TW202142587A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition that can obtain a cured product with low dielectric tangent, excellent adhesion, and excellent residue removal; a resin sheet containing the resin composition; and a printed wiring equipped with an insulating layer formed using the resin composition Board; and semiconductor device. A resin composition comprising (A) epoxy resin, (B) active ester hardener, (C) polyester polyol resin with aromatic structure, and (D) inorganic filler.

Description

Resin composition

The present invention relates to a resin composition. In addition, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device containing the resin composition.

The manufacturing technology of the printed wiring board, for example, a build-up method of alternately laminating an insulating layer and a conductor layer on an inner circuit board is known. The insulating layer is generally formed by hardening a resin composition.

For example, Patent Document 1 describes a thermosetting resin composition containing (A) a thermosetting resin, (B) a thermosetting agent, and (C) a modified resin. In addition, Patent Document 2 describes an active energy ray curable composition containing an acid group-containing epoxy (meth)acrylate resin, an epoxy-based curing agent, and a modified resin. In addition, Patent Document 3 describes a curable resin composition containing (A) an epoxy resin, (B) an active ester curing agent and/or a cyanate ester curing agent, and (C) a polyester resin having a turquoise structure. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2019/131413 [Patent Document 2] International Publication No. 2019/044803 [Patent Document 3] JP 2014-159512 A

[The problem to be solved by the invention]

In recent years, in the manufacture of multilayer printed wiring boards, the cured product of the resin composition used to form the insulating layer requires low dielectric tangent and high adhesion to copper foil. In addition, it has the ability to remove residues to ensure the reliability of conduction. .

As a result of the review by the inventors, it was found that a cured product of a resin composition containing a material that lowers the dielectric tangent and improves adhesion has low residue removal properties for ensuring the reliability of conduction. Therefore, it is currently impossible to provide a resin composition with a low dielectric tangent, excellent adhesion, and excellent residue removal.

The subject of the present invention is to provide a resin composition that can obtain a cured product with low dielectric tangent, excellent adhesion, and excellent residue removal; a resin sheet containing the resin composition; and an insulating layer formed using the resin composition Printed wiring boards; and semiconductor devices. [Means to solve the problem]

In order to solve the aforementioned problems, the inventor of the present invention conducted a careful review and found that by combining (A) an epoxy resin, (B) an active ester curing agent, (C) a polyester polyol resin having an aromatic structure, and ( D) The resin composition of the inorganic filler can solve the aforementioned problems, thus completing the present invention. That is, the present invention includes the following contents.

[1] A resin composition comprising (A) Epoxy resin, (B) Active ester hardener, (C) Polyester polyol resin with aromatic structure, and (D) Inorganic filler. [2] The resin composition according to [1], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 0.1% by mass or more and 10% by mass or less. [3] The resin composition according to [1] or [2], wherein the component (C) has a bisphenol skeleton. [4] The resin composition according to [3], wherein the component (C) has a hydroxyl group at the terminal. [5] The resin composition according to any one of [1] to [4], wherein the hydroxyl value of component (C) is 2 mgKOH/g or more and 450 mgKOH/g or less. [6] The resin composition of any one of [1] to [5], wherein the viscosity of component (C) at 75°C is 0.5 Pa･s or more and 25 Pa･s or less. [7] The resin composition according to any one of [1] to [6], wherein the number average molecular weight of the component (C) is 500 or more and 7000 or less. [8] The resin composition according to any one of [1] to [7], wherein the component (B) contains at least one selected from the group consisting of dicyclopentadiene-type active ester hardeners and naphthalene-type active ester hardeners 1 kind. [9] The resin composition of any one of [1] to [8], wherein the non-volatile content in the resin composition is set to 100% by mass when the content of component (B) is b1, and the content of the resin composition is When the content of the (C) component when the non-volatile content is 100% by mass is c1, b1/c1 is 3 or more and 30 or less. [10] The resin composition according to any one of [1] to [9], wherein when the non-volatile content in the resin composition is set to 100% by mass, the content of the component (D) is 50% by mass or more. [11] The resin composition of any one of [1] to [10], which further contains (E) a hardener. [12] The resin composition according to [11], wherein (E) the hardener contains a phenol-based hardener. [13] The resin composition of any one of [1] to [12], which is used for insulation purposes. [14] The resin composition of any one of [1] to [13], which is used for forming an insulating layer. [15] The resin composition of any one of [1] to [14], which is used for forming an insulating layer for forming a conductive layer. [16] A resin sheet comprising: a support and a resin composition layer including the resin composition of any one of [1] to [15] provided on the support. [17] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition of any one of [1] to [15]. [18] A semiconductor device comprising the printed wiring board as in [17]. [Effects of the invention]

According to the present invention, it is possible to provide a resin composition that can obtain a cured product with low dielectric tangent, excellent adhesion, and excellent residue removal; a resin sheet containing the resin composition; and an insulation formed by using the resin composition Layers of printed wiring boards; and semiconductor devices. [The form of implementing the invention]

Hereinafter, embodiments and exemplified materials are shown to explain the present invention in detail. However, the present invention is not limited to the following embodiments and exemplified materials, and can be implemented with any changes within the scope that does not deviate from the scope of the present invention and its equivalent scope.

[Resin composition] The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) an active ester curing agent, (C) a polyester polyol resin having an aromatic structure, and (D) an inorganic filler. By using this resin composition, it is possible to obtain a cured product with excellent residue removal, low dielectric tangent, and excellent adhesion.

The resin composition system combines the components (A) to (D), and may further contain arbitrary components. The optional components include, for example, (E) curing agent, (F) thermoplastic resin, (G) curing accelerator, and (H) other additives. Hereinafter, each component contained in the resin composition will be explained in detail.

＜(A) Epoxy resin＞ (A) The epoxy resin includes, for example, bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin. , Dicyclopentadiene 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 , Linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane epoxy resin, cyclohexane Alkylene dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin (A). From the viewpoint of clearly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile content of the epoxy resin (A) is preferably 50 Mass% or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

Epoxy resins are classified into liquid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") at a temperature of 20°C and solid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") at a temperature of 20°C. Solid epoxy resin"). Among them, the resin composition may include only a liquid epoxy resin as the epoxy resin (A), or may include only a solid epoxy resin, and is preferably a combination of a liquid epoxy resin and a solid epoxy resin. As the epoxy resin (A), by using a liquid epoxy resin and a solid epoxy resin in combination, sufficient flexibility can be obtained when used in the form of a resin sheet, or the cured product of the resin composition can be improved Breaking strength.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

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 glycidyl ester type epoxy resin. Glyceryl amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type Epoxy resins and epoxy resins having a butadiene structure are more preferably bisphenol A type epoxy resins and bisphenol F type epoxy resins.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical. , "Epikote828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Oxygen resin); "630" and "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical; "ZX1059" (bisphenol A epoxy resin and bisphenol F A mixture of epoxy resins); "EX-721" (glycidyl ester epoxy resin) made by nagase Chemtex; "CELLOXID2021P" (alicyclic epoxy resin with ester skeleton) made by DAICEL; "PB-3600" (an epoxy resin with a butadiene structure) manufactured by DAICEL; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Epoxy resin) and so on. These can be used in one type alone or in combination of two or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in a molecule, and more preferably an aromatic solid ring having 3 or more epoxy groups in a molecule Oxy resin.

Solid epoxy resin, preferably bis-xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin , Triphenol 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, bisphenol AF type epoxy resin Resin, tetraphenylethane type epoxy resin, more preferably naphthol type epoxy resin and biphenyl type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC ; "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolak epoxy resin) made by DIC; "HP-7200" made by DIC (Dicyclopentadiene epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", manufactured by DIC Corporation "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Corporation; "NC7000L" manufactured by Nippon Kayaku Corporation (Naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co.; "Nippon Steel & Sumikin Chemical Co., Ltd." ESN475V" (naphthol type epoxy resin); "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H", "YX4000", "YL6121" manufactured by Mitsubishi Chemical Company ( Biphenyl type epoxy resin); "YX4000HK" (bis-xylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; and "YX8800" manufactured by Osaka Gas Chemical Co., Ltd. PG-100", "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical; manufactured by Mitsubishi Chemical "JER1010" (solid bisphenol A type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical, etc. These can be used in one type alone or in combination of two or more types.

As (A) the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio of their amounts (liquid epoxy resin: solid epoxy resin) by mass ratio is preferably 1: 0.1~1:20, more preferably 1:1~1:10, particularly preferably 1:1.5~1:5. When the ratio of the liquid epoxy resin to the solid epoxy resin is in this range, the desired effect of the present invention can be clearly obtained. In addition, when it is generally used in the form of a resin sheet, moderate adhesiveness can be obtained. In addition, when it is generally used in the form of a resin sheet, sufficient flexibility can be obtained, and the operability can be improved. In addition, a hardened product having sufficient breaking strength can usually be obtained.

(A) The epoxy equivalent of epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., still more preferably 80g/eq.~2000g/eq. , More preferably 110g/eq.~1000g/eq. Within this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is from the viewpoint that the desired effect of the present invention is clearly obtained, and it is preferably 100 to 5000, more preferably 100 to 4000, and even more preferably 200 to 5000. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC) method in terms of polystyrene.

(A) The content of epoxy resin, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, when the non-volatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, and more It is preferably 5 mass% or more, and more preferably 10 mass% or more. The upper limit of the content of the epoxy resin is, from the viewpoint that the desired effect of the present invention is clearly obtained, it is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. In addition, in the present invention, when the content of each component in the resin composition is not specifically stated, it is a value when the non-volatile component in the resin composition is set to 100% by mass.

＜(B) Active ester hardener＞ The resin composition contains (B) an active ester curing agent. When an active ester-based hardener is used, the dielectric tangent can generally be lowered, the adhesion is excellent, and the residue removal performance is poor. However, when the resin composition of the present invention contains the component (C) in combination, the dielectric tangent can be reduced, and the adhesiveness is excellent, and at the same time, a cured product having excellent residue removal properties can be obtained. (B) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) Active ester hardeners, generally preferably phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc., which have two or more reactions in one molecule Highly active ester-based compound. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable . Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Phenol compounds or naphthol compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol Phenol 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 phenolic aldehyde Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, the component (B) is preferably a dicyclopentadiene-type active ester hardener, a naphthalene-type active ester hardener containing a naphthalene structure, and an active ester hardener containing an acetate of phenol novolak , The active ester hardener containing the benzoate of phenol novolac, more preferably at least one selected from the group consisting of dicyclopentadiene active ester hardener and naphthalene active ester hardener, and More preferably, it is a dicyclopentadiene-type active ester hardener. The dicyclopentadiene-type active ester-based curing agent is preferably an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure. The "dicyclopentadiene-type diphenol structure" means a bivalent structural unit composed of phenylene-dicyclopentyl-phenylene.

(B) Commercially available active ester hardeners, active ester hardeners containing dicyclopentadiene-type diphenol structure, including "EXB9451" (manufactured by DIC Corporation, active ester group equivalent 223), "EXB9460" (Manufactured by DIC, active ester equivalent of 223), "EXB9460S" (manufactured by DIC, active ester equivalent of 223), "HPC-8000-65T" (manufactured by DIC, active ester equivalent of 223), "HPC-8000H -65TM" (manufactured by DIC, active ester equivalent of 224), "HPC-8000L-65TM" (manufactured by DIC, active ester equivalent of 220), active ester hardeners containing naphthalene structure, including "EXB-8100L -65T" (manufactured by DIC, active ester equivalent of 234), "EXB8150-60T" (manufactured by DIC, active ester equivalent of 226), "EXB9416-70BK" (manufactured by DIC, active ester equivalent of 274), " PC1300-02" (manufactured by AIR WATER, active ester equivalent of 200), phosphorus-containing active ester hardeners, including "EXB9401" (manufactured by DIC, active ester equivalent of 307), phenol novolac acetate Examples of active ester hardeners include "DC808" (manufactured by Mitsubishi Chemical, active ester equivalent of 149), active ester hardeners for benzoic phenolic novolacs, including "YLH1026" (manufactured by Mitsubishi Chemical) ), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

(B) The active ester group equivalent of the active ester curing agent can reduce the dielectric tangent and obtain a cured product with excellent adhesion, preferably 50g/eq.~500g/eq., more preferably 50g /eq.~400g/eq., and more preferably 100g/eq.~300g/eq. The active ester group equivalent is the mass of the active ester hardener containing 1 equivalent of active ester group.

The ratio of the amount of (A) epoxy resin to (B) active ester hardener is expressed by the ratio of [total number of epoxy groups of epoxy resin]: [total number of active groups of active ester hardener], It is preferably in the range of 1:0.01 to 1:5, more preferably in the range of 1:0.3 to 1:3, and still more preferably in the range of 1:0.5 to 1:2. Here, "the number of epoxy groups of the epoxy resin" refers to the total value of all the values obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "active base number of the active ester curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the active ester curing agent present in the resin composition by the equivalent of the active ester group. By setting the ratio of the amount of the epoxy resin to the active ester hardener within this range, the effect of the present invention can be remarkably obtained.

(B) The content of the active ester hardener is when the non-volatile component in the resin composition is 100% by mass, preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass above. Moreover, the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. By setting the content of the (B) component within this range, the dielectric tangent can be reduced, and a cured product with excellent adhesion can be obtained.

＜(C) Polyester polyol resin with aromatic structure＞ The resin composition contains (C) a polyester polyol resin having an aromatic structure as the component (C). The resin composition of the present invention contains the component (B) and the component (C) in combination, can reduce the dielectric tangent, has excellent adhesion, and can obtain a cured product having excellent residue removal properties.

The component (C) is preferably a resin having a structure derived from a polyester and a structure derived from a polyol from the viewpoint of improving the adhesion to the conductor layer of copper foil and the like, and further improving the hydrolyzability. This resin can be obtained by reacting polyol and polycarboxylic acid, for example. (C) A component may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, as the component (C), one of the structure derived from polyester and the structure derived from polyol is preferable, and the one having an aromatic structure has the viewpoint that the effect of the present invention is significantly obtained, and the structure derived from polyester and the structure derived from polyol are more preferable. One of the structures of the polyhydric alcohol is one having a bisphenol skeleton, and more preferably the structure derived from the polyhydric alcohol having a bisphenol skeleton. Aromatic structure is generally defined as an aromatic chemical structure, which also includes polycyclic aromatics and aromatic heterocycles. Examples of the bisphenol skeleton include a bisphenol A skeleton, a bisphenol B skeleton, a bisphenol C skeleton, and a bisphenol AF skeleton. The bisphenol A skeleton is preferred.

From the viewpoint of improving the compatibility with the epoxy resin (A) and the adhesion to copper foil, etc. of the component (C), it is preferable that the component (C) has a hydroxyl group at the end of the molecular chain. (C) The number of hydroxyl groups contained in the component is preferably 2 or more in 1 molecule, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, and particularly preferably 2.

Examples of polyhydric alcohols include aliphatics such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butanediol. Polyols; polyols with alicyclic structures such as cyclohexanedimethanol; polyols with aromatic structures such as bisphenol skeletons such as bisphenol A and bisphenol F; the aforementioned polyols with aromatic structure The polyols modified with alkylene oxide (alkylene oxide) and so on. Among them, as the polyol, a polyol having an alicyclic structure, a polyol having an aromatic structure, or a polyol having an aromatic structure modified with alkylene oxide is preferred, and it is more preferred to have Polyols in which aromatic structure polyols are modified with alkylene oxide. A polyol may be used individually by 1 type, and may be used in combination of 2 or more types.

The alkylene oxide used for the modification of the polyol having an aromatic structure includes, for example, alkylene oxide having 2 or more carbon atoms such as ethylene oxide and propylene oxide. The upper limit of the number of carbon atoms of the alkylene oxide having 2 or more carbon atoms is preferably 4 or less, and more preferably 3 or less.

The number average molecular weight of the polyol is preferably 50 or more, preferably 1500 or less, more preferably 1000 or less, and still more preferably 700 or less.

Commercially available polyols can be used. Examples of commercially available products include "Hyprox MDB-561" manufactured by DIC Corporation.

Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and tetradecanedioic acid; terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid And other aromatic polycarboxylic acids; their anhydrides or esters, etc.

The polycarboxylic acid may be used singly or in combination of two or more types. As the polycarboxylic acid, an aliphatic polycarboxylic acid is preferably contained. The content of the aliphatic polycarboxylic acid is based on the total content of the polycarboxylic acid, and is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 100 mol% or less.

A preferred embodiment is to use an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid in combination as the polycarboxylic acid. The content ratio of aromatic polycarboxylic acid and aliphatic polycarboxylic acid (aromatic polycarboxylic acid/aliphatic polycarboxylic acid) is based on molar basis, preferably 1/99 or more, more preferably 30/70 or more, and It is more preferably 50/50 or more, preferably 99/1 or less, more preferably 90/10 or less, and still more preferably 85/15 or less. By setting the content ratio of the aromatic polycarboxylic acid and the aliphatic polycarboxylic acid within this range, the effect of the present invention can be remarkably obtained.

The component (C) may contain an oxyalkylene unit (oxyalkylene unit) having 4 or more carbon atoms to the extent that it does not hinder the purpose of the present invention. The content of alkylene oxide units having 4 or more carbon atoms is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The component (C) can be produced by reacting a polyhydric alcohol with a polycarboxylic acid, for example. The reaction temperature is preferably 190°C or higher, more preferably 200°C or higher, preferably 250°C or lower, and more preferably 240°C or lower. In addition, the reaction time is preferably 1 hour or more, and more preferably 100 hours or less.

During the reaction, a catalyst can be used if necessary. As the catalyst, for example, titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; organic sulfonic acid-based catalysts such as p-toluenesulfonic acid Media etc. One type of catalyst may be used alone, or two or more types may be used in combination.

The content of the catalyst is based on the viewpoint of efficient reaction. It is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and more preferably 0.01 parts by mass relative to the total of 100 parts by mass of polyol and polycarboxylic acid. Hereinafter, it is more preferably 0.005 parts by mass or less.

(C) The hydroxyl value of the component, from the viewpoint of remarkably obtaining the effect of the present invention, is preferably 2 mgKOH/g or more, more preferably 4 mgKOH/g or more, and still more preferably 6 mgKOH/g or more, 10 mgKOH/g or more, 25 mgKOH/g Above, 30 mgKOH/g or more, or 35 mgKOH/g or more, preferably 450 mgKOH/g or less, more preferably 100 mgKOH/g or less, and still more preferably 50 mgKOH/g or less, 45 mgKOH/g or less, or 40 mgKOH/g or less.

(C) The viscosity of the component at 75°C, from the viewpoint of remarkably obtaining the effect of the present invention, is preferably 0.5 Pa･s or more, more preferably 1 Pa･s or more, and still more preferably 2 Pa･s or more, 5 Pa･s or more , Or 10Pa･s or more, preferably 25Pa･s or less, more preferably 20Pa･s or less, and still more preferably 15Pa･s or less. The viscosity can be measured using, for example, an E-type viscometer.

(C) The number average molecular weight of the component, from the viewpoint of improving compatibility with (A) epoxy resin and adhesion to copper foil, etc., is preferably 500 or more, more preferably 1000 or more, and still more preferably 1500 Above, above 2000, or above 2500, preferably below 7000, more preferably below 6000, and still more preferably below 5000. The number average molecular weight is a value calculated from the hydroxyl value.

(C) The glass transition temperature of the component, from the viewpoint of remarkably obtaining the effect of the present invention, is preferably -100°C or higher, more preferably -80°C or higher, still more preferably -70°C or higher, and preferably 50°C or lower, It is more preferably 40°C or less, and still more preferably 30°C or less. The glass transition temperature is a value measured by DSC (differential scanning calorimetry).

(C) The content of the component, from the viewpoint of remarkably obtaining the effect of the present invention, when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more It is preferably 1% by mass or more, more preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less, or 1.5% by mass or less.

When the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is b1, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is c1. , B1/c1 is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting b1/c1 in this range, the dielectric tangent can be lowered, the adhesion is excellent, and a cured product with excellent residue removal properties can be obtained.

＜(D) Inorganic fillers＞ The resin composition contains (D) an inorganic filler. By including the (D) inorganic filler in the resin composition, the dielectric tangent can be reduced, the adhesion is excellent, and a cured product with excellent residue removal properties can be obtained.

The material of the inorganic filler is an inorganic compound. Examples of materials for inorganic fillers include silica, alumina, glass, vilanite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, hydrogen Alumina, magnesium hydroxide, calcium carbonate, magnesium 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, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc. Among these, silicon dioxide is particularly preferred. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, the silica is preferably spherical silica. (D) One type of inorganic filler may be used alone, or two or more types may be used in combination.

(D) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co.; "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS; and "SP507-05" manufactured by Admatechs "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" made by Denka; "SilFileNSS-3N", "SilFileNSS-4N", "SilFileNSS-5N" made by Tokuyama ; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by admatechs; etc.

(D) The average particle size of the inorganic filler, from the viewpoint of clearly obtaining the desired effect of the present invention, is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, and more It is preferably 2 μm or less, and more preferably 1 μm or less.

(D) The average particle size of inorganic fillers can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device is used to prepare the particle size distribution of the inorganic filler on a volume basis, and the median particle size can be measured from the average particle size. The measurement sample can be measured by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a small glass bottle, and dispersing by ultrasonic for 10 minutes. Use a laser diffraction particle size distribution measuring device for the sample to be measured. Use the blue and red wavelengths of the light source to measure (D) the volume-based particle size distribution of the inorganic filler by the flow battery method, and the resulting particle size distribution Using the median particle size, the average particle size was calculated. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd. and the like.

(D) The specific surface area of the inorganic filler, from the viewpoint of clearly obtaining the desired effect of the present invention, is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly ^{preferably 3 m 2} /g or more. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is calculated based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH), adsorbing nitrogen on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Surface treatment agents include, for example, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organosilazane compounds , Titanate coupling agent, etc. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Commercial products of surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (Long-chain epoxy-based silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

Depending on the degree of surface treatment of the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, it is better to store it in a specific range. Specifically, 100 parts by mass of the inorganic filler is preferably surface treated with a surface treatment agent of 0.2 parts by mass to 5 parts by mass, more preferably 0.2 parts by mass to 3 parts by mass for surface treatment, and still more preferably 0.3 parts by mass Part~2 parts by mass for surface treatment.

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 suppressing the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 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 after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the 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, using a carbon analyzer, the amount of carbon per unit surface area of the inorganic filler can be measured. For the carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

In terms of the content of the inorganic filler, the effect of the present invention is significantly obtained. When the non-volatile content in the resin composition is 100% by mass, it is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably It is 70% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.

＜(E) Hardener＞ In addition to the above-mentioned components, the resin composition may contain (E) a hardener as an optional component. (B) Active ester hardener is not included in (E) hardener. (E) Hardeners include, for example, phenol hardeners, naphthol hardeners, benzoxazine hardeners, cyanate ester hardeners, and carbodiimide hardeners. Among them, from the viewpoint of improving insulation reliability, (E) the hardener is preferably any one or more of a phenol-based hardener, a naphthol-based hardener, a cyanate ester-based hardener, and a carbodiimide-based hardener, More preferably, it is any one of a phenol-based hardener and a naphthol-based hardener, and more preferably contains a phenol-based hardener. (E) The curing agent may be used singly or in combination of two or more kinds.

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. Furthermore, 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.

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018-50P", "EXB-9500", etc. manufactured by DIC.

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo 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 resin, phenol novolak, cresol novolac, etc. derived polyfunctional cyanate resin, part of these cyanate ester resins are triazine-treated prepolymers, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan, and "ULL-950S" (polyfunctional cyanate resin) , "BA230", "BA230S75" (part or all of bisphenol A dicyanate is triazine prepolymer), etc.

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

When containing the hardener as component (E), the ratio of the amount of epoxy resin to (B) active ester hardener and (E) hardener is based on [total number of epoxy groups of epoxy resin]: [(B ) The ratio of the active ester hardener and (E) the total number of active groups of the hardener] is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and more preferably 1:0.5~1:2. Here, "the number of epoxy groups of the epoxy resin" refers to the total value of all the values obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active bases of (B) active ester hardener and (E) hardener" refers to the mass of the active ester hardener and the non-volatile components of the hardener present in the resin composition divided by the active group equivalent The total value of all the obtained values. The effect of the present invention can be remarkably obtained by setting the ratio of (B) component and (E) component to epoxy resin within this range.

When containing the hardener as component (E), the ratio of the amount of epoxy resin to all (E) hardeners is based on [total number of epoxy groups of epoxy resin]: [(E) active base of hardener The ratio of the total number] is preferably in the range of 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and still more preferably 1:0.05 to 1:0.1. Here, "the number of active groups of (E) hardener" refers to the total value of all the values obtained by dividing the mass of the non-volatile components of (E) hardener existing in the resin composition by the equivalent of active groups. When the ratio of the amount of the epoxy resin and the hardener as the component (E) is within this range, the effect of the present invention can be remarkably obtained.

(E) The content of the hardener, from the viewpoint of clearly obtaining the desired effect of the present invention, when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, and more preferably 0.2% by mass Above, it is more preferably 0.3% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

When the non-volatile content in the resin composition is set to 100% by mass, the content of component (B) is b1, and when the non-volatile content in the resin composition is set to 100% by mass, the content of component (C) is c1. When the content of (E) component is e1 when the non-volatile component in the resin composition is 100% by mass, b1/(c1+e1) is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting b1/(c1+e1) within this range, a cured product can be obtained that can reduce the dielectric tangent and is excellent in residue removal and adhesion.

＜(F) Thermoplastic resin＞ In addition to the above-mentioned components, the resin composition may contain (F) thermoplastic resin as an optional component.

As the thermoplastic resin of the component (F), for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide resin, poly Ether imine resin, polyether resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. Among them, from the viewpoint of clearly obtaining the desired effect of the present invention, a phenoxy resin is preferred. In addition, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

The phenoxy resin includes, for example, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a sulphur skeleton, and a dicyclopentadiene skeleton. , Norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton constituted by more than one type of phenoxy resin. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical (both are phenoxy resins containing bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical (containing bisphenol S) Frame phenoxy resin); "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Company; Mitsubishi Chemical Company "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" 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 "Denka Butyral4000-2", "Denka Butyral5000-A", "Denka Butyral6000-C", and "Denka Butyral6000-EP" manufactured by Denka Chemical Industry Co., Ltd.; Sekisui Chemical Industry Co., Ltd. Company-made S-Lec BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series; etc.

Specific examples of polyimide resins include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimide described in JP 2006-37083 A). Modified polyimides such as polyimides containing polysiloxane skeletons (polyimides described in Japanese Unexamined Patent Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386), etc. amine.

Specific examples of polyimide resins include "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyimide resins include modified polyimide imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyimide imide) manufactured by Hitachi Chemical Co., Ltd. .

Specific examples of polyether sulfite resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

Specific examples of the polyphenylene ether resin include oligophenylene ether and styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Corporation.

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

(F) The weight average molecular weight (Mw) of the thermoplastic resin, from the viewpoint of clearly obtaining the desired effect of the present invention, is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 or less, more preferably It is less than 60,000, particularly preferably less than 50,000.

(F) The content of the thermoplastic resin, from the viewpoint of clearly obtaining the desired effect of the present invention, when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more , And more preferably 0.3% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

＜(G) Hardening accelerator＞ In addition to the above-mentioned components, the resin composition may further contain (G) a hardening accelerator as an optional component.

Examples of the hardening accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, and the like. Among them, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a metal-based hardening accelerator are preferable, and an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a metal-based hardening accelerator are more preferable. One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Phosphorus-based hardening accelerators include, for example, triphenyl phosphine, phosphonium borate compounds, 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,-tri( Dimethylaminomethyl)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-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Imidazolium 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'-methylimidazole -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotriazine Polycyanic acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Imidazole compounds such as imidazoline and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, commercially available products can 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 dicyanide Amine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal 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 organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(G) The content of the hardening accelerator, from the viewpoint of clearly obtaining the desired effect of the present invention, when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.03% by mass Above, it is more preferably 0.05% by mass or more, more preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less.

＜(H) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Such additives include, for example, organic fillers; resin additives such as tackifiers, defoamers, flattening agents, and adhesion imparting agents; and the like. These additives can be used alone or in combination of two or more types.

＜Physical properties and uses of resin composition＞ The cured product obtained by thermally curing the resin composition at 100°C for 30 minutes and then at 170°C for 30 minutes exhibits excellent residue removal properties. Therefore, when the aforementioned hardened material forms a via hole, an insulating layer whose maximum residue length at the bottom of the via hole is less than 5 μm is formed. The residue removability can be measured by the method described in the below-mentioned examples.

The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits low dielectric tangent characteristics. Therefore, the aforementioned hardened product forms an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.013 or less, more preferably 0.011 or less, and 0.009 or less. In addition, the lower limit of the dielectric tangent is not particularly limited, and may be 0.001 or more. The evaluation of the aforementioned dielectric tangent can be measured in accordance with the method described in the following examples.

The resin composition is heat-cured at 100°C for 30 minutes, at 170°C for 30 minutes, and then at 200°C for 90 minutes. The cured product exhibits excellent adhesion (peel strength) to the copper foil. Therefore, the aforementioned cured product forms an insulating layer excellent in adhesion to the copper foil. The adhesion to copper foil is preferably 0.5 kgf/cm or more, more preferably 0.6 kgf/cm or more, and still more preferably 0.7 kgf/cm or more. In addition, the upper limit of the adhesion is not particularly limited, and may be 5 kgf/cm or less. The evaluation of the aforementioned adhesion can be measured in accordance with the method described in the following Examples.

The resin composition of the present invention can form an insulating layer that can reduce the dielectric tangent, is excellent in adhesion, and is also excellent in residue removal. Therefore, the resin composition of the present invention is suitable for use as a resin composition for insulation purposes. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductive layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer.

In addition, in the multilayer printed wiring board described later, it is suitable as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and a resin for forming an interlayer insulating layer of a printed wiring board The composition (resin composition for forming the interlayer insulating layer of a printed wiring board) is used.

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is suitable as a resin composition for a rewiring forming layer (rewiring layer) for forming an insulating layer for a rewiring layer. Used as a resin composition for forming a formation layer and a resin composition for encapsulating semiconductor chips (resin composition for encapsulating semiconductor chips). When semiconductor chip packaging is manufactured, a rewiring layer can be formed on the sealing layer. (1) The step of laminating the temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) A step of forming a rewiring forming layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film are peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer.

In addition, the resin composition of the present invention can form an insulating layer with good parts embedding properties, so it is also suitable for use when a printed wiring board is a circuit board with a built-in part.

[Resin Sheet] The resin sheet of the present invention includes a support and a resin composition layer formed on the support and formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint that the thickness of the printed wiring board is reduced, and the cured product of the resin composition is a film, and a cured product with excellent insulation properties can be provided. It is more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be 5 μm or more, 10 μm or more.

As the support body, for example, a film made of a plastic material, a metal foil, and release paper, and a film made of a plastic material, and a metal foil are preferred.

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter referred to as Sometimes referred to as "PEN") and other polyesters; polycarbonate (hereinafter sometimes referred to as "PC"); polymethylmethacrylate (PMMA) and other acrylic polymers; cyclic polyolefins; triacetyl Cellulose (TAC); Polyether Sulfide (PES); Polyetherketone; 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 the support, examples of the metal foil include copper foil, aluminum foil, and the like. Among them, copper foil is preferred. The copper foil can be a foil made of a single metal of copper, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The support body can be subjected to matting treatment, corona treatment, antistatic treatment and other treatments on the surface that is joined with the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined with a resin composition layer can 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. For the support with a release layer, commercially available products can be used. Examples include PET films having a release layer mainly composed of an alkyd resin-based release agent. Examples include "SK-1" and "Lintec". "AL-5", "AL-7"; "lumirror T60" manufactured by Toray Corporation; "Purex" manufactured by Teijin Corporation; "unipeel" manufactured by Unitika Corporation; etc.

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

In one embodiment, the resin sheet may further contain other layers if necessary. Examples of the other layer include a support-based protective film provided on a surface that is not bonded to the support of the resin composition layer (that is, the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. With the laminated protective film, it is possible to suppress adhesion or damage to the surface of the resin composition layer, such as dirt.

For the resin sheet, for example, a resin varnish in which the resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied using a die coater or the like, coated on a support, and dried to form a resin composition layer to produce a resin sheet.

Organic solvents include, for example, 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 alcohol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone and other amide-based solvents. 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. The drying conditions are not particularly limited, but the content of the organic solvent in the resin composition layer is dried until the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. It also varies with the boiling point of the organic solvent in the resin varnish. For example, when a resin varnish containing 30% to 60% by mass of organic solvent is used, it can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes. Resin composition layer.

The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

The printed wiring board is manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet, for example. (I) The step of bonding the resin composition layer of the resin sheet to the inner substrate to be laminated on the inner substrate (II) The step of thermally curing the resin composition layer to form an insulating layer

The "inner substrate" used in step (I) is a member that becomes the substrate of the printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting poly Phenyl ether substrates, etc. In addition, the substrate may have a conductive layer on one side or on both sides, and the conductive layer may also be patterned. An inner layer substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and/or a conductor layer is further formed is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner-layer substrate with built-in parts can also be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner layer substrate from the support side. The member for heat-compressing the resin sheet 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 resin sheet, the resin sheet sufficiently follows the surface irregularities of the inner substrate and is preferably pressed through an elastic material such as heat-resistant rubber.

The lamination of the inner substrate and the resin sheet 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~ In the range of 1.47MPa, the heating and crimping time is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. Laminating is preferably carried out under reduced pressure at a pressure of 26.7 hPa or less.

Laminating can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiji Seisakusho, a vacuum coater manufactured by nikko-materials, and a batch vacuum pressurized laminator.

After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heating and pressing member from the support side, the layered resin sheet can also be smoothed. The pressing conditions of the smoothing treatment may be the same conditions as the heating and pressing conditions of the above-mentioned build-up. The smoothing process can be performed by a commercially available laminate machine. In addition, the layering and smoothing treatment can also be performed continuously using the above-mentioned commercially available vacuum layering machine.

The support can be removed between step (I) and step (II), or 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 when forming the insulating layer of the printed wiring board, the commonly used conditions can be used.

For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc. The curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C . The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, 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 is usually heated at a temperature above 50°C and below 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less). Preheat for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of making holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further implemented. These steps (III) to (V) can be implemented in accordance with various methods known to those skilled in the art used in the manufacture of printed wiring boards. In addition, when the support is removed after step (II), the support can be removed between step (II) and step (III), step (III) and step (IV), or step (IV) Implemented between step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer of step (II) to step (V) can be repeated to form a multilayer wiring board.

Step (III) is a step of making holes in the insulating layer. By making holes, 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 wiring board.

Step (IV) is a step of roughening the insulating layer. Usually in this step (IV), the residue is also removed. The order and conditions of the roughening treatment are not particularly limited, and the well-known order and conditions generally used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened in the order of swelling treatment with swelling liquid, roughening treatment with oxidizing agent, and neutralization treatment with neutralization liquid. The swelling liquid used in the roughening treatment is not particularly limited, and an alkali solution, a surfactant solution, etc. can 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, the swelling treatment can be performed by immersing the insulating layer in a 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 preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples 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 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 100°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 alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. In addition, the neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction solution Securiganth P" manufactured by atotech Japan. The treatment with the neutralization solution can be carried out by immersing the 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 the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, but may preferably be 0.5 nm or more, more preferably 1 nm or more. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but may preferably be 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured with a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, forming a conductor layer on the insulating 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. The alloy layer may be formed of, for example, two or more metal alloys selected from the above group (for example, nickel･chromium alloy, copper･nickel alloy, and copper･titanium alloy)的层。 The layer. Among them, from the viewpoints of 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 is preferred. ･Chromium alloy, copper･nickel alloy, copper･titanium alloy alloy layer, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel･chromium alloy layer , And more preferably a single metal layer of copper.

The conductor layer may have a single-layer structure, or may be a multilayer structure in which two or more layers of single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer is 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 nickel-chromium alloy.

The thickness of the conductor layer varies depending on the desired printed wiring board design, and 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, by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method and a full-additive method, a conductor layer with a desired wiring pattern can be formed. From the viewpoint of ease of manufacture, by The semi-additive method is better. The following shows an example of forming the conductor layer by the semi-additive method.

First, on the surface of the insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed electroplating seed layer, a mask pattern corresponding to the desired wiring pattern is formed so that a part of the electroplating seed layer is exposed. After the metal layer is formed by electroplating on the exposed electroplating seed layer, the mask pattern is removed. Then, by removing the unnecessary plating seed 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 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.

Semiconductor devices include electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and various semiconductor devices that provide transportation (for example, motorcycles, automobiles, trams, ships, and airplanes, etc.).

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

The mounting method of the semiconductor wafer during the manufacture of the semiconductor device is not particularly limited as long as the semiconductor wafer can effectively perform its functions. Specifically, it can include wire bonding mounting methods, flip chip mounting methods, and bumpless build-up layers ( BBUL) installation method, anisotropic conductive film (ACF) installation method, non-conductive film (NCF) installation method, 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 wiring board and the semiconductor chip is connected to the wiring on the printed wiring board".

[Example]

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In addition, in the following description, the "parts" and "%" indicating the amount indicate "parts by mass" and "% by mass", unless otherwise specified. In addition, the operations described below indicate that they are performed in an environment of normal temperature and pressure unless otherwise specified.

<Synthesis example 1: Synthesis of polyester polyol resin A with aromatic structure> In the reaction device, 779.1 parts by mass of bisphenol A glycol ether (Hyprox MDB-561, manufactured by DIC Corporation), 132.9 parts by mass of isophthalic acid, and 40.4 parts by mass of sebacic acid were introduced, and the temperature increase and stirring were started. Next, after raising the internal temperature to 230°C, 0.10 parts by mass of tetraisopropyl titanate was added, and the reaction was carried out at 230°C for 24 hours to synthesize a polyester polyol resin A having an aromatic structure. The obtained polyester polyol resin A with aromatic structure has a hydroxyl value of 36.9mgKOH/g, a number average molecular weight of 3040, a glass transition temperature of -14°C, and a viscosity of 9Pa･s at 75°C.

<Synthesis Example 2: Synthesis of Polyester Polyol Resin B> In the reaction device, 395.6 parts by mass of ethylene glycol and 838.8 parts by mass of adipic acid were added, and the temperature increase and stirring were started. Next, after raising the internal temperature to 220° C., 0.03 parts by mass of tetraisopropyl titanate was added, and the reaction was carried out at 220° C. for 24 hours to synthesize polyester polyol resin B. The obtained polyester polyol resin B has a hydroxyl value of 56.2 mgKOH/g, a number average molecular weight of 2000, and a viscosity of 0.6 Pa･s at 75° C. The glass transition temperature is not shown.

<Example 1> Dissolve 20 parts of bisphenol type epoxy resin (“ZX1059” manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) and 40 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.) in MEK (methyl ethyl ketone) 20 share. 330 parts of spherical silica (average particle size 0.77μm, "SO-C2" manufactured by Admatechs) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and active ester-based hardener are added (DIC company "HPC-8000-65T", solid content 60% by mass toluene solution) 90 parts, triazine-containing cresol novolac resin (DIC company "LA-3018-50P", solid content 50% by mass Oxypropanol solution) 5 parts, phenoxy resin (Mitsubishi Chemical "YX7553BH30", 30% by mass solid content MEK･cyclohexanone solution) 5 parts, the polyester polyol resin A obtained in Synthesis Example 1 5 Parts, 0.1 part of 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd., abbreviated as "DMAP"), uniformly dispersed using a high-speed rotary mixer to produce a resin varnish.

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lindek Corporation, thickness 38 μm) provided with a release layer was prepared. The release layer of the support is uniformly coated with the aforementioned resin varnish so that the thickness of the resin composition layer after drying becomes 40 μm. Then, the resin varnish was dried at 80 to 100°C (average 90°C) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

<Example 2> In Example 1, except that 40 parts of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., NC3000L) was changed to 40 parts of naphthol-type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., ESN475V), the active ester system was cured The amount of the agent (manufactured by DIC, HPC-8000-65T) was changed from 90 parts to 85 parts. Except for the above matters, a resin composition 2 was produced in the same manner as in Example 1.

<Example 3> In Example 1, except that 90 parts of an active ester curing agent (manufactured by DIC Corporation, HPC-8000-65T) was changed to 95 parts of an active ester curing agent (manufactured by DIC Corporation, HPC-8150-62T). Except for the above matters, a resin composition 3 was produced in the same manner as in Example 1.

<Example 4> In Example 1, 90 parts of an active ester curing agent (manufactured by DIC Corporation, HPC-8000-65T) was changed to 90 parts of an active ester curing agent (manufactured by DIC Corporation, HPC-8000L-65TM). The resin composition 4 was produced in the same manner as in Example 1 except for the above matters.

<Example 5> In Example 3, in addition to changing the amount of polyester polyol resin A with aromatic structure from 5 parts to 10 parts, the amount of inorganic filler (manufactured by Admatechs, SO-C2) was changed from 330 parts to 340 parts . The resin composition 5 was produced in the same manner as in Example 3 except for the above matters.

<Example 6> In Example 3, except that the amount of the polyester polyol resin A having an aromatic structure was changed from 5 parts to 2.5 parts. The resin composition 6 was produced in the same manner as in Example 3 except for the above matters.

<Example 7> In Example 3, the amount of the active ester hardener (manufactured by DIC Corporation, HPC-8150-62T) was changed from 95 parts to 60 parts, and the amount of inorganic filler (manufactured by Admatechs, SO-C2) was changed from 330 parts Changed to 270 parts, and the amount of polyester polyol resin A was changed from 5 parts to 4 parts. The resin composition 7 was produced in the same manner as in Example 3 except for the above matters.

<Comparative example 1> In Example 1, except for changing 5 parts of polyester polyol resin A with aromatic structure to 5 parts of polyester polyol resin B. The resin composition 8 was produced in the same manner as in Example 1 except for the above matters.

＜Comparative example 2＞ In Example 1, 5 parts of the polyester polyol resin A having an aromatic structure was changed to 5 parts of an epoxy resin (manufactured by DAICEL, PB3600) having a butadiene structure. Except for the above matters, a resin composition 9 was produced in the same manner as in Example 1.

＜Comparative example 3＞ In Example 1, 5 parts of polyester polyol resin A having an aromatic structure were not used. The resin composition 10 was produced in the same manner as in Example 1 except for the above matters.

＜Evaluation of residue removal ability＞ (1) The base treatment of the built-in substrate: As the inner substrate, a glass cloth base epoxy resin with copper foil on the surface is prepared with a copper laminate on both sides (the thickness of the copper foil is 18μm, the thickness of the substrate is 0.8mm, "R1515A" made by Panasonic). The copper foil on the surface of this inner layer substrate was etched with a copper etching amount of 1 μm using a micro-etching agent ("CZ8101" manufactured by MEC Corporation), and roughened. Then, it was dried at 190°C for 30 minutes.

(2) Laminate of resin flakes and hardening: Using a batch-type vacuum pressure laminator (manufactured by nikko-materials, two-stage (2 stage) build-up laminator "CVP700"), the resin flakes obtained in the above examples and comparative examples were used to layer the resin composition with The aforementioned method of bonding the inner layer substrates is laminated on both sides of the inner layer substrate. After reducing the pressure for 30 seconds of this laminated system, the air pressure was set to 13 hPa or less, and the pressure bonding was carried out for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa. Next, the laminated resin sheet was smoothed by hot pressing at 100°C and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. This was put into an oven at 100°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes.

(3) Through hole formation: Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Viamechanics, the insulating layer is processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and a number of shots of 3 Processed to form a via hole with a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 50 μm on the bottom surface of the insulating layer. Then, the support was peeled off to obtain a circuit board.

(4) Roughening treatment: The circuit board was immersed in a swelling liquid Swelling Dip Securiganth P manufactured by atotech Japan at 60°C for 10 minutes. Next, it was immersed in a roughening liquid Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by atotech Japan company at 80°C for 25 minutes. Finally, it was immersed in a neutralization solution, Reduction solution Securiganth P manufactured by atotech Japan, at 40°C for 5 minutes.

(5) Evaluation of residue removal (residue evaluation at the bottom of vias): Observe the periphery of the bottom of the via with a scanning electron microscope (SEM), and determine the maximum residue length from the wall at the bottom of the via from the resulting image, and evaluate it based on the following criteria. ○: The maximum residue length is less than 5μm ×: The maximum residue length is 5μm or more

＜Measurement of Dielectric Tangent＞ The resin sheets obtained in the foregoing Examples and Comparative Examples were cured in an oven at 190°C for 90 minutes, and the support was peeled off to obtain a cured product. The cured 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 a cavity perturbation method using an HP8362B device manufactured by Agilent Technologies (Agilent Technologies). The two test pieces were measured, and the average value was calculated.

＜Measurement of copper foil adhesion (peel strength)＞ (Production of substrate for adhesion evaluation) As the inner substrate, a glass cloth base epoxy resin with copper foil on the surface is prepared with a copper laminate on both sides (the thickness of the copper foil is 18μm, the thickness of the substrate is 0.8mm, "R1515A" made by Panasonic). All the copper foil on the surface of the inner substrate is etched and removed. Then, it was dried at 190°C for 30 minutes.

The resin sheet obtained in the above examples and comparative examples is used in a batch-type vacuum pressure laminator (manufactured by nikko-materials, two-stage build-up laminator "CVP700") to join the resin composition layer to the aforementioned inner substrate , Laminated on both sides of the inner substrate. After reducing the pressure for 30 seconds of this laminated system, the air pressure was set to 13 hPa or less, and the pressure bonding was carried out for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa.

Next, the laminated resin sheet was smoothed by hot pressing at 100°C and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. Then, the support was peeled off, and an "intermediate multilayer body I" including the resin composition layer, the inner substrate, and the resin composition layer in the order was obtained.

In addition, a copper foil having a glossy surface (thickness 35 μm, "3EC-III" manufactured by Mitsui Metals Co., Ltd.) was prepared. The glossy surface of this copper foil was etched with a copper etching amount of 1 μm using a micro-etching agent ("CZ8101" manufactured by MEC Corporation) and roughened. The resulting copper foil is called "roughened copper foil".

This roughened copper foil is laminated on both sides of the intermediate multilayer body I by joining the roughened surface of the roughened copper foil and the resin composition layer of the intermediate multilayer body I. This lamination is carried out under the same conditions as the lamination of the resin sheet of the aforementioned inner substrate. Thereby, an "intermediate composite II" including the roughened copper foil, the resin composition layer, the inner substrate, the resin composition layer, and the roughened copper foil in this order is obtained.

This intermediate multilayer body II was put into an oven at 100°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes. Next, after taking out the intermediate multilayer body II from the oven in a room temperature environment, it was put into an oven at 200° C. and heated for an additional 90 minutes. Thereby, thermal curing of the resin composition layer is performed, and an insulating layer that is a cured product of the resin composition layer, an inner substrate, an insulating layer that is a cured product of the resin composition layer, and a roughened copper foil are obtained in this order. "Evaluation substrate A" of chemical copper foil. In this evaluation substrate A, the roughened copper foil corresponds to the conductor layer.

(Measurement of copper foil adhesion (peel strength)) Using the aforementioned evaluation substrate A, the peel strength between the roughened copper foil and the insulating layer was measured. The measurement of the peel strength is performed in accordance with JIS C6481. Specifically, the peel strength was measured by the following operation.

On the roughened copper foil of the evaluation substrate A, a rectangular part with a width of 10 mm and a length of 100 mm was cut. One end of this rectangular part was peeled off and grasped with a gripper (Autocom type testing machine "AC-50C-SL", manufactured by T.S.E). The 35 mm length of the rectangular portion was peeled in the vertical direction, and the load (kgf/cm) at the time of peeling was measured as the peel strength. The aforementioned peeling was performed at a speed of 50 mm/min at room temperature.

In Examples 1 to 7, even if the components (E) to (G) are not included, there are differences in degree, but it is confirmed that they are summarized in the same results as the above-mentioned examples.

Claims (18)

A resin composition, which contains (A) Epoxy resin, (B) Active ester hardener, (C) Polyester polyol resin with aromatic structure, and (D) Inorganic filler. For the resin composition of claim 1, in which the non-volatile content in the resin composition is set to 100% by mass, the content of component (C) is 0.1% by mass to 10% by mass. The resin composition of claim 1, wherein the component (C) has a bisphenol skeleton. The resin composition of claim 3, wherein the component (C) has a hydroxyl group at the terminal. The resin composition of claim 1, wherein the hydroxyl value of component (C) is 2 mgKOH/g or more and 450 mgKOH/g or less. Such as the resin composition of claim 1, wherein the viscosity of component (C) at 75°C is 0.5Pa･s or more and 25Pa･s or less. The resin composition of claim 1, wherein the number average molecular weight of component (C) is 500 or more and 7000 or less. The resin composition of claim 1, wherein the component (B) contains at least one selected from the group consisting of a dicyclopentadiene-type active ester-based curing agent and a naphthalene-type active ester-based curing agent. Such as the resin composition of claim 1, wherein the content of component (B) when the non-volatile content in the resin composition is set to 100% by mass is b1, and when the non-volatile content in the resin composition is set to 100% by mass ( C) When the content of the component is c1, b1/c1 is 3 or more and 30 or less. For the resin composition of claim 1, in which the non-volatile content in the resin composition is set to 100% by mass, the content of the component (D) is 50% by mass or more. Such as the resin composition of claim 1, which further contains (E) a hardener. The resin composition of claim 11, wherein (E) the hardener contains a phenolic hardener. Such as the resin composition of claim 1, which is used for insulation purposes. The resin composition of claim 1, which is used for forming an insulating layer. Such as the resin composition of claim 1, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising: a support body, and a resin composition layer containing the resin composition according to any one of claims 1 to 15 provided on the support body. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor device including the printed wiring board as claimed in claim 17.