JP2023161487A - resin composition - Google Patents

Abstract

To provide a resin composition that can yield a cured product with superior crack resistance.SOLUTION: A resin composition includes (A) an epoxy resin, (B) a curing agent, and (C) a thermoplastic resin with a hyperbranched structure.SELECTED DRAWING: None

Description

The present invention relates to a resin composition. Furthermore, the present invention relates to resin sheets, printed wiring boards, and semiconductor devices obtained using the resin composition.

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 is known.

As an insulating material for a printed wiring board used for such an insulating layer, for example, a resin composition is disclosed in Patent Document 1.

JP 2018-53092 Publication

Incidentally, in recent years, for example, insulating layers used in wiring boards having embedded wiring layers are required to have excellent crack resistance (suppression of crack generation) in order to improve yield.

An object of the present invention is to provide a resin composition from which a cured product with excellent crack resistance can be obtained; a resin sheet containing the resin composition; a printed wiring board having an insulating layer formed using the resin composition; The purpose of the present invention is to provide semiconductor devices.

As a result of intensive studies on the above-mentioned problems, the present inventors discovered that the above-mentioned problems could be solved by containing a combination of an epoxy resin, a curing agent, and a thermoplastic resin having a hyperbranched structure, and completed the present invention. I ended up doing it.

That is, the present invention includes the following contents.
[1] (A) Epoxy resin,
A resin composition comprising (B) a curing agent and (C) a thermoplastic resin having a hyperbranched structure.
[2] The resin composition according to [1], wherein the component (C) has a cyclic structure.
[3] The resin composition according to [1] or [2], wherein the component (C) has a phenylene ether skeleton.
[4] The resin composition according to any one of [1] to [3], wherein the component (C) has a siloxane structure.
[5] The resin composition according to any one of [1] to [4], wherein component (C) has a triazine ring.
[6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of component (C) is 1,000 or more and 40,000 or less.
[7] Component (C) has a multi-branched structure in which a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound are alternately bonded, and the terminal has a structure derived from a monofunctional compound, [ The resin composition according to any one of [1] to [6].
[8] The resin composition according to any one of [1] to [7], wherein component (C) is a resin having a glass transition temperature of 50° C. or higher and 150° C. or lower.
[9] The resin composition according to any one of [1] to [8], wherein the terminal of component (C) contains either an alkoxysilyl group or an arylalkoxy group.
[10] (D) The resin composition according to any one of [1] to [9], which contains an inorganic filler.
[11] The resin composition according to [10], wherein the content of component (D) is 50% by mass or more when the resin component in the resin composition is 100% by mass.
[12] The resin composition according to any one of [1] to [11], wherein component (B) contains an active ester curing agent.
[13] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [12].
[14] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [12].
[15] A semiconductor device comprising the printed wiring board according to [14].

According to the present invention, a resin composition from which a cured product with excellent crack resistance can be obtained; a resin sheet containing the resin composition; a printed wiring board having an insulating layer formed using the resin composition; A semiconductor device can be provided.

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

[Resin composition]
The resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) a thermoplastic resin having a hyperbranched structure. In the present invention, by including components (A) to (C) in combination in a resin composition, a cured product with excellent crack resistance can be obtained. Moreover, according to the cured product of the resin composition of the present invention, a cured product that is generally excellent in dielectric loss tangent and plating adhesion can also be obtained.

The resin composition may further contain arbitrary components in combination with components (A) to (C). Examples of the optional components include (D) an inorganic filler, (E) a radically polymerizable compound, (F) a curing accelerator, (G) a thermoplastic resin, and (H) other additives. Each component contained in the resin composition will be explained in detail below.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin as the (A) component. (A) Epoxy resins include, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol 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, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin , biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy Examples include resins and trimethylol-type epoxy resins. (A) Epoxy resins may be used alone or in combination of two or more.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, based on 100% by mass of the nonvolatile components of the epoxy resin. It is more preferably 60% by mass or more, particularly preferably 70% by mass or more.

Epoxy resins are classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition may contain only liquid epoxy resin or only solid epoxy resin as the epoxy resin, but from the viewpoint of significantly obtaining the effects of the present invention, liquid epoxy resin and solid epoxy resin may be used. It is preferable to include it in combination with an epoxy resin.

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

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, and ester skeleton. Alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure are preferred, and bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Corporation. 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; manufactured by Mitsubishi Chemical “630” and “630LSD” (glycidylamine type epoxy resin); “ZX1059” manufactured by Nippon Steel Chemical & Materials (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); manufactured by Nagase ChemteX Co., Ltd. "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celoxide 2021P" (alicyclic epoxy resin with ester skeleton); Daicel's "PB-3600" (epoxy resin with butadiene structure) Examples include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials. These may be used alone or in combination of two or more.

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 bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, and naphthol. Type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins are preferred, and biphenyl type epoxy resins are more preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" (manufactured by DIC). Cresol novolac type epoxy resin), "N-695" (Cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311" ”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000”, “HP6000L” (naphthylene ether type epoxy resin); “EPPN” manufactured by Nippon Kayaku Co., Ltd. -502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolak type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin); Nippon Steel Chemical & Materials Co., Ltd. "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation. resin), "YX8800" (anthracene type epoxy resin), "157S70" (novolac type epoxy resin); "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., "YX7760" manufactured by Mitsubishi Chemical Company ( Bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), and the like. These may be used alone or in combination of two or more.

When a solid epoxy resin and a liquid epoxy resin are used in combination as the epoxy resin, their mass ratio (solid epoxy resin: liquid epoxy resin) is preferably 1:0.01 to 1:50, more preferably The ratio is 1:0.05 to 1:20, particularly preferably 1:0.1 to 1:10. By setting the ratio of the liquid epoxy resin to the solid epoxy resin within such a range, 1) appropriate tackiness is provided when used in the form of a resin sheet, and 2) when used in the form of a resin sheet. The following effects can be obtained: 3) sufficient flexibility can be obtained, handling properties are improved, and 3) a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5000g/eq. , more preferably 50g/eq. ～3000g/eq. , more preferably 80g/eq. ～2000g/eq. , even more preferably 110 g/eq. ～1000g/eq. It is. Within this range, a cured product of the resin composition with sufficient crosslinking density can be obtained. Epoxy equivalent is the mass of epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, even more preferably from 400 to 1,500, from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 1% by mass or more, more preferably 3% by mass when the nonvolatile component in the resin composition is 100% by mass. It is at least 5% by mass, more preferably at least 5% by mass. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(B) Curing agent>
The resin composition contains a (B) curing agent as the (B) component. The curing agent (B) as the component (B) does not include those corresponding to the above-mentioned component (A). (B) The curing agent has the function of curing the (A) epoxy resin. (B) The curing agent may be used alone or in combination of two or more.

(B) The curing agent is not particularly limited as long as it has the function of curing the epoxy resin (A), and examples include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, and cyanates. Examples include ester-based curing agents and carbodiimide-based curing agents. Among these, the curing agent preferably contains one or more selected from phenolic curing agents, active ester curing agents, and carbodiimide curing agents, from the viewpoint of significantly obtaining the effects of the present invention. It is more preferable to include a curing agent.

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 adhesion strength with the conductor layer, a nitrogen-containing phenol curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenol curing agent 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 strength with the conductor layer. These may be used alone or in combination of two or more.

The active ester curing agent is not particularly limited, but generally one molecule of an ester group with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is used. Compounds having two or more in them are preferably used. The active ester compound 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 compounds obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester compounds 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.

Examples of active ester curing agents include dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolak, and active ester compounds containing benzoylated products of phenol novolak. Ester compounds are preferred, and at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.

Commercially available active ester curing agents include "EXB9451," "EXB9460," "EXB9460S," "HPC-8000L-65TM," and "HPC-8000-65T," which are active ester compounds containing a dicyclopentadiene-type diphenol structure. ", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); "HP-B-8151-62T", "EXB-8100L-65T", "EXB- 9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC); as a phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC), an active ester compound that is an acetylated product of phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoylated products of phenol novolak, active ester compounds containing a styryl group and a naphthalene structure. Examples include "PC1300-02-65MA" (manufactured by Air Water).

Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", Nippon Steel Chemical & Materials' "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", " Examples include "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

Specific examples of benzoxazine curing agents include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

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-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Examples include polyfunctional cyanate resins derived from novolacs and cresol novolaks, and prepolymers in which these cyanate resins are partially triazinized. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinized to form a trimer), and the like.

The carbodiimide curing agent is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and the carbodiimide curing agent is preferably a compound having two or more carbodiimide groups in one molecule. .

As specific examples of carbodiimide curing agents, commercially available carbodiimide curing agents include Carbodilite V-03 (carbodiimide group equivalent: 216), V-05 (carbodiimide group equivalent: 262), manufactured by Nisshinbo Chemical Co., Ltd. 07 (carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200); Stabaxol P (carbodiimide group equivalent: 302) manufactured by Rhein Chemie.

The quantitative ratio of the epoxy resin to the curing agent is the ratio of [total number of epoxy groups in the epoxy resin]:[total number of active groups in the curing agent], and is preferably in the range of 1:0.01 to 1:10. The ratio is more preferably 1:0.3 to 1:5, and even more preferably 1:0.5 to 1:3. Here, "the number of epoxy groups in the epoxy resin" is the sum of all the values obtained by dividing the mass of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Moreover, "the number of active groups of a curing agent" is the total value of all the values obtained by dividing the mass of nonvolatile components of the curing agent present in the resin composition by the active group equivalent. By setting the amount ratio of the curing agent to the epoxy resin within this range, the effects of the present invention can be significantly obtained.

From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less.

<(C) Thermoplastic resin having hyperbranched structure>
The resin composition contains (C) a thermoplastic resin having a hyperbranched structure as the (C) component. By incorporating component (C) into the resin composition, it becomes possible to obtain a cured product with excellent crack resistance. Component (C) may be used alone or in combination of two or more.

(A) Thermoplastic resin having a hyperbranched structure refers to a thermoplastic resin having a multi-branched structure having a plurality of branches. The thermoplastic resin having a hyperbranched structure preferably has two or more branched chains, more preferably three or more branches, still more preferably four or more, five or more, six or more, and eight or more. (C) The thermoplastic resin having a hyperbranched structure preferably has a multi-branched structure in which a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound are alternately bonded, and a monofunctional compound at the terminal. Refers to a resin with a structure derived from

A thermoplastic resin having such a preferred hyperbranched structure can be obtained by reacting a trifunctional or higher functional compound, a bifunctional compound, which forms the center of the molecular structure, and a monofunctional compound, which forms the terminal end of the molecule. Since the thermoplastic resin having a hyperbranched structure has a multi-branched structure, it can have free space around the branched portions. By having a free space, even when the resin composition is cured, it is difficult to shrink and stress is not easily generated, and as a result, it is thought that the occurrence of cracks is suppressed.

The terminal end of component (C) is preferably a group having no ethylenically unsaturated bond, such as a vinyl (-CH=CH ₂ ) group, from the viewpoint of improving crack resistance. That is, component (C) is excluded if the terminal has an ethylenically unsaturated bond. If the terminal of component (C) has an ethylenically unsaturated bond, it is excluded, so component (C) functions as a thermoplastic resin. It is thought that this alleviates stress in the cured product of the resin composition containing component (C), thereby improving crack resistance. The terminals of component (C) are preferably either alkoxysilyl groups or aryloxy groups, and more preferably all terminals are alkoxysilyl groups.

Examples of the alkoxysilyl group include trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, methoxydimethylsilyl group, diethoxymethylsilyl group, ethoxydimethylsilyl group, dimethoxyphenylsilyl group, diethoxyphenylsilyl group, etc.

Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an anthracenyloxy group, and the like.

Component (C) preferably contains a cyclic structure, and the cyclic structure preferably contains an aromatic structure, from the viewpoint of significantly obtaining the effects of the present invention. The aromatic structure is a chemical structure that is generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

Examples of the cyclic structure include a heterocyclic skeleton, a bisphenol skeleton, a phenylene ether skeleton, a phenylene skeleton, a naphthylene skeleton, a dimethylmethylenebiscyclohexylene skeleton, an anthracene skeleton, and the like, with a heterocyclic skeleton and a bisphenol skeleton being preferred. Examples of the heterocyclic skeleton include nitrogen atom-containing heterocyclic skeletons such as a triazine ring and a pyridine ring, with a triazine ring being preferred. Bisphenol skeletons include bisphenol A skeleton, bisphenol F skeleton, bisphenol AP skeleton, bisphenol AF skeleton, bisphenol B skeleton, bisphenol BP skeleton, bisphenol S skeleton, bisphenol Z skeleton, bisphenol C skeleton, bisphenol TMC skeleton, bisphenol AF skeleton, and bisphenol. Examples include E skeleton, bisphenol G skeleton, bisphenol M skeleton, bisphenol PH skeleton, and bisphenol TMC and bisphenol AF skeletons are preferred. Among these, component (C) preferably contains a cyclic structure of either a heterocyclic skeleton or a phenylene ether skeleton, more preferably a cyclic structure of a triazine ring or a phenylene ether skeleton, and a triazine ring or a phenylene ether skeleton. It is more preferable to have two types of cyclic structures.

The cyclic structure is preferably included in any one of a structure derived from a trifunctional or higher functional compound, a bifunctional compound derived structure, and a monofunctional compound derived structure, and a structure derived from a trifunctional or higher functional compound, and a bifunctional compound. More preferably, it is included in the original structure.

The ring in the cyclic structure may have a substituent. Examples of such substituents include halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups, arylalkyl groups having 7 to 12 carbon atoms, silyl groups, acyl groups, Examples include acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, and oxo group.

Component (C) preferably has a siloxane structure (-Si-O-Si-) from the viewpoint of significantly obtaining the effects of the present invention. The siloxane structure is preferably included in any of a structure derived from a trifunctional or higher functional compound, a structure derived from a bifunctional compound, and a structure derived from a monofunctional compound, and a structure derived from a bifunctional compound and a structure derived from a monofunctional compound. More preferably, it is included in the structure of The structure derived from a bifunctional compound preferably includes a structure derived from a bifunctional compound having a siloxane structure and a structure derived from a bifunctional compound not having a siloxane structure in one molecule.

Content ratio of a structure derived from a bifunctional compound having a siloxane structure and a structure derived from a bifunctional compound not having a siloxane structure in one molecule of component (C) (Structure derived from a bifunctional compound having a siloxane structure/ From the viewpoint of significantly obtaining the effects of the present invention, the structure derived from a bifunctional compound that does not have a siloxane structure is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more. Yes, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less. The content ratio is a value calculated from the molar ratio of the charged amounts of reaction raw materials.

The trifunctional or higher functional compound is a compound that can have a structure derived from a trifunctional or higher functional compound, and can serve as the core of a hyperbranched structure. Further, the trifunctional or higher functional compound has a functional group that can react with a bifunctional compound and a monofunctional compound. The trifunctional or higher functional compound has a structure derived from the trifunctional or higher functional compound in a hyperbranched structure. The trifunctional or higher functional compound is preferably a trifunctional compound or a tetrafunctional compound, more preferably a trifunctional compound.

Examples of functional groups possessed by trifunctional or higher functional compounds include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; OH groups (including phenolic hydroxyl groups); amino groups; epoxy groups; glycidyl ether groups, etc. are mentioned, with halogen atoms being preferred.

The trifunctional or higher functional compound preferably contains a cyclic structure from the viewpoint of significantly obtaining the effects of the present invention. The cyclic structure preferably includes an aromatic structure, preferably a heterocyclic skeleton, more preferably an aromatic heterocycle, further preferably an aromatic heterocycle containing a nitrogen atom, and particularly preferably a triazine ring. The number of nitrogen atoms contained in the aromatic heterocycle containing a nitrogen atom is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, particularly preferably 3 It is.

Specific examples of trifunctional or higher functional compounds include cyanuric acid chloride, 2,4,6-trichloropyrimidine, 2,4,6-trichloropyridine, and the like. Among these, cyanuric acid chloride is preferred as the trifunctional or higher functional compound.

A bifunctional compound is a compound that can bond with either a functional group of a trifunctional or higher functional compound or a functional group of a monofunctional compound, and a functional group that can react with a functional group of a trifunctional or higher functional compound and a functional group of a monofunctional compound. It has a group. A bifunctional compound has a structure derived from a bifunctional compound in a hyperbranched structure.

Examples of the functional group that the bifunctional compound has include an OH group (including a phenolic hydroxyl group), an epoxy group, a glycidyl ether group, and an amino group, with either the OH group or the amino group being preferred.

From the viewpoint of improving crack resistance, the bifunctional compound preferably contains a combination of a bifunctional compound containing a siloxane structure (-Si-O-Si-) and a bifunctional compound not containing a siloxane structure. The content ratio in one molecule of a bifunctional compound containing a siloxane structure and a bifunctional compound not containing a siloxane structure is determined by the content ratio of a bifunctional compound containing a siloxane structure and a bifunctional compound originating from a bifunctional compound not having a siloxane structure. It is the same as the content ratio of the structure.

From the viewpoint of significantly obtaining the effects of the present invention, the bifunctional compound may contain a cyclic structure, and the cyclic structure preferably contains an aromatic structure, and more preferably contains a phenylene skeleton or a phenylene ether skeleton. It is more preferable that it contains a phenylene ether skeleton. The phenylene ether skeleton is preferably contained in a bifunctional compound that does not contain a siloxane structure, from the viewpoint of significantly obtaining the effects of the present invention.

Specific examples of the bifunctional compound include compounds represented by the following formulas (1) to (50). In formula (32), X represents a phenyl group and Y represents a methyl group. In formulas (33) to (38), n represents an integer of 1 to 300, and in formulas (37) to (42), m represents an integer of 1 to 300. In formula (38), Y represents an oxygen atom, a methylene group, or a dimethylmethylene group. In formulas (39) to (42), R represents a methylene group or a phenylene group. In formula (40), R ^a represents a methyl group or a phenyl group.

As the bifunctional compound, a compound obtained by reacting a trifunctional compound with a monofunctional compound described below may be used. Examples of such bifunctional compounds include compounds represented by the following formulas (43) to (50). In formula (43), R represents an isopropyl group.

Among these, as the bifunctional compound, compounds represented by formulas (24), (25), and (38) to (42) are preferred.

A commercially available product may be used as the bifunctional compound. Commercially available products include, for example, "KF-2201" and "KF-8010" manufactured by Shin-Etsu Silicone Co., Ltd., "KF-8010", "X-22-9409", and "KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd. Examples include "SA90" manufactured by SABIC Innovative Plastics.

A monofunctional compound is a compound that can bond with either the functional group of a trifunctional or higher functional compound or the functional group of a bifunctional compound, and reacts with either the functional group of a trifunctional or higher functional compound or the functional group of a bifunctional compound. It has a functional group that can Further, the monofunctional compound can be the terminal of the component (C) as a structure derived from the monofunctional compound.

Examples of the functional groups that the monofunctional compound has include: amino group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; OH group (including phenolic hydroxyl group); thiol group; amino group; epoxy group; Examples include glycidyl ether groups, and amino groups, thiol groups, and OH groups are preferred.

From the viewpoint of significantly obtaining the effects of the present invention, the monofunctional compound preferably contains a siloxane bond (-Si-O-), and is more preferably an alkoxysilane compound having the above-mentioned functional group.

Specific examples of monofunctional compounds include compounds represented by the following formulas (1-1) to (1-24). In the following formula, R represents an isopropyl group. In formulas (1-13) to (1-16), n represents an integer of 1 to 300.

Among these, monofunctional compounds include compounds represented by formula (1-10), compounds represented by formula (1-22), compounds represented by formula (1-23), and compounds represented by formula (1-24). ) are preferred.

A commercially available monofunctional compound may be used. Commercially available products include, for example, "X-22-170BX" and "X-22-170DX" manufactured by Shin-Etsu Silicone Co., Ltd., and "KBM903", "KBE903", "KBM603", "KBM573", and "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. KBM802'', etc.

(C) A thermoplastic resin having a hyperbranched structure can be prepared by reacting a trifunctional or higher functional compound, a bifunctional compound, and a monofunctional compound. Further, the bifunctional compound is preferably prepared by combining a bifunctional compound having a siloxane structure and a bifunctional compound not containing a siloxane structure.

The reaction temperature is preferably 10°C or higher, more preferably 30°C or higher, even more preferably 40°C or higher, and preferably 100°C or lower, more preferably 80°C or lower, and still more preferably 60°C or lower. Particularly preferred is 50°C.

The reaction time is preferably 1 hour or more, more preferably 5 hours or more, even more preferably 10 hours or more, and preferably 50 hours or less, more preferably 24 hours or less, and still more preferably 15 hours or less. Particularly preferred is overnight (12 hours).

(C) Specific examples of the thermoplastic resin having a hyperbranched structure include the following, but the present invention is not limited thereto. In the following formula, the broken line means that a multi-branched structure in which a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound are alternately bonded is further bonded. R represents a methylene group or a phenylene group.

The weight average molecular weight of component (C) is preferably 1,000 or more, more preferably 1,200 or more, even more preferably 1,400 or more, and preferably 40,000 or less, more preferably 30,000 or more, from the viewpoint of significantly obtaining the effects of the present invention. Below, it is more preferably 20,000 or less, 10,000 or less, and 6,000 or less. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The glass transition temperature (Tg) of component (C) is preferably 50°C or higher, more preferably 60°C or higher, still more preferably 70°C or higher, and preferably 150°C or higher, from the viewpoint of significantly obtaining the effects of the present invention. The temperature is preferably 140°C or lower, more preferably 130°C or lower. Glass transition temperature can be measured by differential scanning calorimetry (DSC). Component (C) may have multiple glass transition temperatures. In that case, the plurality of glass transition temperatures are preferably within such ranges.

From the viewpoint of obtaining a cured product with excellent crack resistance, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more when the nonvolatile component in the resin composition is 100% by mass. 3% by mass or more, more preferably 0.5% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, 5% by mass or less, 3% by mass or less. be.

<(D) Inorganic filler>
The resin composition may contain an optional component (D) inorganic filler as the component (D). (D) By incorporating the inorganic filler into the resin composition, it is possible to obtain a cured product with a low dielectric loss tangent.

An inorganic compound is used as the material for the inorganic filler. Examples of inorganic filler materials 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 these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (D) Inorganic fillers may be used alone or in combination of two or more.

(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", "SO-C1", and "SC2050-SXF" manufactured by Admatex.

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

(D) 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 scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of an inorganic filler, 10 g of methyl ethyl ketone, and 0.1 g of a dispersant ("SN9228" manufactured by San Nopco Co., Ltd.) into a vial, and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size is calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, "SALD-2200" manufactured by Shimadzu Corporation, and the like.

(D) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, particularly preferably 3 m ² /g or more, from the viewpoint of significantly obtaining the desired effects of the present invention. be. Although there is no particular limit to the upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is determined by adsorbing nitrogen gas onto the sample surface using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), and calculating the specific surface area using the BET multi-point method. It can be obtained by measuring the specific surface area of the material.

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, Aminosilane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane; Epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane; Mercaptosilane cups such as 3-mercaptopropyltrimethoxysilane Ring agents; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; titanate coupling agents; and the like. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kagaku Kogyo, "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "SZ-31" manufactured by Shin-Etsu Chemical ( hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBM-4803" (long chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical, "KBM-" manufactured by Shin-Etsu Chemical 7103'' (3,3,3-trifluoropropyltrimethoxysilane).

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 suppressing an increase in the melt viscosity of the resin varnish and 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.

(D) 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) From the viewpoint of obtaining a cured product with a low dielectric loss tangent, the content of the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass when the nonvolatile component in the resin composition is 100% by mass. % or more, more preferably 70% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.

<(E) Radical polymerizable compound>
The resin composition may further contain (E) a radically polymerizable compound as an optional component in combination with the above-mentioned components (A) to (C). The radically polymerizable compound (E) as the component (E) does not include those corresponding to the components (A) to (D) described above. (E) The radically polymerizable compound may be used alone or in combination of two or more.

(E) The radically polymerizable compound may have an ethylenically unsaturated bond. (E) The radically polymerizable compound is an unsaturated hydrocarbon group such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, an m-vinylphenyl group, an o-vinylphenyl group, etc. ; a radically polymerizable group such as an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group, a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group); may have. (E) The radically polymerizable compound preferably has two or more radically polymerizable groups.

(E) Examples of the radically polymerizable compound include (meth)acrylic radically polymerizable compounds, styrene radically polymerizable compounds, allyl radically polymerizable compounds, maleimide radically polymerizable compounds, and the like.

The (meth)acrylic radically polymerizable compound is, for example, a compound having one or more, preferably two or more, acryloyl groups and/or methacryloyl groups. Examples of (meth)acrylic radically polymerizable compounds include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic ester compounds such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6, 9-Trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene , ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and other low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds; tris(3-hydroxypropyl)isocyanurate tris Low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanurate tri(meth)acrylate; Examples include high molecular weight (molecular weight 1000 or more) acrylic ester compounds such as (meth)acrylic modified polyphenylene ether resin. Commercially available (meth)acrylic radically polymerizable compounds include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. and "DCP-A" (tricyclodextrin diacrylate) manufactured by Kyoeisha Chemical Co., Ltd. Candimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), Nippon Kayaku Co., Ltd.'s "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol) diacrylate), "SA-9000" and "SA-9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

The styrenic radically polymerizable compound is, for example, a compound having one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of styrenic radically polymerizable compounds include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4 -Low molecular weight (molecular weight less than 1000) styrenic compounds such as vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; vinylbenzyl-modified polyphenylene ether resin, styrene- Examples include high molecular weight (molecular weight 1000 or more) styrene compounds such as divinylbenzene copolymers. Commercially available styrene-based radically polymerizable compounds include, for example, "ODV-XET (X03)," "ODV-XET (X04)," and "ODV-XET (X05)" manufactured by Nippon Steel Chemical & Materials (styrene -divinylbenzene copolymer), "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

The allyl radically polymerizable compound is, for example, a compound having one or more allyl groups, preferably two or more allyl groups. Examples of allyl-based radically polymerizable compounds include diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenecarboxylate, etc. Aromatic carboxylic acid allyl ester compounds; Isocyanuric acid allyl ester compounds such as 1,3,5-triallylisocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis[3-allyl-4 Epoxy-containing aromatic allyl compounds such as -(glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane, etc. Examples thereof include benzoxazine-containing aromatic allyl compounds; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allylsilane compounds such as diallyldiphenylsilane. Commercially available allyl-based radically polymerizable compounds include, for example, "TAIC" (1,3,5-triallylisocyanurate) manufactured by Nippon Kasei Co., Ltd., and "DAD" (diallyl diphenate) manufactured by Nippon Kasei Co., Ltd. , “TRIAM-705” (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., “DAND” (diallyl 2,3-naphthalenecarboxylate) manufactured by Nippon Distilling Industry Co., Ltd., “ALP-” manufactured by Shikoku Kasei Kogyo Co., Ltd. d” (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane), “RE-810NM” manufactured by Nippon Kayaku Co., Ltd. (2, 2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd., and the like.

The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Commercial products of maleimide-based radically polymerizable compounds include, for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., and "BMI-1500", "BMI-1700", and "BMI-3000J" manufactured by Designer Molecules. , "BMI-689", "BMI-2500" (maleimide compound containing dimer diamine structure), "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, "MIR-5000" manufactured by Nippon Kayaku Co., Ltd. -60T", "MIR-3000-70MT" (biphenylaralkyl maleimide compound), "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300" manufactured by Daiwa Kasei Co., Ltd., " BMI-TMH" etc. Furthermore, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Japan Institute of Invention and Innovation Publication No. 2020-500211 may be used.

(E) The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g/eq. ～3000g/eq. , more preferably 50g/eq. ～2500g/eq. , more preferably 70g/eq. ～2000g/eq. , particularly preferably 90 g/eq. ～1500g/eq. It is. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.

The weight average molecular weight (Mw) of the radically polymerizable compound (E) is preferably 40,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more.

(E) The content of the radically polymerizable compound may be 0% by mass, preferably 0.01% by mass or more, and more preferably 0.01% by mass or more, when the nonvolatile components in the resin composition are 100% by mass. The content is 5% by mass or more, more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less.

<(F) Curing accelerator>
The resin composition may further contain (F) a curing accelerator as an optional component in combination with the above-mentioned components (A) to (D). The (F) curing accelerator as the (F) component does not include those corresponding to the above-mentioned components (A) to (E). (F) The curing accelerator has a function as a curing catalyst that promotes curing of the epoxy resin (A).

As the curing accelerator (F), a compound that accelerates the effect of the epoxy resin (A) can be used. Examples of such curing accelerators (F) include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. can be mentioned. (F) The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl) )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

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 -allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

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 , imidazole compounds such as 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Commercially available imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA-OK-" manufactured by Shikoku Kasei Kogyo Co., Ltd. PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; "P200-H50" manufactured by Mitsubishi Chemical Corporation, and the like.

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.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo. Examples include (5,4,0)-undecene and the like. As the amine curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno.

(F) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.01% by mass or more, when the nonvolatile components in the resin composition are 100% by mass. The content is 1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less.

<(G) Thermoplastic resin>
The resin composition further contains (G) a thermoplastic resin (excluding those corresponding to component (C)) as an optional component in combination with the above-mentioned components (A) to (C). Good too. The thermoplastic resin (G) as the component (G) does not include those corresponding to the components (A) to (F) described above.

(G) Thermoplastic resins include, for example, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyetheretherketone resin, polyester resin, and the like. (G) The thermoplastic resin may be used alone or in combination of two or more.

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," "YL7482," and "YL7891BH30."

Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shinnihon Rika Co., Ltd., and the like.

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.

Examples of polyolefin resins include ethylene copolymers such as low density polyethylene, ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin; Examples include polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing polybutadiene resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

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 polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

A specific example of the polyphenylene ether resin includes "NORYL SA90" manufactured by SABIC. A specific example of the polyetherimide resin includes "Ultem" manufactured by GE.

Examples of the polycarbonate resin include hydroxy group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and the like. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090" and "C-2090" manufactured by Kuraray Corporation. , "C-3090" (polycarbonate diol), and the like. Specific examples of polyetheretherketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, and the like.

The weight average molecular weight (Mw) of the thermoplastic resin (G) is preferably larger than 5,000, more preferably 8,000 or more, even more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably is 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, particularly preferably 50,000 or less.

(G) The content of the thermoplastic resin may be 0% by mass or greater than 0% by mass, preferably 0.01% by mass when the nonvolatile components in the resin composition are 100% by mass. % or more, more preferably 0.10% by mass or more, more preferably 0.2% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 2% by mass or less.

<(H) Optional additive>
In combination with the above-mentioned components (A) to (C), the resin composition may further contain (H) any additive as any non-volatile component. (H) Optional additives include, for example, polymerization initiators; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, oxidation Coloring agents such as titanium and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Thickeners such as bentone and montmorillonite; Silicone antifoaming agents Antifoaming agents such as acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; Ultraviolet absorbers such as benzotriazole ultraviolet absorbers; Adhesion improvers such as urea silane; Triazole adhesion Adhesion-imparting agents such as adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; Antioxidants such as hindered phenol-based antioxidants; Fluorescent brighteners such as stilbene derivatives; Fluorine-based surfactants Surfactants such as silicone surfactants; phosphorus flame retardants (e.g. phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, Flame retardants such as inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants, etc. Dispersants; Stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydride stabilizers; tertiary Examples include photopolymerization initiation aids such as amines; photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (H) The optional additives may be used alone or in combination of two or more.

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.

<Physical properties and uses of resin composition>
Since the resin composition contains a combination of components (A) to (C), the occurrence of cracks is suppressed, and furthermore, it is usually possible to obtain a cured product with excellent dielectric loss tangent and plating adhesion.

A cured product obtained by thermally curing the resin composition at 130° C. for 30 minutes and then at 180° C. for 30 minutes exhibits the characteristic that the generation of cracks is suppressed. Therefore, the cured product provides an insulating layer with excellent crack resistance. Specifically, a resin composition layer is obtained by laminating a resin composition on an inner layer substrate having circuit conductors on both sides. A cured substrate is obtained by thermally curing the inner layer substrate on which the resin composition layer is laminated at 130° C. for 30 minutes and then at 180° C. for 30 minutes. A sample is obtained by desmearing a cured substrate, and the surface of the insulating layer of the sample after desmearing is observed. Out of 100 samples, the percentage of cracks occurring is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and 80% or more. The upper limit is not particularly limited, but may be 100% or less, 95% or less, etc. The cracks can be measured in detail according to the method described in the Examples below.

A cured product obtained by thermally curing a resin composition at 130° C. for 30 minutes and then at 180° C. for 30 minutes usually exhibits excellent adhesion to the plating. Therefore, the cured product provides an insulating layer with excellent adhesion to the plated conductor layer. Plating adhesion (peel strength) is preferably 0.30 kgf/cm or more, more preferably 0.35 kgf/cm or more, still more preferably 0.40 kgf/cm or more. The upper limit of plating adhesion may be 10 kgf/cm or less. Plating adhesion can be measured according to the method described in the Examples below.

A cured product obtained by thermally curing a resin composition at 200° C. for 90 minutes usually exhibits a low dielectric loss tangent. Therefore, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.004 or less, more preferably 0.0035 or less, and still more preferably 0.003 or less. On the other hand, the lower limit of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples described later.

A cured product having excellent crack resistance can be obtained from the resin composition. 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).

In addition, in the multilayer printed wiring board described below, a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and an interlayer insulating layer of a printed wiring board are used. It can be suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board.

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

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

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, more preferably 30 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.

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 resin sheet may further include other layers as necessary. Examples of such other layers include, for example, 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 resin sheet, 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 resin sheet can be stored by winding it up into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

A printed wiring board can be manufactured, for example, using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(I) Step of laminating the resin composition layer of the resin sheet on the inner layer substrate so as to bond with the inner layer substrate. (II) Step of thermosetting the resin composition layer to form an insulating layer.

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. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

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

The inner layer substrate and the resin sheet 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 resin sheets 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 thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are normally employed when 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 115°C or lower, more preferably 70°C or higher and 110°C or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 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.

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, in this step (IV), smear is also removed. 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", "Swelling Dip Securigance SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. It will be done. 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 permanganate 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 1 minute to 30 minutes. From the viewpoint of workability, etc., 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 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic mean roughness (Ra) 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. A metal layer is more preferred.

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.

[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.

EXAMPLES Hereinafter, the present invention will be explained in more detail using Examples, but the present invention is not limited to these Examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass," respectively.

<Synthesis Example 1: Synthesis of thermoplastic resin A having hyperbranched structure>
After adding acetone to 1.94 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and dissolving it in a reaction container, add 0.922 g of cyanuric acid chloride, both terminal amine-modified silicone oil (Shin-Etsu Co., Ltd.) Add 0.946 g of "KF-8010" manufactured by Kagaku Kogyo Co., Ltd. and 0.553 g of N-phenyl-3-aminopropyltrimethoxysilane ("KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd.) and react overnight at 50 ° C. I let it happen. Thereafter, ethyl acetate was added to perform extraction, and insoluble materials were removed by filtration. Next, the filtrate was washed with water, dehydrated with anhydrous magnesium sulfate, and the solvent was concentrated and distilled off. The residue was crystallized with methanol to obtain a thermoplastic resin A having a hyperbranched structure as shown below (R represents a methylene group or a phenylene group). The weight average molecular weight of thermoplastic resin A was measured to be 21,600. Further, the glass transition temperature of thermoplastic resin A was measured and found to be 80°C.

<Synthesis Example 2: Synthesis of thermoplastic resin B having hyperbranched structure>
In Synthesis Example 1,
1.94 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was changed to 2.37 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.
A thermoplastic resin B having a hyperbranched structure having the following structure was obtained in the same manner as in Synthesis Example 1 except for the above matters. The weight average molecular weight of thermoplastic resin B was measured to be 10,200. Further, the glass transition temperature of thermoplastic resin B was measured and found to be 86°C.

<Synthesis Example 3: Synthesis of thermoplastic resin C having hyperbranched structure>
In Synthesis Example 2,
The amount of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene was changed from 2.37g to 2.65g,
The amount of silicone oil modified with amines at both ends (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 0.946 g to 0.301 g.
A thermoplastic resin C having a hyperbranched structure was obtained in the same manner as in Synthesis Example 2 except for the above matters. The weight average molecular weight of the thermoplastic resin C was measured to be 8,800. Further, the glass transition temperature of the thermoplastic resin C was measured and found to be 92°C.

<Synthesis Example 4: Synthesis of thermoplastic resin D having hyperbranched structure>
In a reaction vessel, 1.24 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 3.83 g of bisphenol having a phenylene ether structure (SA90 manufactured by SABIC Innovative Plastics) were added to tetrahydrofuran. After adding and dissolving 0.922 g of cyanuric acid chloride, 0.946 g of silicone oil modified with amine at both ends (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.), and N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), 0.553 g of "KBE-903" (manufactured by Kagaku Kogyo Co., Ltd.) was added and reacted overnight at 50°C. Thereafter, ethyl acetate was added to perform extraction, and insoluble materials were removed by filtration. Next, the filtrate was washed with water, dehydrated with anhydrous magnesium sulfate, and the solvent was concentrated and distilled off. Thermoplastic resin D having a hyperbranched structure was obtained by crystallizing the residue with methanol. The weight average molecular weight of thermoplastic resin D was measured to be 14,200. Furthermore, the glass transition temperature of thermoplastic resin D was measured and was 76°C.

<Synthesis Example 5: Synthesis of thermoplastic resin E having hyperbranched structure>
In Synthesis Example 1,
The amount of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was changed from 1.94 g to 1.24 g,
The amount of silicone oil modified with amines at both ends (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 0.946 g to 2.88 g.
A thermoplastic resin E having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1 except for the above matters. The weight average molecular weight of thermoplastic resin E was measured to be 20,200. Further, the glass transition temperature of thermoplastic resin E was measured and found to be 78°C.

<Synthesis Example 6: Synthesis of thermoplastic resin F having hyperbranched structure>
In Synthesis Example 1,
0.553 g of N-phenyl-3-aminopropyltrimethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with N-phenyl-3-aminopropyltrimethoxysilane (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.638g.
A thermoplastic resin F having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1 except for the above matters. The weight average molecular weight of thermoplastic resin F was measured to be 24,500. Further, the glass transition temperature of the thermoplastic resin F was measured and was 76°C.

<Synthesis Example 7: Synthesis of thermoplastic resin G having hyperbranched structure>
In Synthesis Example 1,
0.553 g of N-phenyl-3-aminopropyltrimethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.451 g of 3-mercaptopropylmethyldimethoxysilane (“KBM-802” manufactured by Shin-Etsu Chemical Co., Ltd.) changed to
A thermoplastic resin G having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1 except for the above matters. The weight average molecular weight of the thermoplastic resin G was measured to be 18,900. Further, the glass transition temperature of the thermoplastic resin G was measured and found to be 76°C.

<Synthesis Example 8: Synthesis of thermoplastic resin H having hyperbranched structure>
After adding and dissolving 1.94 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 0.36 g of 1-naphthol in tetrahydrofuran in a reaction vessel, 0.922 g of cyanuric acid chloride, 0.946 g of silicone oil modified with amines at both ends (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was reacted at 50° C. overnight. Thereafter, ethyl acetate was added to perform extraction, and insoluble materials were removed by filtration. Next, the filtrate was washed with water, dehydrated with anhydrous magnesium sulfate, and the solvent was concentrated and distilled off. A thermoplastic resin H having a hyperbranched structure was obtained by crystallizing the residue with methanol. The weight average molecular weight of the thermoplastic resin H was measured to be 14,500. Further, the glass transition temperature of the thermoplastic resin H was measured and found to be 94°C.

<Synthesis Example 9: Synthesis of thermoplastic resin I having hyperbranched structure>
In Synthesis Example 1,
0.946 g of silicone oil modified with amines at both ends (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 1.47 g of silicone oil modified with amines at both ends (“X-22-9409” manufactured by Shin-Etsu Chemical Co., Ltd.).
A thermoplastic resin I having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1 except for the above matters. The weight average molecular weight of thermoplastic resin I was measured to be 19,200. Further, the glass transition temperature of the thermoplastic resin I was measured and found to be 78°C.

<Synthesis Example 10: Synthesis of thermoplastic resin J having hyperbranched structure>
In Synthesis Example 8,
0.946 g of silicone oil modified with amine at both ends (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with 3.24 g of silicone oil modified with phenol at both ends (KF-2201, manufactured by Shin-Etsu Chemical Co., Ltd.).
A thermoplastic resin J having a hyperbranched structure was obtained in the same manner as in Synthesis Example 8 except for the above matters. The weight average molecular weight of thermoplastic resin J was measured to be 28,400. Furthermore, the glass transition temperature of the thermoplastic resin J was measured and found to be 95°C.

<Synthesis Example 11: Synthesis of thermoplastic resin K having hyperbranched structure>
In Synthesis Example 6,
0.946 g of silicone oil modified with amine at both ends (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with 1.03 g of silicone oil modified with carbinol at both ends (KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.).
A thermoplastic resin K having a hyperbranched structure was obtained in the same manner as in Synthesis Example 6 except for the above matters. The weight average molecular weight of thermoplastic resin K was measured to be 9,800. Further, the glass transition temperature of thermoplastic resin K was measured and was found to be 81°C.

[Example 1. Preparation of resin composition 1]
Liquid epoxy resin (Nippon Steel Chemical & Materials "ZX1059", 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (mass ratio), epoxy equivalent: 169 g/eq) 5 parts, biphenyl type Heat 15 parts of epoxy resin (Nippon Kayaku Co., Ltd. "NC3000H", epoxy equivalent: approx. 290) and 2 parts of thermoplastic resin A with a hyperbranched structure synthesized in Synthesis Example 1 to 20 parts of toluene and 20 parts of MEK with stirring. Dissolved. After cooling the obtained solution to room temperature, 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent: 238, solid content 62% toluene solution), containing a triazine skeleton. 4 parts of phenolic curing agent (“LA-3018-50P” manufactured by DIC, 2-methoxypropanol solution with a hydroxyl equivalent of approximately 151 g/eq, solid content 50%), phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, non-volatile content) 10 parts of a 1:1 solution of MEK and cyclohexanone (30% by mass), 3 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution with a solid content of 10% by mass), an inorganic filler (amine-based silane coupling) Mix 150 parts of spherical silica (“SO-C2” manufactured by Admatex, average particle size 0.5 μm) surface-treated with a chemical agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) and disperse uniformly with a high-speed rotating mixer. Resin composition 1 was obtained.

[Example 2. Preparation of resin composition 2]
In Example 1, 6 parts of a carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent: about 216 g/eq, toluene solution with solid content of 50%) was used.
Resin composition 2 was obtained in the same manner as in Example 1 except for the above matters.

[Example 3. Preparation of resin composition 3]
In Example 1, 6 parts of a thermosetting resin having a phenylene ether structure ("SA-9000" manufactured by SABIC Innovative Plastics, a toluene solution with a solid content of 50%) was used.
Resin composition 3 was obtained in the same manner as in Example 1 except for the above matters.

[Example 4. Preparation of resin composition 4]
In Example 1, 3 parts of a maleimide compound ("BMI689" manufactured by Designer Molecules, maleimide group equivalent: 345) was used.
Resin composition 4 was obtained in the same manner as in Example 1 except for the above matters.

[Example 5. Preparation of resin composition 5]
In Example 2, 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent: 238, solid content 62% toluene solution) was mixed with an active ester curing agent (air water solution). The solution was changed to 40 parts of "PC1300-02-65MA" manufactured by Co., Ltd., a methyl amyl ketone solution with an active group equivalent of 199 g/eq and a solid content of 65% by mass.
Resin composition 5 was obtained in the same manner as in Example 2 except for the above matters.

[Example 6. Preparation of resin composition 6]
In Example 1, the amount of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was changed from 2 parts to 12 parts.
Resin composition 6 was obtained in the same manner as in Example 1 except for the above matters.

[Example 7. Preparation of resin composition 7]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin B having a hyperbranched structure synthesized in Synthesis Example 2.
Resin composition 7 was obtained in the same manner as in Example 2 except for the above matters.

[Example 8. Preparation of resin composition 8]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin C having a hyperbranched structure synthesized in Synthesis Example 3.
Resin composition 8 was obtained in the same manner as in Example 2 except for the above matters.

[Example 9. Preparation of resin composition 9]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin D having a hyperbranched structure synthesized in Synthesis Example 4.
Resin composition 9 was obtained in the same manner as in Example 2 except for the above matters.

[Example 10. Preparation of resin composition 10]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin E having a hyperbranched structure synthesized in Synthesis Example 5.
Resin composition 10 was obtained in the same manner as in Example 2 except for the above matters.

[Example 11. Preparation of resin composition 11]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin F having a hyperbranched structure synthesized in Synthesis Example 6.
Resin composition 11 was obtained in the same manner as in Example 2 except for the above matters.

[Example 12. Preparation of resin composition 12]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin G having a hyperbranched structure synthesized in Synthesis Example 7.
Resin composition 12 was obtained in the same manner as in Example 2 except for the above matters.

[Example 13. Preparation of resin composition 13]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin H having a hyperbranched structure synthesized in Synthesis Example 8.
Resin composition 13 was obtained in the same manner as in Example 2 except for the above matters.

[Example 14. Preparation of resin composition 14]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin I having a hyperbranched structure synthesized in Synthesis Example 9.
Resin composition 14 was obtained in the same manner as in Example 2 except for the above matters.

[Example 15. Preparation of resin composition 15]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin J having a hyperbranched structure synthesized in Synthesis Example 10.
Resin composition 15 was obtained in the same manner as in Example 2 except for the above matters.

[Example 16. Preparation of resin composition 16]
In Example 2, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was replaced with 2 parts of thermoplastic resin K having a hyperbranched structure synthesized in Synthesis Example 11.
Resin composition 16 was obtained in the same manner as in Example 2 except for the above matters.

[Comparative Example 1. Preparation of resin composition 17]
In Example 1, 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was not used.
Resin composition 17 was obtained in the same manner as in Example 1 except for the above matters.

[Preparation of resin sheet]
As a support, a polyethylene terephthalate film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C.) that was subjected to mold release treatment with an alkyd resin mold release agent ("AL-5" manufactured by Lintec Corporation) was prepared. .

Resin compositions 1 to 17 were each applied uniformly onto a support using a die coater so that the thickness of the resin composition layer after drying was 30 μm, and by drying at 70° C. to 95° C. for 3 minutes, A resin composition layer was formed on the support. Next, a rough surface of a polypropylene film ("Alphan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) was laminated as a protective film to the surface of the resin composition layer that was not bonded to the support. Thereby, a resin sheet A having a support, a resin composition layer, and a protective film in this order was obtained.

[Measurement of adhesion (peel strength) with plated conductor layer]
(1) Preparation of inner layer board Both sides of the glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) on which the inner layer circuit was formed are micro-coated. The copper surface was roughened by etching to a depth of 1 μm using an etching agent (“CZ8101” manufactured by MEC Corporation).

(2) Lamination of resin sheet The protective film was peeled off from resin sheet A to expose the resin composition layer. Using a batch vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then press-bonding at 120° C. and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of the resin composition layer Thereafter, the inner layer substrate on which the resin sheet was laminated was placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 180°C and heated for 30 minutes, The resin composition layer was thermally cured to form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate B having an insulating layer, an inner layer substrate, and an insulating layer in this order.

(4) Roughening treatment The cured substrate B was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

(Wet desmear treatment)
The cured substrate B was immersed in a swelling solution ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then immersed in an oxidizing agent solution (Atotech Japan Co., Ltd.). ``Concentrate Compact CP'' manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) at 80°C for 20 minutes, and then a neutralizing solution (Atotech Japan's ``Reduction''). Solution Securigant P" (sulfuric acid aqueous solution) was immersed at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Formation of conductor layer A conductor layer was formed on the roughened surface of the insulating layer according to a semi-additive method. That is, the cured substrate B after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then in an electroless copper plating solution at 25° C. for 20 minutes. Next, after performing an annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm, and annealing treatment was performed at 200° C. for 60 minutes. The obtained board is referred to as "evaluation board C."

(6) Measurement of peel strength The peel strength of the insulating layer and the plated conductor layer was measured in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut with a width of 10 mm and a length of 100 mm is made in the conductor layer of the evaluation board C, one end of which is peeled off, gripped with a grip, and cut vertically at a speed of 50 mm/min at room temperature. The load (kgf/cm) when 35 mm was peeled off was measured to determine the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Measurement of dielectric loss tangent]
The protective film was peeled off from resin sheet A, and the resin composition layer was thermally cured by heating at 200° C. for 90 minutes, and then the support was peeled off. The obtained cured product is referred to as "cured product D for evaluation." The cured product D for evaluation was cut into test pieces with a width of 2 mm and a length of 80 mm. Regarding the test piece, the dielectric loss tangent was measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using "HP8362B" manufactured by Agilent Technologies. Measurements were performed on three test pieces, and the average value was calculated.

[Measurement and evaluation of crack resistance]
(1) Lamination of resin sheet A Inner layer board (“MCL-E700G” manufactured by Hitachi Chemical Co., Ltd.) having circuit conductors (copper) formed on both sides with a wiring pattern of L/S = 8 μm/8 μm, thickness of conductor layer Resin sheet A, with the protective film removed, was laminated on both sides of the 35 μm, total thickness of 0.4 mm, residual copper rate of 40% so that the resin composition layer was in contact with the inner layer substrate. Such lamination is performed using a vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), and after vacuum suction at a temperature of 120°C for 30 seconds, the lamination is performed on a support under conditions of a temperature of 120°C and a pressure of 0.7 MPa. Then, it was laminated by pressing for 30 seconds through heat-resistant rubber. Next, pressing was performed for 60 seconds at a temperature of 120° C. and a pressure of 0.55 MPa using an SUS end plate under atmospheric pressure.

(2) Thermal curing of the resin composition layer Thereafter, the inner layer substrate on which the resin sheet was laminated was placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 180°C and heated for 30 minutes, The resin composition layer was thermally cured to form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate E having an insulating layer, an inner layer substrate, and an insulating layer in this order.

(3) Roughening treatment The cured substrate E was subjected to a desmear treatment as a roughening treatment. The desmear treatment was carried out in the same manner as (wet desmear treatment) described in the above [Adhesion with plated conductor layer] column to obtain a sample.

(4) Evaluation of crack resistance Of the insulating layer surfaces of the sample after desmear treatment, the insulating layer surface directly above the wiring pattern (L/S=8 μm/8 μm) of the inner layer substrate was observed. For 100 samples, it was confirmed whether or not cracks were generated on the surface of the insulating layer along the pattern shape of the inner layer substrate, and the percentage of samples with no cracks was determined. This ratio was calculated as "yield" and evaluated based on the following criteria.
〇: Yield is 50% or more ×: Yield is less than 50%

In Examples 1 to 16, it was confirmed that even when components (D) to (G) were not contained, the same results as in the above Examples were obtained, although there were differences in degree.

Claims (15)

(A) epoxy resin,
A resin composition comprising (B) a curing agent and (C) a thermoplastic resin having a hyperbranched structure. The resin composition according to claim 1, wherein component (C) has a cyclic structure. The resin composition according to claim 1, wherein component (C) has a phenylene ether skeleton. The resin composition according to claim 1, wherein component (C) has a siloxane structure. The resin composition according to claim 1, wherein component (C) has a triazine ring. The resin composition according to claim 1, wherein the weight average molecular weight of component (C) is 1,000 or more and 40,000 or less. Component (C) has a multi-branched structure in which a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound are alternately bonded, and the terminal has a structure derived from a monofunctional compound. The resin composition described. The resin composition according to claim 1, wherein component (C) is a resin having a glass transition temperature of 50°C or more and 150°C or less. The resin composition according to claim 1, wherein the terminal of component (C) contains either an alkoxysilyl group or an arylalkoxy group. (D) The resin composition according to claim 1, comprising an inorganic filler. The resin composition according to claim 10, wherein the content of component (D) is 50% by mass or more when the resin component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein component (B) contains an active ester curing agent. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 12 provided on the support. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 12. A semiconductor device comprising the printed wiring board according to claim 14.