JP7435695B2 - Resin compositions, sheet-like laminated materials, printed wiring boards and semiconductor devices - Google Patents

Description

The present invention relates to a resin composition. Furthermore, the present invention relates to sheet-like laminated materials, printed wiring boards, and semiconductor devices.

As a manufacturing technique for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed from a cured product of a resin composition.

For example, Patent Document 1 describes (A) a phosphonate compound having one or more ethylenically unsaturated bonds in the molecule; (B) a phosphonate compound having two or more ethylenically unsaturated bonds and one or more aromatic compounds in the molecule; A resin composition is disclosed, which contains a radically polymerizable compound having a hydrocarbon or an alicyclic hydrocarbon, and (C) an inorganic filler, and in which the (A) component and the (B) component are different compounds.

Furthermore, Patent Document 2 discloses a resin composition characterized by containing (A) a radically polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. .

JP2016-210856A Japanese Patent Application Publication No. 2014-034580

In recent years, there has been an increasing demand for resin compositions that can form an insulating layer with a low dielectric loss tangent. Further, as electronic devices become smaller and more sophisticated, printed wiring boards have multi-layered build-up layers, and there is a demand for finer and higher-density wiring.

In order to achieve further miniaturization and higher density wiring, there is a need for a resin composition that can yield a cured product with a low dielectric loss tangent, excellent smear removability, and excellent adhesion to the conductor layer. It will be done. Regarding adhesion, from the viewpoint of extending life, excellent adhesion is required, especially after high temperature and high humidity environmental testing (HAST). However, at present, all of these requirements have not been fully satisfied.

Therefore, the object of the present invention is to provide a resin composition that can yield a cured product that has a low dielectric loss tangent, excellent smear removability, and excellent adhesion to a conductor layer; a sheet-like laminate containing the resin composition; The object of the present invention is to provide a printed wiring board including an insulating layer made of a cured product formed using the resin composition; and a semiconductor device including the cured product of the resin composition.

As a result of intensive studies on the above-mentioned problems, the present inventors have formulated a combination of (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent in a specific amount. The inventors have discovered that the above-mentioned problems can be achieved by doing so, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent, wherein the (A) component is (A-1) Containing a glycidylamine type epoxy resin, when the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass, and ( A resin composition in which the content of component (A-1) is 3 to 250 parts by mass when the content of component B) is 100 parts by mass.
[2] The resin composition according to [1], wherein the component (A-1) is a difunctional or trifunctional glycidylamine type epoxy resin.
[3] The resin composition according to [1] or [2], wherein the content of component (A-1) is 0.20 to 10 parts by mass when the nonvolatile component in the resin composition is 100 parts by mass. thing.
[4] Component (C) is selected from the group consisting of an active ester curing agent, a phenol curing agent, a carbodiimide curing agent, and a benzoxazine curing agent, in any one of [1] to [3]. The resin composition described.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) is a (meth)acrylic ester.
[6] The resin composition according to any one of [1] to [5], wherein the content of component (A) is 100 to 1000 parts by mass when the content of component (B) is 100 parts by mass. .
[7] The resin composition according to any one of [1] to [6], further comprising (D) an inorganic filler.
[8] The resin composition according to [7], wherein the content of component (D) is 65 parts by mass or more when the nonvolatile component in the resin composition is 100 parts by mass.
[9] The resin composition according to any one of [1] to [8], further comprising (E) a thermoplastic resin.
[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer for forming a conductor layer.
[11] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer of a printed wiring board.
[12] A sheet-like laminate material containing the resin composition according to any one of [1] to [9].
[13] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].
[14] A semiconductor device comprising a cured product of the resin composition according to any one of [1] to [9].

According to the resin composition of the present invention, a cured product having a low dielectric loss tangent, excellent smear removability, and excellent adhesion with a conductor layer; a sheet-like laminate material containing the resin composition; It is possible to obtain a printed wiring board including an insulating layer made of a cured product formed using the resin composition; and a semiconductor device including a cured product of the resin composition.

Hereinafter, the present invention will be explained in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

<Resin composition>
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent, wherein the (A) component is (A-1) Contains a glycidylamine type epoxy resin, and when the content of components (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass parts, and when the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass.

By using such a resin composition, the desired effects of the present invention, such as being able to obtain a cured product with a low dielectric loss tangent, excellent adhesion with the conductor layer, and excellent smear removability, can be obtained. It will be done.

The resin composition of the present invention may further contain arbitrary components in addition to (A) an epoxy resin, (B) a resin having a radically polymerizable unsaturated group, and (C) an epoxy resin curing agent. Examples of the optional components include (D) an inorganic filler, (E) a thermoplastic resin, (F) a curing accelerator, (G) a polymerization initiator, and (H) other additives. Each component contained in the resin composition will be explained in detail below.

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as component (A). Component (A) contains (A-1) a glycidylamine type epoxy resin, and further contains other epoxy resins apart from component (A-1).

When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (A) in the resin composition is preferably 2 parts by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. parts or more, more preferably 5 parts or more, still more preferably 8 parts or more. The upper limit is preferably 60 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

When the content of component (B) is 100 parts by mass, the content of component (A) in the resin composition is preferably 100 parts by mass or more, more preferably from the viewpoint of obtaining a cured product with excellent adhesion. is 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit thereof is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 550 parts by mass or less, from the viewpoint of obtaining a cured product with a low dielectric loss tangent.

<Epoxy resin other than component (A-1)>
Epoxy resins other than component (A-1) (that is, component (A) other than component (A-1)) include, for example, bisphenol-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol novolak. type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin , linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, and tetraphenylethane type epoxy resin. Epoxy resins other than component (A-1) may be used alone or in combination of two or more.

Bisphenol type epoxy resin refers to an epoxy resin having a bisphenol structure, and includes, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin.

A biphenyl type epoxy resin refers to an epoxy resin having a biphenyl structure, and the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, bixylenol type epoxy resins and biphenylaralkyl type epoxy resins are also included in biphenyl type epoxy resins.

As the epoxy resin other than the component (A-1), aromatic epoxy resins are preferred. Here, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule. The aromatic ring includes not only a monocyclic structure such as a benzene ring but also a polycyclic aromatic structure such as a naphthalene ring and an aromatic heterocyclic structure. Among them, from the viewpoint of achieving excellent adhesion in combination with component (A-1) and component (B), epoxy resins other than component (A-1) include bisphenol-type epoxy resin, biphenyl-type epoxy resin, and naphthyl-type epoxy resin. One or more types selected from the group consisting of renether type epoxy resin, naphthalene type tetrafunctional epoxy resin, and naphthol type epoxy resin are preferable, and one or more type selected from the group consisting of bisphenol type epoxy resin and naphthol type epoxy resin is more preferable. More preferably, one or more selected from the group consisting of , bisphenol A type epoxy resin, and naphthol type epoxy resin.

Epoxy resins other than component (A-1) preferably have two or more epoxy groups in one molecule. When the nonvolatile components of the epoxy resin other than the component (A-1) are 100% by mass, the proportion of the epoxy resin other than the component (A-1) having two or more epoxy groups in one molecule is preferably 50%. It is at least 60% by mass, more preferably at least 60% by mass, even more preferably at least 70% by mass.

Generally, epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resins"). be. The resin composition of the present invention may contain a liquid epoxy resin alone, a solid epoxy resin alone, or a liquid epoxy resin and a solid epoxy resin other than the component (A-1). It may be included in combination with a epoxy resin. Among these, the resin composition of the present invention preferably contains a solid epoxy resin alone or a combination of a solid epoxy resin and a liquid epoxy resin as the epoxy resin other than the component (A-1).

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Solid epoxy resins include biphenyl-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, and biphenyl-type epoxy resins. Epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol type epoxy resins, and tetraphenylethane type epoxy resins are preferred, and bixylenol type epoxy resins, biphenylaralkyl type epoxy resins, naphthylene ether type epoxy resins, and naphthalene type epoxy resins are preferred. Tetrafunctional epoxy resins and naphthol-type epoxy resins are more preferred, and naphthol-type epoxy resins are even more preferred.

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 type epoxy resin) manufactured by DIC; “N-695” (cresol novolac type epoxy resin) manufactured by DIC; “HP-7200” (dicyclopentadiene type epoxy resin) manufactured by DIC; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenylaralkyl epoxy resin); “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; “ESN485” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Novolac type epoxy resin); “YX4000H”, “YX4000”, “YL6121” manufactured by Mitsubishi Chemical (biphenyl type epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin); "PG-100", "CG-500" (bisphenol AF type epoxy resin) manufactured by Osaka Gas Chemical Company; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation ; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical ; can be mentioned. These may be used alone or in combination of two or more.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable.

Liquid epoxy resins include bisphenol type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, Epoxy resins having a and butadiene structure are preferred, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins and naphthalene epoxy resins are more preferred, and bisphenol A epoxy resins are particularly preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "Epicote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX (glycidyl ester type epoxy resin); manufactured by Daicel Corporation "Celoxide 2021P" (alicyclic epoxy resin with ester skeleton); "PB-3600" manufactured by Daicel (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (liquid 1, 4-glycidylcyclohexane type epoxy resin); and the like. These may be used alone or in combination of two or more.

When using a combination of liquid epoxy resin and solid epoxy resin as the epoxy resin other than component (A-1), the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1. ~1:15, more preferably 1:0.5~1:10, still more preferably 1:1~1:8, particularly preferably 1:2~1:5. By having the mass ratio of liquid epoxy resin and solid epoxy resin in the above range, i) adequate adhesion is provided when used in the form of a sheet-like laminate material, and ii) form of the sheet-like laminate material. When used in , sufficient flexibility is obtained, handling properties are improved, and iii) an insulating layer having sufficient breaking strength can be obtained.

The epoxy equivalent of the epoxy resin other than component (A-1) is preferably 50 to 5000 g/eq, more preferably 50 to 3000 g/eq, even more preferably 80 to 2000 g/eq, particularly preferably 110 to 1000 g/eq. be. When the epoxy equivalent of the epoxy resin is within the above range, the crosslinking density of the cured product of the resin composition is sufficient, and an insulating layer with small surface roughness can be obtained. Note that the epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy group, and can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. Note that the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

When the nonvolatile component in the resin composition is 100 parts by mass, the content of epoxy resin other than the component (A-1) in the resin composition is determined from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability. , preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, still more preferably 2.5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(A-1) Glycidylamine type epoxy resin>
(A-1) Glycidylamine type epoxy resin refers to an epoxy resin containing at least one glycidylamino group and/or diglycidylamino group. A glycidylamino group contains one epoxy group, and a diglycidylamino group contains two epoxy groups.

(A-1) The glycidylamine type epoxy resin is preferably a difunctional or higher functional glycidylamine type epoxy resin having two or more epoxy groups in one molecule, from the viewpoint of obtaining a cured product with excellent heat resistance. More preferably, it is a bifunctional or trifunctional glycidylamine type epoxy resin having two or three epoxy groups in one molecule. Here, the epoxy group is not limited to those derived from glycidylamino groups and diglycidylamino groups. When the nonvolatile component of the glycidylamine type epoxy resin is 100 parts by mass, the proportion of the difunctional or higher glycidylamine type epoxy resin is preferably 50 parts by mass or more, more preferably 60 parts by mass, from the viewpoint of increasing the heat resistance of the cured product. The amount is at least 70 parts by mass, more preferably at least 70 parts by mass. Component (A-1) may be used alone or in combination of two or more.

(A-1) The glycidylamine type epoxy resin preferably has an aromatic ring in the molecule from the viewpoint of further improving heat resistance and lowering the coefficient of linear thermal expansion. Examples of the aromatic ring include a benzene ring and a naphthalene ring.

Examples of the glycidylamine type epoxy resin (A-1) that are preferable from the viewpoint of significantly obtaining the desired effects of the present invention include those represented by the following formula (a1).

In formula (a1), R ¹¹ each independently represents a glycidyloxy group or an alkyl group. When R ¹¹ is a glycidyloxy group, R ¹¹ is preferably bonded to the para position with respect to the bonding site between the nitrogen atom and the benzene ring. Further, when R ¹¹ is an alkyl group, R ¹¹ is preferably bonded to the ortho position with respect to the bonding site between the nitrogen atom and the benzene ring.

The alkyl group refers to a linear or branched monovalent aliphatic saturated hydrocarbon group. Alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 5 carbon atoms are more preferred. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, and the like.

In formula (a1), R ¹² represents a hydrogen atom or a mono- to trivalent hydrocarbon group. Examples of the hydrocarbon group include monovalent hydrocarbon groups such as an alkyl group and an aryl group, and divalent hydrocarbon groups such as an alkylene group and an arylene group. Among these, when m is 1, from the viewpoint of obtaining the desired effects of the present invention, R ¹² is preferably an alkyl group, and more preferably a methyl group. Further, when m is 2, from the viewpoint of obtaining the desired effects of the present invention, R ¹² is preferably an alkylene group, and more preferably a methylene group.

The aryl group refers to a monovalent aromatic hydrocarbon group. Aryl groups having 6 to 14 carbon atoms are preferred, and aryl groups having 6 to 10 carbon atoms are more preferred. Examples include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl, and the like.

The alkylene group refers to a straight or branched chain divalent aliphatic saturated hydrocarbon group. Alkylene groups having 1 to 10 carbon atoms are preferred, and alkylene groups having 1 to 5 carbon atoms are more preferred. Examples include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group, and the bonding positions thereof are not particularly limited.

The arylene group refers to a divalent aromatic hydrocarbon group. Arylene groups having 6 to 14 carbon atoms are preferred, and arylene groups having 6 to 10 carbon atoms are more preferred. Examples include a phenylene group, a naphthylene group, a biphenylene group, and the bonding positions thereof are not particularly limited.

In formula (a1), n each independently represents an integer of 0 to 4. Among these, n is preferably an integer of 0 to 3, more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

In formula (a1), m represents an integer from 1 to 3. Among these, m is preferably 1 or 2, and more preferably 1.

(A-1) Specific examples of glycidylamine type epoxy resins include Mitsubishi Chemical's "630" (as shown in the formula below), "630LSD", ADEKA's "EP3980S" (as shown in the following formula), " Examples include "EP3950S", "EP3950L", "ELM-100" (as shown in the formula below), "ELM-100H", "ELM-434" (as shown in the formula below), and "ELM-434L" manufactured by Sumitomo Chemical. It will be done. These may be used alone or in combination of two or more.

(A-1) The epoxy equivalent of the glycidylamine type epoxy resin is preferably 50 to 5000 g/eq, more preferably 50 to 3000 g/eq, even more preferably 60 to 2000 g/eq, particularly preferably 70 to 1000 g/eq. be. When the epoxy equivalent of the glycidylamine type epoxy resin is within the above range, the crosslinking density of the cured product of the resin composition is sufficient, and an insulating layer with small surface roughness can be obtained.

(A-1) The weight average molecular weight (Mw) of the glycidylamine type epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500.

When the non-volatile component in the resin composition is 100 parts by mass, the content of component (A-1) in the resin composition is preferably from the viewpoint of improving the smear removability and adhesion of the cured product. The amount is 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, even more preferably 0.25 parts by mass or more. The upper limit thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, from the viewpoint of obtaining a cured product with a particularly low dielectric loss tangent.

When the content of component (A) other than component (A-1) in the resin composition is 100 parts by mass, the content of component (A-1) in the resin composition is based on smear removability and adhesion. From the viewpoint of obtaining a cured product with excellent properties, the amount is 2 parts by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is 250 parts by mass or less, preferably 200 parts by mass or less, and more preferably 100 parts by mass or less, from the viewpoint of obtaining a cured product with a low dielectric loss tangent.

When the content of component (B) in the resin composition is 100 parts by mass, the content of component (A-1) in the resin composition is determined from the viewpoint of obtaining a cured product with excellent smear removability and adhesion. from 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit is 250 parts by mass or less, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less, from the viewpoint of obtaining a cured product with a low dielectric loss tangent. It is.

<(B) Resin having radically polymerizable unsaturated group>
The resin composition of the present invention contains a resin having a radically polymerizable unsaturated group (hereinafter also referred to as "unsaturated resin") as component (B). By containing component (B), it becomes possible to lower the dielectric loss tangent and to obtain a cured product with excellent smear removability.

(B) A cured product of a resin composition containing an unsaturated resin usually contains a molecular structure site formed by reaction of the unsaturated bond sites of the unsaturated resin (B). Thereby, the polarity of the cured product becomes small, and the value of the dielectric loss tangent can be kept low.

Only one radically polymerizable unsaturated group may be contained in one molecule of the unsaturated resin (B), or a plurality of radically polymerizable unsaturated groups may be contained in one molecule. (B) The unsaturated resin preferably has two or more radically polymerizable unsaturated groups per molecule, from the viewpoint of obtaining a cured product with a low dielectric loss tangent and excellent smear removability.

The radically polymerizable unsaturated group is preferably a group having a carbon-carbon double bond. Examples of radically polymerizable unsaturated groups include acryloyl group (-CO-CH=CH ₂ ), methacryloyl group (-CO-C(CH ₃ )=CH ₂ ), and styryl group (-CH=CH-C ₆ H ₅ ), allyl group (-CH ₂ -CH=CH ₂ ), maleimide group (-NC ₄ O ₂ H ₂ ), and the like. Among these, an acryloyl group or a methacryloyl group is preferred. That is, it is preferable that the unsaturated resin is a (meth)acrylic ester. The term "(meth)acrylic ester" includes acrylic esters, methacrylic esters, and combinations thereof.

(B) The unsaturated resin preferably has a cyclic group from the viewpoint of lowering the dielectric loss tangent and obtaining a cured product with excellent smear removability. The cyclic group may be either a non-aromatic cyclic group or an aromatic cyclic group. Among these, non-aromatic cyclic groups are preferred from the viewpoint of significantly obtaining the desired effects of the present invention.

From the viewpoint of significantly obtaining the desired effects of the present invention, the cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, even more preferably a 5-membered ring or more, and preferably a 25-membered ring or less, and more preferably a 25-membered ring or less. Preferably it is a 20-membered ring or less, more preferably a 15-membered ring or less. Further, the cyclic group may have a monocyclic structure or a polycyclic structure.

In the ring in the cyclic group, the ring skeleton may be composed of heteroatoms in addition to carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and the like, with an oxygen atom being preferred. The ring may contain one or more heteroatoms.

Specific examples of the cyclic group include the following divalent groups (i) to (xi). Among these, (x) or (xi) is preferable as the cyclic group.

The cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, Examples include a mercapto group and an oxo group, with an alkyl group being preferred.

An alkoxy group refers to a monovalent group formed by bonding an alkyl group to an oxygen atom. An alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, and the like.

An arylalkyl group refers to a monovalent group formed by replacing any hydrogen atom of an alkyl group with an aryl group. For example, a benzyl group and the like can be mentioned.

The acyl group refers to a group represented by RCO- (where R represents an alkyl group, an aryl group, an arylalkyl group, etc.). Examples include an acetyl group and a benzoyl group.

The radically polymerizable unsaturated group may be bonded directly to the cyclic group or may be bonded to the cyclic group via a divalent linking group. Examples of the divalent linking group include alkylene group, alkenylene group, arylene group, heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) Examples include N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and a combination of two or more of these may be used.

An alkenylene group refers to a straight or branched chain divalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. Alkylene groups having 2 to 10 carbon atoms are preferred, and alkylene groups having 2 to 5 carbon atoms are more preferred. For example, ethenyl, 1-propenyl, 2-propenyl (allyl), 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl , 3-pentenyl, 4-pentenyl and the like.

The heteroarylene group refers to a divalent aromatic heterocyclic group containing a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom in an aromatic ring. A 5- or 6-membered heteroarylene group is preferred. The number of heteroatoms is preferably 1 to 4. Examples include pyridine-2,6-diyl and thiazole-5,4-diyl.

(B) The unsaturated resin is preferably a compound represented by the following formula (1).

(In formula (1), R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, R ² and R ³ each independently represent a divalent linking group, and Ring A represents a cyclic group. .)

R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, preferably an acryloyl group or a methacryloyl group, and more preferably an acryloyl group. R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the above divalent linking group. Ring A represents a cyclic group. Ring A is the same as the above-mentioned cyclic group. Ring A may have a substituent. The substituent is the same as the substituent that the above-mentioned cyclic group may have.

A specific example of the unsaturated resin represented by formula (1) is "A-DOG" manufactured by Shin Nakamura Chemical Co., Ltd. (dioxane acrylic monomer glycol diacrylate, number average molecular weight 326, represented by the following formula (2) compound), "A-DCP" manufactured by Shin Nakamura Chemical Industry Co., Ltd. (tricyclodecane dimethanol diacrylate, number average molecular weight 304, compound represented by the following formula (3)), etc., but is limited to these. It's not a thing.

Specific examples of unsaturated resins other than the unsaturated resin represented by formula (1) include "YL7776" manufactured by Mitsubishi Chemical Corporation (bixylenol diallyl ether resin, number average molecular weight 331, represented by the following formula (4) Compound), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (biphenylmaleimide resin, compound represented by the following formula (5)), etc., but is not limited to these.

In formula (5), n represents 1 to 5.

The number average molecular weight of the unsaturated resin (B) is preferably 100 or more, more preferably 200 or more, and preferably 10,000 or less, more preferably 3,000 or less. When the number average molecular weight of the unsaturated resin (B) is within the above range, volatilization of the resin varnish during drying can be suppressed, and melt viscosity of the resin composition can be suppressed from becoming excessive. The number average molecular weight can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC). To measure the number average molecular weight by the GPC method, for example, "LC-9A/RID-6A" manufactured by Shimadzu Corporation is used as a measuring device, and "Shodex K-800P/K-804L/K-804L" manufactured by Showa Denko Co., Ltd. is used as a column. can be measured at a column temperature of 40°C using chloroform as the mobile phase.

When the resin component in the resin composition is 100 parts by mass, the content of component (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it is 5 parts by mass or more. The upper limit thereof is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less. The "resin component" of the resin composition refers to the nonvolatile components contained in the resin composition excluding (D) the inorganic filler.

When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (B) in the resin composition is determined from the viewpoint of obtaining a resin composition that has excellent smear removability and provides a cured product with a low dielectric loss tangent. , preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, or 7% by mass, from the viewpoint of improving the compatibility of the resin composition and particularly increasing the adhesion after HAST. % or less.

<(C) Epoxy resin curing agent>
The resin composition of the present invention contains (C) an epoxy resin curing agent as the (C) component. (C) The epoxy resin curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples include phenol curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate esters. Examples include curing agents based on curing agents and carbodiimide curing agents. One type of curing agent may be used alone, or two or more types may be used in combination.

The epoxy resin curing agent is preferably a curing agent selected from the group consisting of active ester curing agents, phenol curing agents, carbodiimide curing agents, and benzoxazine curing agents.

From the viewpoint of obtaining a cured product with excellent heat resistance, low dielectric loss tangent, excellent smear removability, and excellent adhesion with the conductor layer, component (C) should contain an active ester curing agent. is preferred. When the total component (C) is 100 parts by mass, the content of the active ester curing agent is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass or more.

As the phenol curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenol curing agent having a novolak structure or a naphthol curing agent having a novolak structure is preferable. Further, from the viewpoint of improving adhesion to the conductor layer, a nitrogen-containing phenol curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenol curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among these, triazine skeleton-containing phenol novolac resins are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer. Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "MEH-7851" manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090" manufactured by DIC Corporation ” etc.

The active ester curing agent is not particularly limited, but generally contains ester groups with high reactivity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac are preferred. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene diphenol structure. ), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolak, and benzoyl phenol novolac. Examples of active ester compounds containing compounds include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Kobunshi Co., Ltd. and "P" manufactured by Shikoku Kasei Kogyo Co., Ltd. -d", "Fa", etc.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4, 4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5- difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; Examples include polyfunctional cyanate resins derived from phenol novolacs and cresol novolaks, and prepolymers in which these cyanate resins are partially triazine-formed. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., and "BA230" (part or all of bisphenol A dicyanate). is triazinated to form a trimer).

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

When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (C) in the resin composition is preferably 5% by mass or more, more preferably Preferably it is 8% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.

The quantitative ratio of (A) epoxy resin and (C) epoxy resin curing agent is the ratio of [total number of epoxy groups in epoxy resin]:[total number of reactive groups in curing agent] from 1:0.2 to The ratio is preferably in the range of 1:2, more preferably 1:0.3 to 1:1.5, even more preferably 1:0.4 to 1:1.2. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, etc., and differs depending on the type of curing agent. In addition, the total number of epoxy groups in an epoxy resin is the sum of the solid mass of each epoxy resin divided by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the curing agent is: This value is the sum of the solid mass of each curing agent divided by the reactive group equivalent for all curing agents. By setting the ratio of the epoxy resin to the curing agent within this range, the heat resistance of the resulting insulating layer is further improved.

<(D) Inorganic filler>
The resin composition of the present invention may further contain an inorganic filler as component (D). By including an inorganic filler, a cured product with a lower coefficient of linear thermal expansion and lower dielectric loss tangent can be realized.

(D) The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium 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 tungstate phosphate, among which silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. One type of inorganic filler may be used alone, or two or more types may be used in combination.

(D) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; “Silfill NSS-3N”, “Silfill NSS-4N”, “Silfill NSS-” manufactured by Tokuyama Examples include "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatex.

The average particle size of the inorganic filler is preferably 4 μm or less, more preferably 3 μm or less, even more preferably 2.5 μm or less, even more preferably 2 μm or less, particularly preferably 1 μm or less, 0.7 μm or less, or 0.5 μm. It is as follows. The lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction particle size distribution measuring device, and using the median diameter as the average particle size. As the measurement sample, one in which an inorganic filler is dispersed in water using ultrasonic waves can be preferably used. As the laser diffraction particle size distribution analyzer, "LA-500", "LA-750", "LA-950", etc. manufactured by Horiba, Ltd. can be used.

Inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, etc. from the viewpoint of improving moisture resistance and dispersibility. Preferably, it is treated with one or more surface treating agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co. "KBM-4803" (long chain epoxy type silane coupling agent) ), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and preferably 0.2 parts by mass to 3 parts by mass. Preferably, the surface treatment is carried out in an amount of 0.3 parts by mass to 2 parts by mass.

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 is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less. preferable.

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 whose surface has been treated with a surface treatment agent, and the mixture is subjected to ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

(D) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 1.5 m 2 /g or more, particularly preferably 2 m ² /g or more, from the viewpoint of further improving the effects of ^the present invention. be. The upper limit is not particularly limited, but is preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler can be measured by the BET method.

When the nonvolatile component in the resin composition is 100 parts by mass, the content of the inorganic filler (D) in the resin composition is preferably 50 parts by mass from the viewpoint of obtaining a cured product with a low linear thermal expansion coefficient and dielectric loss tangent. The content is at least 55% by mass, preferably at least 60% by mass, or at least 65% by mass. The upper limit thereof is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the cured product obtained.

<(E) Thermoplastic resin>
The resin composition of the present invention may further contain (E) a thermoplastic resin as an optional component in addition to the above-mentioned components.

Examples of the thermoplastic resin as component (E) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , polycarbonate resin, polyetheretherketone resin, polyester resin, etc. Among these, phenoxy resin is preferred from the viewpoint of significantly obtaining the desired effects of the present invention and from the viewpoint of obtaining an insulating layer with low surface roughness and particularly excellent adhesion to the conductor layer. Moreover, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. Examples include phenoxy resins having one or more types of skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol S skeleton); "YX6954" (phenoxy resin containing bisphenolacetophenone skeleton) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, Examples include "YL7769BH30," "YL6794," "YL7213," "YL7290," and "YL7482."

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resin include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Denki Kagaku Kogyo; Sekisui Chemical Co., Ltd. Examples include the S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by the company.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nihon Rika Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimide described in JP-A No. 2006-37083), polysiloxane skeletons, etc. Examples include modified polyimides such as polyimides containing polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386, etc.).

Specific examples of the polyamide-imide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical.

A specific example of the polyether sulfone resin includes "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

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

(E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of significantly obtaining the desired effects of the present invention. and is preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

When the nonvolatile component in the resin composition is 100 parts by mass, the content of the thermoplastic resin (E) is preferably 0.1 part by mass or more, more preferably is 0.3 parts by mass or more, more preferably 0.5 parts by mass or more. The upper limit thereof is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less.

<(F) Curing accelerator>
In addition to the components mentioned above, the resin composition may further contain (F) a curing accelerator as an optional component.

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

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole curing accelerator, commercially available products may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Examples of the metal hardening accelerator 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 (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the nonvolatile component in the resin composition is 100 parts by mass, the content of the curing accelerator (F) is preferably 0.001 parts by mass or more, more preferably is 0.01 part by mass or more, more preferably 0.05 part by mass or more. The upper limit thereof is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, still more preferably 0.1 part by mass or less.

<(G) Polymerization initiator>
The resin composition may further contain (G) a polymerization initiator as an optional component in addition to the components described above. (G) The polymerization initiator usually has a function of promoting crosslinking of the radically polymerizable unsaturated group in the component (B). (G) Polymerization initiators may be used alone or in combination of two or more.

Examples of the polymerization initiator (G) include t-butylcumyl peroxide, t-butylperoxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butylperoxylaurate, and t-butylperoxyacetate. Examples include peroxides such as -butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

(G) Commercially available polymerization initiators include, for example, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "Perbutyl ND", and "Perbutyl ND" manufactured by NOF Corporation. ``Perbutyl Z'', ``Percmil P'', ``Percyl D'', etc.

When the nonvolatile components in the resin composition are 100 parts by mass, the content of the polymerization initiator (G) is preferably 0.001 parts by mass or more, more preferably is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.5 parts 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. Examples of such additives include organic fillers; resin additives such as thickeners, antifoaming agents, leveling agents, and adhesion agents; and the like. These additives may be used alone or in combination of two or more. The content of each can be set as appropriate by those skilled in the art.

<Preparation and physical properties of resin composition>
The method for preparing the resin composition of the present invention is not particularly limited, and includes, for example, a method in which the ingredients are mixed and dispersed using a rotary mixer or the like, adding a solvent or the like if necessary.

According to the resin composition of the present invention, a cured product having a low dielectric loss tangent, excellent smear removability, and excellent adhesion to a conductor layer can be obtained. The present inventor conjectures that the mechanism by which such excellent effects are obtained is as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

According to studies by the present inventors, it has been found that by combining (A) epoxy resin with (B) unsaturated resin, the dielectric loss tangent and smear removability of the cured product can be improved. However, since the (A) epoxy resin and the (B) unsaturated resin usually have different polarities, their compatibility is low and they tend to separate at a minute level in the cured product. Therefore, a cured product of a resin composition containing a combination of (A) an epoxy resin and (B) an unsaturated resin generally has a reduced mechanical strength and is more likely to cause delamination when subjected to a high-temperature, high-humidity environmental test. Therefore, conventionally, it has been difficult to obtain a cured product with excellent adhesion to the conductor layer after a high-temperature, high-humidity test.

On the other hand, (A-1) glycidylamine type epoxy resin is compatible with both (A) epoxy resin other than the (A-1) glycidylamine type epoxy resin and (B) unsaturated resin. Excellent in Therefore, by using (A-1) glycidylamine type epoxy resin, separation of (A) epoxy resin other than (A-1) glycidylamine type epoxy resin and (B) unsaturated resin can be suppressed. Decrease in mechanical strength of cured products due to high humidity tests can be suppressed. Furthermore, the glycidylamine type epoxy resin (A-1) has the effect of improving the smear removability and adhesion of the cured product. Therefore, by combining appropriate amounts of (A) epoxy resin other than (A-1) glycidylamine type epoxy resin, (A-1) glycidylamine type epoxy resin, and (B) unsaturated resin, Since delamination can be suppressed without impairing good dielectric loss tangent and smear removability, it is possible to realize a cured product that is excellent in all of dielectric loss tangent, smear removability, and adhesion.

An insulating layer made of a cured product of the resin composition of the present invention exhibits excellent adhesion (peel strength) with a conductor layer such as copper foil. The copper foil adhesion (adhesion strength) before high temperature and high humidity environment test (HAST) is preferably 0.62 kgf/cm or more, more preferably 0.65 kgf/cm or more, and even more preferably 0.70 kgf/cm or more. be. The copper foil adhesion after HAST is preferably 0.25 kgf/cm or more, more preferably 0.30 kgf/cm or more, still more preferably 0.35 kgf/cm or more, particularly preferably 0.40 kgf/cm or more. . On the other hand, the upper limit of adhesion (adhesion strength) is not particularly limited, but may be 5 kgf/cm or less. The copper foil adhesion can be measured according to the method described in Examples below.

The cured product of the resin composition of the present invention exhibits a low dielectric loss tangent. The dielectric loss tangent of the cured product is preferably less than 0.0054, more preferably less than 0.0052, still more preferably less than 0.0050, and even more preferably less than 0.0048. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be evaluated according to the method described in the Examples described later.

Furthermore, the cured product of the resin composition of the present invention exhibits excellent smear removability. The maximum smear length of the cured product is preferably less than 5 μm. "Maximum smear length" means the maximum length of the smear from the circumference of the bottom of the via to the center of the circle. The maximum smear length can be evaluated according to the method described in Examples below.

The resin composition of the present invention can lower the dielectric loss tangent and provide an insulating layer with excellent smear removability and adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, a resin composition for forming an insulating layer (including a rewiring layer) formed on an insulating layer (a resin for forming an insulating layer for forming a conductor layer) is used. composition). Further, in a printed wiring board to be described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in adhesive films, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, component embedding resins, etc. that require resin compositions. Can be used in a wide range of applications.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be used as a rewiring formation layer as an insulating layer for forming a rewiring layer. It can also be suitably used as a resin composition (resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) The step of laminating a temporary fixing film on the base material,
(2) Temporarily fixing the semiconductor chip on the temporary fixing film,
(3) forming a sealing layer on the semiconductor chip;
(4) Peeling the base material and temporary fixing film from the semiconductor chip,
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled; and (6) Forming a rewiring layer as a conductive layer on the rewiring layer. Forming process

Moreover, since the resin composition of the present invention provides an insulating layer with good component embeddability, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be used by applying it in the form of a varnish, it is generally preferable for industrial use to use it in the form of a sheet-like laminate material containing the resin composition.

As the sheet-like laminated material, adhesive films (hereinafter also referred to as "resin sheets") and prepregs shown below are preferable.

In one embodiment, the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is made of the resin composition of the present invention. formed from.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 50 μm or less, from the viewpoint of making the printed wiring board thinner and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. Preferably it is 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

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

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., with copper foil being preferred. As the copper foil, a foil made of a single metal such as copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

The surface of the support to be bonded to the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

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 using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

In one embodiment, the adhesive film may further include an arbitrary layer as necessary. Examples of such an arbitrary layer include a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). It will be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

For the adhesive film, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, and this resin varnish is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured by

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve and butyl carbitol, etc. carbitols; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying may be performed by a known method such as heating or blowing hot air. Although drying conditions are not particularly limited, drying is performed so that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of organic solvent, the resin composition can be adjusted by drying at 50°C to 150°C for 3 to 10 minutes. A material layer can be formed.

The adhesive film can be wound up into a roll and stored. If the adhesive film has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of making the printed wiring board thinner, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

Prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

In the present invention, which uses a resin composition containing a combination of component (A), component (B), and component (C) in a specific content, the resin composition has a high glass transition temperature, a low dielectric loss tangent, and a high resistance to the conductive layer. It is possible to realize a sheet-like laminate material that provides a cured product with good adhesion and is extremely useful in the production of printed wiring boards.

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). It can be suitably used for interlayer insulating layers of wiring boards).

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

A printed wiring board can be manufactured, for example, using the above-mentioned adhesive film by a method including the steps (I) and (II) below.
(I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Forming an insulating layer by curing (e.g., thermosetting) the resin composition layer process of doing

The "inner layer substrate" used in step (I) is a member that becomes a substrate of a printed wiring board, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. Further, the substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one or both sides of the board is sometimes referred to as an "inner layer circuit board." Further, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductive layer is further formed is also included in the "inner layer substrate" as referred to in the present invention. If the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The inner layer substrate and the adhesive film can be laminated, for example, by heat-pressing the adhesive film to the inner layer substrate from the support side. Examples of the member for heat-pressing the adhesive film to the inner layer substrate (hereinafter also referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll). It should be noted that, rather than pressing the thermocompression bonding member directly onto the adhesive film, it is preferable to press it through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the adhesive film may be laminated by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0. The pressure is in the range of .29 MPa to 1.47 MPa, and the heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressure laminator.

After lamination, the laminated adhesive films may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the conditions for the heat-pressing of the lamination described above. The smoothing process can be performed using a commercially available laminator. Note that the lamination and smoothing treatment may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly employed for forming an insulating layer of a printed wiring board may be used.

For example, the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but 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. It is ℃. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even 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, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50°C or higher and lower than 120°C, preferably 60°C or higher and lower than 115°C, more preferably 70°C or higher and lower than 110°C. Preheating may be performed for at least 5 minutes, preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, and even more preferably for 15 minutes to 100 minutes.

When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. Note that when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or during step (IV). IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductive layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

In other embodiments, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when using an adhesive film.

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

Step (IV) is a step of roughening the insulating layer. Usually, smear is also removed in this step (IV). The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used in forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid in this order.

The swelling liquid used in the roughening treatment is not particularly limited, but includes alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. Swelling treatment with a swelling liquid is not particularly limited, but can be carried out, for example, 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 in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, but includes, for example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

Further, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and a commercially available product includes, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

The treatment with the neutralizing liquid can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in the neutralizing liquid at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes.

In one embodiment, the arithmetic mean roughness (Ra) 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 is preferably 0.5 nm or more, more preferably 1 nm or more. Further, 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 is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-chromium alloy, a copper-chromium alloy, etc.). nickel alloys and copper-titanium alloys). Among these, from the viewpoint of versatility in forming conductor layers, cost, ease of patterning, etc., monometallic layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, nickel-chromium alloys, copper, etc. An alloy layer of nickel alloy or copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy is more preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferable. More preferred is a metal layer.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer using a conventionally known technique such as a semi-additive method or a fully additive method. It is preferable to form by a method. An example of forming a conductor layer by a semi-additive method will be shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layers can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

In other embodiments, the conductive layer may be formed using metal foil. When forming a conductor layer using metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by vacuum lamination. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventional known technique such as a subtractive method or a modified semi-additive method.

Metal foil can be manufactured by a known method such as an electrolytic method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd.

When manufacturing a printed wiring board using the resin composition of the present invention containing a combination of component (A), component (B), and component (C) in a specific content, the conductor layer may be formed by plating. Regardless of whether the conductive layer and the insulating layer are formed using metal foil, the adhesion between the conductive layer and the insulating layer can be significantly improved.

<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.

Examples of semiconductor devices include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.), vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.), and the like.

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on conductive parts of a printed wiring board. A "conducting location" is a "location on a printed wiring board that transmits electrical signals," and the location may be on the surface or embedded. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method for semiconductor chips when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chip functions effectively, but specifically, wire bonding mounting method, flip chip mounting method, bumpless buildup layer, etc. Examples include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, "a mounting method using a bumpless buildup layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." It is.

Hereinafter, the present invention will be specifically explained by showing examples. However, the present invention is not limited to the examples shown below. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

First, a measurement and evaluation method for evaluating physical properties in this specification will be explained.

<Preparation of sample for measuring copper foil adhesion>
(1) Surface treatment of copper foil The shiny surface of electrolytic copper foil (“3EC-III” manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness 35 μm) is immersed in a micro-etching agent (“CZ-8101” manufactured by MEC Co., Ltd.). The copper surface was subjected to a roughening treatment (Ra value = 1 μm), and then a rust prevention treatment was performed using a rust prevention solution (“CL8300” manufactured by MEC Co., Ltd.). The obtained copper foil is called CZ copper foil. Furthermore, it was heat-treated in an oven at 130°C for 30 minutes.

(2) Copper foil lamination and insulation layer formation As an inner layer circuit board, a glass cloth base epoxy resin double-sided copper clad laminate with an inner layer circuit formed (copper foil thickness 18 μm, board thickness 0.4 mm, Panasonic Corporation) "R1515A") was prepared. Next, the resin sheets obtained in the following Examples and Comparative Examples were heated using a batch vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) so that the resin composition layer was the same as the inner layer circuit board. It was laminated on both sides of the inner layer circuit board so as to be bonded. Lamination was carried out by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. After lamination, the PET film was peeled off. The treated surface of the CZ copper foil was laminated on the exposed resin composition layer under the same conditions as above. Then, by curing the resin composition layer under curing conditions of 190°C for 90 minutes to form an insulating layer, a sample having the structure of CZ copper foil/insulating layer/inner layer circuit board/insulating layer/CZ copper foil was prepared. Created.

<Measurement of copper foil adhesion (adhesion 1) before high temperature and high humidity environment test (HAST)>
The prepared sample was cut into small pieces of 150 x 30 mm. Use a cutter to cut a 10 mm wide and 100 mm long cut into the copper foil part of the small piece, peel off one end in the length direction of the copper foil, and use a grip (made by TSE Co., Ltd. "AC-50C-"). SL") and peeled off 35 mm in the vertical direction at room temperature using an Instron universal testing machine at a speed of 50 mm/min. The load was measured in accordance with JIS C6481. The load measured in this manner is referred to as "adhesion 1".

<Measurement of copper foil adhesion (adhesion 2) after high temperature and high humidity environment test (HAST)>
The prepared sample was subjected to a high temperature and high humidity environment test for 100 hours at 130° C. and 85% RH using a highly accelerated life test device (“PM422” manufactured by Kusumoto Kasei Co., Ltd.). After that, in the same way as in the measurement of adhesion 1, after making a cut, peel off one end of the copper foil in the length direction and grasp it with a grip ("AC-50C-SL" made by TSE Co., Ltd.), and Using a testing machine, the load when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature was measured in accordance with JIS C6481. The load measured in this manner is referred to as "adhesion 2."

A case where the measurement result for adhesion 2 was less than 0.25 kgf/cm was evaluated as "x", and a case where the measurement result was 0.25 kgf/cm or more was evaluated as "○".

<Measurement of dielectric loss tangent>
After heat-curing the resin sheets obtained in Examples and Comparative Examples at 200° C. for 90 minutes, the PET film was peeled off to prepare samples for evaluation of cured physical properties.

A test piece with a width of 2 mm and a length of 80 mm was cut from the sample for evaluating cured physical properties. Regarding the test piece, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Measurements were performed on two test pieces, and the average value was calculated.

When the average value of dielectric loss tangent was less than 0.0054, it was evaluated as "○", and when it was 0.0054 or more, it was evaluated as "x".

<Evaluation of smear removability and arithmetic mean roughness (Ra)>
(1) Base treatment for interior board As the inner board, glass cloth base epoxy resin double-sided copper-clad laminate with copper foil on the surface (copper foil thickness 18 μm, board thickness 0.8 mm, Panasonic "R1515A" ”) was prepared. The copper foil on the surface of this inner layer substrate was roughened by etching with a copper etching amount of 1 μm using a micro-etching agent (“CZ8101” manufactured by MEC Corporation). Thereafter, drying was performed at 190° C. for 30 minutes.

(2) Lamination and curing of resin sheets The resin sheets obtained in the above-mentioned examples and comparative examples were laminated using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials). Both sides of the inner layer substrate were laminated so that the composition layer was bonded to the inner layer substrate. This lamination was carried out by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds.

Next, the laminated resin sheet was smoothed by hot pressing under atmospheric pressure at 100° C. and a pressure of 0.5 MPa for 60 seconds. Further, this was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes.

(3) Via hole formation Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics, the insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and the number of shots of 3. A via hole was formed with a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 40 μm on the bottom surface of the insulating layer. The top diameter represents the diameter of the opening of the via hole. Furthermore, the PET film was then peeled off.

(4) Roughening treatment The inner layer substrate was immersed in a swelling liquid, Swelling Dip Securigant P manufactured by Atotech Japan, at 60° C. for 10 minutes. Next, it was immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Co., Ltd., which is a roughening liquid, at 80° C. for 20 minutes. Finally, it was immersed in a neutralizing solution, Reduction Solution Securigant P manufactured by Atotech Japan, at 40° C. for 5 minutes. The obtained board was designated as evaluation board A.

<Evaluation of smear removal performance>
The area around the bottom of the via hole of evaluation board A was observed using a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image, and evaluated based on the following criteria.
○: Maximum smear length is less than 5 μm.
×: Maximum smear length is 5 μm or more.

<Example 1>
Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent: 180 g/eq) 5 parts, naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent: 330 g/eq) 15 parts, glycidylamine type epoxy Three parts of a resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq) was dissolved in 30 parts of methyl ethyl ketone (MEK) by heating with stirring, and then cooled to room temperature. To the obtained resin solution, 30 parts of active ester resin ("HPC-8000-65T" manufactured by DIC Corporation, active ester group equivalent: 223 g/eq, toluene solution with non-volatile content 65% by mass) and phenol resin ("LA" manufactured by DIC Corporation) were added. -3018-50P'', phenolic hydroxyl equivalent 151 g/eq, 5 parts of 2-methoxypropanol solution with non-volatile content 50% by mass), acrylic ester (``A-DOG'' manufactured by Shin Nakamura Chemical Co., Ltd., acrylic equivalent 156 g/eq) ), 10 parts of phenoxy resin (YL7553BH30 manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with 30% by mass of non-volatile content), 5 parts of curing accelerator (4-dimethylaminopyridine (DMAP), 5 mass of non-volatile content) % MEK solution), 0.6 parts of dicumyl peroxide ("Percumil D" manufactured by NOF Corporation), and spherical silica surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 120 parts of "SO-C2" manufactured by Admatex (average particle size 0.5 μm) were mixed and dispersed uniformly with a high-speed rotating mixer, and then filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to obtain a resin varnish. 1 was prepared.

Next, a resin varnish was applied onto the release layer of the PET film with an alkyd resin release layer (“AL-5” manufactured by Lintec Corporation, thickness 38 μm) so that the thickness of the resin composition layer after drying was 40 μm. 1 was uniformly applied using a die coater and dried at 80 to 110°C (average 95°C) for 5 minutes to prepare resin sheet 1.

<Example 2>
Resin varnish 2 and resin were prepared in the same manner as in Example 1, except that 5 parts of carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent: 216 g/eq, toluene solution with non-volatile content of 50% by mass) was added. Sheet 2 was produced.

<Example 3>
Resin varnish 3 and resin sheet 3 were produced in the same manner as in Example 1, except that 3 parts of a benzoxazine curing agent ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was added.

<Example 4>
Resin varnish 4 and resin sheet were prepared in the same manner as in Example 1, except that the amount of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq) was changed from 3 parts to 0.5 parts. 4 was produced.

<Example 5>
Bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828US", epoxy equivalent: 180 g/eq) was not blended, and glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent: 95 g/eq) was blended in an amount of 3. Same as Example 1, except that the amount of acrylic acid ester ("A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., acrylic equivalent weight 156 g / eq) was changed from 10 parts to 5 parts. Resin varnish 5 and resin sheet 5 were produced.

<Example 6>
The amount of naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 330 g/eq) was changed from 15 parts to 5 parts, and the amount of active ester resin ("HPC-8000-65T" manufactured by DIC Corporation, active ester) was changed from 15 parts to 5 parts. Resin varnish 6 and resin sheet 6 were produced in the same manner as in Example 5, except that the amount of toluene solution with a base equivalent of 223 g/eq and a nonvolatile content of 65% by mass was changed from 30 parts to 50 parts.

<Example 7>
Instead of 10 parts of acrylic ester ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent weight 156 g/eq), 10 parts of acrylic ester ("A-DCP" manufactured by Kyoeisha Chemical Co., Ltd., acrylic equivalent weight 152 g/eq) Resin varnish 7 and resin sheet 7 were produced in the same manner as in Example 1 except that varnish was used.

<Example 8>
Instead of 3 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent weight 95 g/eq), 3 parts of glycidylamine type epoxy resin ("EP3980S" manufactured by ADEKA Corporation, epoxy equivalent weight 115 g/eq) was used. Resin varnish 8 and resin sheet 8 were produced in the same manner as in Example 1 except for this.

<Example 9>
Instead of 3 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent weight 95 g/eq), 3 parts of glycidylamine type epoxy resin ("ELM-434" manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent weight 98 g/eq) Resin varnish 9 and resin sheet 9 were produced in the same manner as in Example 1, except that varnish was used.

<Example 10>
Instead of 3 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 95 g/eq), 3 parts of glycidylamine type epoxy resin ("ELM-100" manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent weight 105 g/eq) Resin varnish 10 and resin sheet 10 were produced in the same manner as in Example 1, except that .

<Comparative example 1>
Resin varnish 11 and resin sheet 11 were produced in the same manner as in Example 1, except that a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq) was not blended.

<Comparative example 2>
Resin varnish 12 and resin sheet were prepared in the same manner as in Example 1, except that the amount of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq) was changed from 3 parts to 0.1 part. 12 were produced.

<Comparative example 3>
The amount of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g/eq) was changed from 3 parts to 0.5 parts, and the amount of acrylic ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 3 parts to 0.5 parts. , acrylic equivalent: 156 g/eq) was changed from 10 parts to 50 parts, and the amount of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm) was changed from 120 parts to 200 parts. Resin varnish 13 and resin sheet 13 were produced in the same manner as in Example 1, except that the amount of methyl ethyl ketone (MEK) used was changed from 30 parts to 60 parts.

<Comparative example 4>
The amount of bisphenol A type epoxy resin (Mitsubishi Chemical "828US", epoxy equivalent: 180 g/eq) was changed from 5 parts to 15 parts, and the glycidylamine type epoxy resin (Mitsubishi Chemical "630", epoxy equivalent: 95 g) was used. /eq) was changed from 3 parts to 0.1 part, and the amount of acrylic acid ester ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent weight 156 g/eq) was changed from 10 parts to 2 parts. Resin varnish 14 and resin sheet 14 were produced in the same manner as in Example 1 except for the changes.

<Comparative example 5>
The amount of naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 330 g/eq) was changed from 15 parts to 5 parts, and the amount of glycidylamine-type epoxy resin ("630", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g) was changed from 15 parts to 5 parts. /eq) was changed from 3 parts to 30 parts, and the amount of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm) was changed from 120 parts to 150 parts. A resin varnish 15 and a resin sheet 15 were produced in the same manner as in Example 1.

<Comparative example 6>
The amount of bisphenol A type epoxy resin (Mitsubishi Chemical "828US", epoxy equivalent: 180 g/eq) was changed from 5 parts to 15 parts, and the glycidylamine type epoxy resin (Mitsubishi Chemical "630", epoxy equivalent: 95 g) was used. /eq) was changed from 3 parts to 30 parts, and the amount of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm) was changed from 120 parts to 200 parts. A resin varnish 16 and a resin sheet 16 were produced in the same manner as in Example 1.

<Comparative example 7>
The amount of naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 330 g/eq) was changed from 15 parts to 5 parts, and the amount of glycidylamine-type epoxy resin ("630", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g) was changed from 15 parts to 5 parts. /eq) was changed from 3 parts to 30 parts, and the amount of acrylic acid ester ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., acrylic equivalent weight 156 g/eq) was changed from 10 parts to 30 parts. , Resin varnish 17 and resin sheet 17 were prepared in the same manner as in Example 1, except that the amount of spherical silica (“SO-C2” manufactured by Admatex, average particle size 0.5 μm) was changed from 120 parts to 200 parts. was created.

Table 1 shows the evaluation results of Examples and Comparative Examples.

From the above results, when using a resin composition containing a combination of components (A), (B), and (C) in a specific content, the dielectric loss tangent is low, the smear removability is excellent, and the conductor It can be seen that a cured product with excellent adhesion between the layers can be obtained.

In Examples 1 to 10, it has been confirmed that even when components (D) to (G) are not contained, the results are similar to those of the above examples, although there are differences in degree.

Claims (20)

(A) Epoxy resin, (B) resin having two or more radically polymerizable unsaturated groups per molecule selected from acryloyl groups and methacryloyl groups and having a number average molecular weight of 200 to 3000, (C) epoxy A resin composition comprising a resin curing agent and (D) an inorganic filler,
(A) component contains (A-1) glycidylamine type epoxy resin and epoxy resin other than component (A-1),
(C) component contains an active ester curing agent,
Component (C) further contains one or more curing agents selected from a nitrogen-containing phenol curing agent, a nitrogen-containing naphthol curing agent, a carbodiimide curing agent, and a benzoxazine curing agent,
When the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass,
When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (A-1) is 0.20 to 10 parts by mass,
When the nonvolatile components in the resin composition are 100 parts by mass, the content of component (C) is 5 to 40 parts by mass,
A resin composition in which the content of component (D) is 50 to 90 parts by mass when the nonvolatile components in the resin composition are 100 parts by mass. (A) Epoxy resin, (B) resin having two or more radically polymerizable unsaturated groups per molecule selected from acryloyl groups and methacryloyl groups and having a number average molecular weight of 200 to 3000, (C) epoxy A resin composition comprising a resin curing agent and (D) an inorganic filler,
(A) component contains (A-1) glycidylamine type epoxy resin and epoxy resin other than component (A-1),
(C) component contains an active ester curing agent (excluding an active ester compound having a structural unit represented by the following formula (α)),
(D) the component contains silica,
When the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass,
When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (A-1) is 0.20 to 10 parts by mass,
When the nonvolatile components in the resin composition are 100 parts by mass, the content of component (C) is 5 to 40 parts by mass,
A resin composition in which the content of component (D) is 50 to 90 parts by mass when the nonvolatile components in the resin composition are 100 parts by mass.
(In formula (α), l is each independently an integer of 0 or more and 6 or less, m is each independently an integer of 1 or more and 5 or less, and n is an integer of 1 or more and 6 or less.) The resin composition according to claim 1 or 2 , wherein component (C) contains a carbodiimide curing agent. The resin composition according to claim 1 or 2 , wherein component (C) contains a curing agent selected from a nitrogen-containing phenol curing agent and a nitrogen-containing naphthol curing agent. The resin composition according to claim 1 or 2 , further comprising (E) a thermoplastic resin. The resin composition according to claim 5 , wherein component (E) contains a phenoxy resin. The resin composition according to claim 1 or 2 , further comprising (G) a polymerization initiator, and component (G) comprising a peroxide. The resin composition according to claim 1 or 2 , wherein the content of component (D) is 55% by mass or more when the nonvolatile component in the resin composition is 100 parts by mass. The resin composition according to claim 1 or 2 , wherein the content of component (D) is 65 parts by mass or more when the nonvolatile component in the resin composition is 100 parts by mass. 3. The resin composition according to claim 1 , wherein component (D) has a specific surface area of 2 m ² /g to 10 m ² /g. The resin composition according to claim 1 or 2 , wherein the average particle size of component (D) is 0.1 μm to 1 μm. 3. The resin composition according to claim 1 , wherein component (D) includes one treated with a surface treatment agent. A claim in which the surface treatment agent is one or more selected from aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. 13. The resin composition according to 12 . The resin composition was pressure-bonded to the roughened surface of copper foil (Ra value = 1 μm) at 100°C and 0.74 MPa for 30 seconds, and then cured at 190°C for 90 minutes to form a cured product layer. The adhesion strength when peeling off 35 mm of copper foil in the vertical direction at a speed of 50 mm/min is 0.62 kgf/cm or more, and after being subjected to conditions of 130°C and 85% RH for 100 hours, it is cured. The resin composition according to claim 1 or 2 , wherein the resin composition has an adhesion strength of 0.25 kgf/cm or more when 35 mm of the copper foil is peeled off from the material layer in the vertical direction at a speed of 50 mm/min. The resin composition according to claim 1 or 2 , wherein the dielectric loss tangent of the cured product is less than 0.0054 when measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. (A) Epoxy resin, (B) resin having two or more radically polymerizable unsaturated groups per molecule selected from acryloyl groups and methacryloyl groups and having a number average molecular weight of 200 to 3000, (C) epoxy A resin composition comprising a resin curing agent and (D) an inorganic filler,
(A) component contains (A-1) glycidylamine type epoxy resin and epoxy resin other than component (A-1),
When the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass,
(C) component contains an active ester curing agent,
Component (C) further contains one or more curing agents selected from a nitrogen-containing phenol curing agent, a nitrogen-containing naphthol curing agent, a carbodiimide curing agent, and a benzoxazine curing agent,
When the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass,
When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (A-1) is 0.20 to 10 parts by mass,
When the nonvolatile components in the resin composition are 100 parts by mass, the content of component (C) is 5 to 40 parts by mass,
When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (A-1) is 0.20 to 10 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (D) is 50 to 90 parts by mass (provided that the resin composition contains two or more aromatic rings and three or more glycidyl ethers). an aromatic cationically polymerizable compound having a structure, an aliphatic cationically polymerizable compound having one or more alcoholic hydroxyl groups and two or more glycidyl ether structures, and/or a cationically polymerizable compound having an oxetane group, and one or more a radical polymerizable compound having an alcoholic hydroxyl group and two or more methacrylic groups and/or acrylic groups; a cationic polymerization initiator that is a sulfonium compound or a bis(alkylphenyl)iodonium compound; a radical polymerization initiator; (including all sensitizers, excluding resin compositions). (A) Epoxy resin, (B) resin having two or more radically polymerizable unsaturated groups per molecule selected from acryloyl groups and methacryloyl groups and having a number average molecular weight of 200 to 3000, (C) epoxy A resin composition comprising a resin curing agent and (D) an inorganic filler,
(A) component contains (A-1) glycidylamine type epoxy resin and epoxy resin other than component (A-1),
(C) component contains an active ester curing agent (excluding an active ester compound having a structural unit represented by the following formula (α)),
(D) the component contains silica,
When the content of component (A) other than component (A-1) is 100 parts by mass, the content of component (A-1) is 2 to 250 parts by mass,
When the content of component (B) is 100 parts by mass, the content of component (A-1) is 3 to 250 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (A-1) is 0.20 to 10 parts by mass,
When the nonvolatile components in the resin composition are 100 parts by mass, the content of component (C) is 5 to 40 parts by mass,
When the nonvolatile component in the resin composition is 100 parts by mass, the content of component (D) is 50 to 90 parts by mass (provided that the resin composition contains two or more aromatic rings and three or more glycidyl ethers). an aromatic cationically polymerizable compound having a structure, an aliphatic cationically polymerizable compound having one or more alcoholic hydroxyl groups and two or more glycidyl ether structures, and/or a cationically polymerizable compound having an oxetane group, and one or more a radical polymerizable compound having an alcoholic hydroxyl group and two or more methacrylic groups and/or acrylic groups; a cationic polymerization initiator that is a sulfonium compound or a bis(alkylphenyl)iodonium compound; a radical polymerization initiator; (including all sensitizers, excluding resin compositions).
(In formula (α), l is each independently an integer of 0 or more and 6 or less, m is each independently an integer of 1 or more and 5 or less, and n is an integer of 1 or more and 6 or less.) A sheet-like laminate material containing the resin composition according to any one of claims 1 to 17. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 17. A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 17.