.

< example 3 >

A resin varnish and an adhesive film were produced in the same manner as in example 2, except that 30 parts of a biphenyl type epoxy resin ("NC 3000H" manufactured by japan chemical corporation, having an epoxy equivalent of about 269) was changed to 30 parts of a naphthol type epoxy resin ("ESN 475V" manufactured by shinko chemical industries, inc., having an epoxy equivalent of 332) in example 2.

< example 4 >

A resin varnish and an adhesive film were produced in the same manner as in example 2, except that 30 parts of a biphenyl type epoxy resin ("NC 3000H" manufactured by japan chemical corporation, having an epoxy equivalent of about 269) was changed to 30 parts of a bismethylphenol type epoxy resin ("YX 4000 HK" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 185) in example 2.

< example 5 >

A resin varnish and an adhesive film were produced in the same manner as in example 2, except that 3 parts of methacrylic modified styrene-butadiene rubber particles (メタクリルブタジエンスチレンゴム particles) (EXL-2655, manufactured by Takara chemical Co., Ltd.) were further added to the mixed solution in example 2.

< comparative example 1 >

A resin varnish and an adhesive film were produced in the same manner as in example 1, except that 24 parts of a curing accelerator (a 1: 1 solution of "2, 4, 5-triphenylimidazole" manufactured by tokyo chemical industry, inc., and MEK and cyclohexanone having a solid content of 2.5 mass%) was changed to 6 parts of a curing accelerator (a 1B2PZ ", 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 10 mass%), in example 1.

< comparative example 2 >

A resin varnish and an adhesive film were produced in the same manner as in example 1, except that 24 parts of a curing accelerator (a 1: 1 solution of MEK and cyclohexanone having a solid content of 2.5 mass%) was changed to 6 parts of a curing accelerator (DMAP, 4-dimethylaminopyridine, and a MEK solution having a solid content of 5 mass%) in example 1.

< comparative example 3 >

A resin varnish and an adhesive film were produced in the same manner as in example 1, except that 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, having an active group equivalent of about 223 and a toluene solution containing 65% by mass of nonvolatile matter) was changed to 26 parts of a phenol novolac type polyfunctional cyanate ester resin ("PT 30" manufactured by Lonza Japan, having a cyanate equivalent of 124) in example 1.

[ Table 1]

。

Claims

1. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) a substituted or unsubstituted triphenylimidazole,

when the content of the component (B) is B and the content of the component (C) is C, the ratio of C/B is 0.001 to 0.2, where B and C are expressed in mass% when the nonvolatile content of the resin composition is 100 mass%.

2. The resin composition according to claim 1, wherein the component (C) is any one of triphenylimidazole in which a hydrogen atom of triphenylimidazole is not substituted with a substituent, and triphenylimidazole in which a part or all of a hydrogen atom of triphenylimidazole is substituted with a substituent.

3. The resin composition according to claim 1, wherein the content of the component (B) is 1 to 30% by mass, based on 100% by mass of nonvolatile components in the resin composition.

4. The resin composition according to claim 3, wherein the content of the component (B) is 3% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

5. The resin composition according to claim 3, wherein the content of the component (B) is 5% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

6. The resin composition according to claim 3, wherein the content of the component (B) is 20% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

7. The resin composition according to claim 3, wherein the content of the component (B) is 10% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

8. The resin composition according to claim 1, wherein the content of the component (C) is 0.01 to 5% by mass, based on 100% by mass of nonvolatile components in the resin composition.

9. The resin composition according to claim 8, wherein the content of the component (C) is 0.03% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

10. The resin composition according to claim 8, wherein the content of the component (C) is 0.05% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

11. The resin composition according to claim 8, wherein the content of the component (C) is 3% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

12. The resin composition according to claim 8, wherein the content of the component (C) is 2% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

13. The resin composition according to claim 1, wherein (D) an inorganic filler is contained.

14. The resin composition according to claim 13, wherein the content of the component (D) is 50% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

15. The resin composition according to claim 14, wherein the content of the component (D) is 60% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

16. The resin composition according to claim 14, wherein the content of the component (D) is 95% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

17. The resin composition according to claim 14, wherein the content of the component (D) is 90% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

18. The resin composition according to claim 13, wherein the average particle diameter of the component (D) is 0.01 to 3 μm.

19. The resin composition according to claim 18, wherein the average particle diameter of the component (D) is 2 μm or less.

20. The resin composition according to claim 18, wherein the average particle diameter of the component (D) is 0.1 μm or more.

21. The resin composition according to claim 13, wherein the component (D) is silica.

22. The resin composition according to claim 1, wherein (E) a thermoplastic resin is contained.

23. The resin composition according to claim 22, wherein the (E) component comprises a phenoxy resin.

24. The resin composition according to claim 1, wherein when the content of the component (B) is represented by B and the content of the component (C) is represented by C, the ratio C/B is 0.001 to 0.05, where B and C are represented by mass% when the nonvolatile content of the resin composition is 100 mass%.

25. An adhesive film comprising a support and, provided on the support, a resin composition layer containing the resin composition according to claim 1.

26. The adhesive film according to claim 25, wherein the resin composition layer has a minimum melt viscosity of 3000 poise or less.

27. A bonding film according to claim 26, wherein the resin composition layer has a minimum melt viscosity of 2500 poise or less.

28. The adhesive film according to claim 26, wherein the resin composition layer has a minimum melt viscosity of 100 poise or more.

29. An adhesive film according to any one of claims 25 to 28, wherein the cured resin composition layer has an elongation at break of 1.5% or more.

30. The adhesive film according to claim 29, wherein the elongation at break of the cured resin composition layer is 1.8% or more.

31. The adhesive film according to claim 29, wherein the elongation at break of the cured resin composition layer is 5% or less.

32. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 24.

33. A semiconductor device comprising the printed wiring board according to claim 32.