JP6801608B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions, adhesive films, circuit boards, and semiconductor devices.

As a circuit board manufacturing technique, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer board is known. The insulating layer is generally formed by obtaining a resin composition layer as a coating film of a resin varnish containing the resin composition and curing the resin composition layer. For example, Patent Document 1 describes a resin composition containing an epoxy resin, a curing agent, and a fluororesin filler, and the content of the fluororesin filler is 50 with respect to the solid content of the resin composition. A resin composition having a mass% to 85% by mass has been described.

Japanese Unexamined Patent Publication No. 2016-166347

The resin composition for forming the insulating layer generally contains a large amount of thermosetting resin from the viewpoint of achieving high insulating performance. As the thermosetting resin, an epoxy resin or a curing agent thereof is usually used. It is also known that an inorganic filler is used as the filler to reduce the coefficient of thermal expansion of the cured product of the resin composition. On the other hand, the present inventor has studied the use of a fluorine-based filler as a filler in order to develop an insulating layer having a low dielectric constant.

However, the insulating layer formed by the cured product of the resin composition containing the fluorine-based filler tends to have low adhesion to the conductive layer formed on the insulating layer. Above all, the adhesion of the insulating layer was particularly low after passing through the ultra-accelerated high temperature and high humidity life test (HAST test). In order to improve the insulation reliability over a long period of time, it is desired that the insulating layer can exhibit high adhesion to the conductor layer even after the HAST test.

Further, when an adhesive film was produced using a resin composition containing a fluorine-based filler, the adhesive film tended to have a large resin flow when laminated with an inner layer substrate. Here, the resin flow refers to a phenomenon in which the resin composition flows out from a portion between the support of the adhesive film and the inner layer substrate when the adhesive film and the inner layer substrate are laminated. When this resin flow occurs, the resin composition layer usually protrudes outside the edge of the support of the adhesive film. Then, when the resin flow occurs, the thickness of the resin composition layer tends to be reduced at the end of the adhesive film by the amount of the outflowed resin composition. Therefore, when a large resin flow occurs, the thickness of the resin composition layer becomes non-uniform, making it difficult to control the thickness.

The present invention has been devised in view of the above problems, and it is possible to obtain an insulating layer having a low dielectric constant and high adhesion to the conductor layer after the HAST test, and further, it is possible to suppress the resin flow. It is an object of the present invention to provide an adhesive film having a layer containing the resin composition; a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition;

As a result of diligent studies to solve the above problems, the present inventor combines (A) an epoxy resin, (B) a curing agent, a predetermined amount of (C) rubber particles, and (D) a fluorine-based filler. As a result, it was found that the above-mentioned problems could be solved, and the present invention was completed.
That is, the present invention includes the following.

[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler.
A resin composition in which the amount of the component (C) is 0.1% by mass to 3% by mass with respect to 100% by mass of the non-volatile component in the resin composition.
[2] The resin composition according to [1], wherein the component (D) is a fluoropolymer particle.
[3] The resin composition according to [2], wherein the component (D) is polytetrafluoroethylene particles.
[4] The resin composition according to any one of [1] to [3], which comprises (E) an inorganic filler.
[5] The resin composition according to [4], wherein the component (E) is silica.
[6] The resin composition according to [4] or [5], wherein the amount of the component (E) is 5% by mass to 70% by mass with respect to 100% by mass of the non-volatile component in the resin composition.
[7] The item according to any one of [1] to [6], wherein the amount of the component (D) is 10% by mass to 80% by mass with respect to 100% by mass of the non-volatile component in the resin composition. Resin composition.
[8] The component (A) is selected from the group consisting of bisphenol A type epoxy resin, bixilenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type tetrafunctional epoxy resin and naphthol type epoxy resin. The resin composition according to any one of [1] to [7], which is one or more types of epoxy resins.
[9] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer of a circuit board.
[10] An adhesive film having a support and a resin composition layer containing the resin composition according to any one of [1] to [9] provided on the support.
[11] A circuit board including an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].
[12] A semiconductor device including the circuit board according to [11].

According to the present invention, an insulating layer having a low dielectric constant and having high adhesion to a conductor layer can be obtained after the HAST test, and further, a resin composition capable of suppressing a resin flow; An adhesive film having a layer containing the resin; a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition; can be provided.

FIG. 1 is a top view schematically showing the periphery of the end portion of the adhesive film laminated on the inner layer substrate in the embodiment.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

In the following description, the amount of each component in the resin composition is a value with respect to 100% by mass of the non-volatile component in the resin composition unless otherwise specified.

In the following description, the term "dielectric constant" refers to the relative permittivity unless otherwise specified.

[1. Outline of resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler. Here, the term "fluorine-based" means that it contains a fluorine atom. Further, the term "fluorine-based filler" refers to a filler containing a compound containing a fluorine atom as a material. Then, in this resin composition, the amount of (C) rubber particles is in a predetermined range.

According to such a resin composition, an insulating layer having a low dielectric constant and high adhesion to the conductor layer can be obtained after the HAST test, and further, the resin flow can be suppressed, which is a desired effect of the present invention. Can be obtained.

[2. (A) Epoxy resin]
Examples of the epoxy resin as the component (A) include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type epoxy resin. Trisphenol type epoxy resin, naphthol novolac 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, cyclohexane type epoxy Examples thereof include resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

As the epoxy resin (A), an aromatic epoxy resin is preferable from the viewpoint of reducing the average linear thermal expansion coefficient of the insulating layer. Here, the aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. Further, the aromatic skeleton is a chemical structure generally defined as aromatic, and includes not only a monocyclic structure such as a benzene ring but also a polycyclic aromatic structure such as a naphthalene ring and an aromatic heterocyclic structure. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, the epoxy resin (A) is a bisphenol A type epoxy resin, a bixylenel type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, and a naphthalene type 4 It is preferably one or more kinds of epoxy resins selected from the group consisting of functional epoxy resins and naphthol type epoxy resins, and bisphenol A type epoxy resins, bixilenol type epoxy resins and naphthol type epoxy resins are particularly preferable.

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

The epoxy resin includes a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") and a solid epoxy resin at a temperature of 20 ° C. (sometimes referred to as "solid epoxy resin"). There is. The resin composition may contain only the liquid epoxy resin or only the solid epoxy resin as the (A) epoxy resin, but may contain a combination of the liquid epoxy resin and the solid epoxy resin. Is preferable. By using the liquid epoxy resin and the solid epoxy resin in combination as the epoxy resin (A), the flexibility of the resin composition layer can be improved, and the breaking strength of the cured product of the resin composition can be improved. ..

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

Examples of the liquid epoxy resin 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 novolac type epoxy resin, and ester skeleton. Alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and glycidylamine type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type Epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "630" and "630LSD" manufactured by Mitsubishi Chemical Co., Ltd. (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; "PB-3600" (epoxy having a butadiene structure) manufactured by Daicel. Resin); "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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.

Examples of the solid epoxy resin include bixilenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Naftor type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenyl ethane type epoxy resin are preferable, and bixilenol type epoxy resin and biphenyl Aralkill type epoxy resin, naphthylene ether type epoxy resin, naphthalene type tetrafunctional epoxy resin and naphthol type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (HP6000) manufactured by DIC. Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" (naphthol) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Novorak type epoxy resin); Mitsubishi Chemical's "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical's "YX4000HK" (bixilenol type epoxy resin); Mitsubishi Chemical's "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" (bisphenol AF type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. Mitsubishi Chemical's "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical's "jER1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical's "jER1031S" (tetraphenylethane type epoxy resin) ; Can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin (A), their mass ratios (liquid epoxy resin: solid epoxy resin) are preferably 1: 0.1 to 1:15. It is more preferably 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 8. When the mass ratio of the liquid epoxy resin and the solid epoxy resin is in the above range, preferable adhesiveness can be obtained when used in the form of an adhesive film. Further, when used in the form of an adhesive film, sufficient flexibility can be obtained and handleability can be improved. Further, the breaking strength of the cured product of the resin composition can be effectively increased.

The epoxy equivalent of the epoxy resin (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and particularly preferably 110 to 1000. When the epoxy equivalent of the epoxy resin (A) is within the above range, the crosslink density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent is the mass of the resin containing 1 equivalent of the epoxy group, and can be measured according to JIS K7236.

The weight average molecular weight of the epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effect of the present invention. The weight average molecular weight of a resin such as an epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The amount of the epoxy resin (A) in the resin composition is preferably 5% by mass or more with respect to 100% by mass of the non-volatile component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. , More preferably 8% by mass or more, particularly preferably 10% by mass or more, preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less.

[3. (B) Hardener]
The curing agent as the component (B) usually has a function of reacting with the epoxy resin (A) to cure the resin composition. Examples of such (B) curing agent include active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. .. Further, the curing agent may be used alone or in combination of two or more.

As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester-based curing agent, two or more ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound having is preferable. The active ester-based curing agent is preferably 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. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Preferred specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. Examples include active ester compounds containing. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester-based curing agent include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC); "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure; acetylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing the above; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as active ester-based curing agents that are benzoylates of phenol novolac. Made); etc.

As the phenol-based curing agent and the naphthol-based curing agent, those having a novolak structure are preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd .; "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; manufactured by DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500"; and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 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-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and the like; prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Ronza Japan. , "BA230S75" (a prepolymer in which a part or all of bisphenol A disyanate is triazined to form a trimer) and the like.

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

Among the above, from the viewpoint of remarkably obtaining the desired effect of the present invention, the (B) curing agent is one or more selected from the group consisting of an active ester-based curing agent, a phenol-based curing agent, and a naphthol-based curing agent. Hardeners are preferred. Furthermore, an active ester-based curing agent is particularly preferable from the viewpoint of effectively lowering the dielectric constant of the cured product of the resin composition. Therefore, the (B) curing agent used in the resin composition preferably contains an active ester-based curing agent.

When an active ester-based curing agent is used, (B) the amount of the active ester-based curing agent with respect to 100% by mass of the curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more. Yes, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less. When the amount of the active ester-based curing agent is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively lowered.

The amount of the curing agent (B) in the resin composition is preferably 0.1% by mass or more, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 0.5% by mass or more, more preferably 1% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.

When the number of epoxy groups of the (A) epoxy resin is 1, the number of active groups of the (B) curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and is preferable. Is 1.5 or less, more preferably 1.2 or less, still more preferably 1 or less, and particularly preferably 0.8 or less. Here, the "(A) number of epoxy groups of the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. The "(B) number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the (B) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the (B) curing agent is in the above range when the number of epoxy groups of the (A) epoxy resin is 1, the desired effect of the present invention can be remarkably obtained, and more usually, the resin composition. The heat resistance of the cured product of the product is further improved.

[4. (C) Rubber particles]
The rubber particles as the component (C) are particles containing rubber, and usually function as an organic filler having rubber elasticity. By containing the rubber particles (C) in a predetermined amount, it is possible to suppress the resin flow of the resin composition and improve the adhesion of the cured product of the resin composition to the conductor layer after the HAST test. .. The amount of the rubber particles (C) in the resin composition is usually 0.1% by mass or more, preferably 0.3% by mass or more, particularly preferably 0.5, based on 100% by mass of the non-volatile component in the resin composition. It is mass% or more, usually 3 mass% or less, preferably 2.6 mass% or less, and particularly preferably 2.2 mass% or less.

As the rubber particles (C), for example, rubber particles that are insoluble in the organic solvent described later and are incompatible with the epoxy resin (A) and the curing agent (B) are used. Such rubber particles (C) can exist in a dispersed state in the resin varnish and the resin composition.

Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles and the like. Among them, core-shell type rubber particles are preferable from the viewpoint of remarkably obtaining the desired effect of the present invention.

The core-shell type rubber particles are rubber particles including a shell layer on the surface of the particles and a core layer inside the shell layer. For example, core-shell type rubber particles including a shell layer formed of a polymer having a relatively high glass transition temperature and a core layer formed of a polymer having a relatively low glass transition temperature can be mentioned. Of these, core-shell type rubber particles in which the shell layer is formed of a glassy polymer and the core layer is formed of a rubber-like polymer are preferable. In such a core-shell type rubber particle, the aggregation of the rubber particle can be suppressed, the dispersibility of the rubber particle in the resin component such as (A) epoxy resin and (B) curing agent can be enhanced by the shell layer, and The core layer can exhibit excellent rubber elasticity.

The core-shell type rubber particles may have a two-layer structure including only the shell layer and the core layer, but may further have a structure of three or more layers including an arbitrary layer. For example, the core-shell type rubber particles may include an arbitrary layer between the shell layer and the core layer, or may include an arbitrary layer inside the core layer. To give a specific example, the core-shell type rubber particles include a shell layer formed of a glassy polymer, a core layer formed of a rubbery polymer, and an arbitrary core layer formed of a glassy polymer inside the core layer. It may have a three-layer structure including a layer of.

In the core-shell type rubber particles, examples of the glassy polymer include acrylic polymers such as polymethylmethacrylate; styrene-based polymers such as polystyrene and styrene / divinylbenzene copolymers; Of these, acrylic polymers are preferable, and polymethylmethacrylate is particularly preferable. On the other hand, examples of the rubber-like polymer include acrylic rubber such as a homopolymer or copolymer of an acrylic monomer such as butyl acrylate; butadiene rubber such as polybutadiene; isoprene rubber; butyl rubber; and the like. Of these, acrylic rubber and butadiene rubber are preferable, and acrylic rubber is particularly preferable. Here, the term "acrylic monomer" includes an acrylic acid ester, a methacrylic acid ester, and a combination thereof.

Specific examples of core-shell type rubber particles include stafyroids "AC3832", "AC3816N", "IM401-Kai 7-17" manufactured by Aica Kogyo Co., Ltd .; "Metabrene KW-4426" manufactured by Mitsubishi Chemical Corporation; Dow Chemical Japan. Examples include the pararoid "EXL-2655" manufactured by the company.

Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include "XER-91" (average particle size 0.5 μm) manufactured by JSR Corporation.
Specific examples of the crosslinked styrene-butadiene rubber (SBR) particles include "XSK-500" (average particle size 0.5 μm) manufactured by JSR Corporation.
Specific examples of the acrylic rubber particles include Metabrene "W300A" (average particle size 0.1 μm) and “W450A” (average particle size 0.2 μm) manufactured by Mitsubishi Chemical Corporation.

(C) One type of rubber particles may be used alone, or two or more types may be used in combination.

The rubber particles (C) usually have an effect of increasing the toughness of the cured product of the resin composition. Therefore, the insulating layer formed of the cured product of the resin composition containing the rubber particles (C) is excellent in mechanical strength. Further, the rubber particles (C) usually have a stress relaxation action. Therefore, in the insulating layer formed of the cured product of the resin composition containing (C) rubber particles, the internal stress generated at the time of formation is relaxed by the (C) rubber particles. Therefore, since the residual stress of the insulating layer can be reduced, the mechanical strength of the insulating layer can also be increased.

The rubber particles (C) can be produced, for example, by increasing the molecular weight of the rubber component to a level at which it does not dissolve in the organic solvent and the resin component to form particles. Further, in particular, core-shell type rubber particles can be produced, for example, by seed-polymerizing one type or two or more types of monomers corresponding to each layer in a plurality of steps.

The average particle size of the rubber particles (C) is preferably 0.005 μm or more, more preferably 0.2 μm or more, preferably 1 μm or less, and more preferably 0.6 μm or less. (C) The average particle size of the rubber particles can be measured by using a dynamic light scattering method. Specifically, the rubber particles are uniformly dispersed in an appropriate organic solvent by a method such as ultrasonic waves, and the particle size distribution of the rubber particles is used using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). Can be prepared on the basis of mass, and its median diameter can be measured as the average particle size.

[5. (D) Fluorine-based filler]
The fluorine-based filler as the component (D) is a filler containing a compound containing a fluorine atom as a material. Fluorine-based fillers are generally particles. Therefore, as the (D) fluorine-based filler, particles containing a compound containing a fluorine atom as a material are usually used.

As the material of the (D) fluorine-based filler, a fluorine-based polymer is preferable from the viewpoint of reducing the dielectric constant of the insulating layer. Therefore, as the (D) fluorine-based filler, fluorine-based polymer particles are preferable.

Examples of the fluoropolymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-perfluorodio. Examples thereof include xol copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). These may be used individually by 1 type, and may be used in combination of 2 or more types.

Among these, polytetrafluoroethylene is preferable as the fluorine-based polymer from the viewpoint of particularly reducing the dielectric constant of the insulating layer. Therefore, as the (D) fluorine-based filler, polytetrafluoroethylene particles as particles containing polytetrafluoroethylene are preferable.

The weight average molecular weight of the fluoropolymer is preferably 5,000,000 or less, more preferably 4000000 or less, and particularly preferably 3000000 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The average particle size of the fluorine-based filler (D) is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, preferably 10 μm or less, more preferably 5 μm or less, particularly. It is preferably 4 μm or less. When the average particle size of the (D) fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and more usually, the (D) fluorine-based filler in the resin composition. Dispersibility can be improved.

(D) The average particle size of particles such as a fluorine-based filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a laser diffraction / scattering type particle size distribution measuring device can measure the particle size distribution of particles on a volume basis, and the average particle size can be obtained as the median diameter from the particle size distribution. As the measurement sample, those in which the particles are dispersed in a solvent by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

(D) Commercially available fluorine-based fillers include, for example, "Lubron L-2", "Lubron L-5", and "Lubron L-5F" manufactured by Daikin Industries, Ltd .; "FluoronPTFE L-170JE" manufactured by Asahi Glass Co., Ltd. , "Fluorine PTFE-172JE", "Fluorine PTFE L-173JE"; "KTL-500F", "KTL-2N", "KTL-1N" manufactured by Kitamura Co., Ltd .; "TLP10F-1" manufactured by Mitsui DuPont Fluorochemical Co., Ltd. ; Etc. can be mentioned.

(D) The fluorine-based filler may be surface-treated. For example, the (D) fluorine-based filler may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants, and anionic surfactants; inorganic fine particles; and the like. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Further, as the above-mentioned fluorine-based surfactant, a suitable non-particle-like fluorine-based polymer or fluorine-based oligomer may be used. Specific examples of fluorine-based surfactants include "Surflon S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co., Ltd .; "Mega Fvck F-251" and "Mega Fvck F-" manufactured by DIC Co., Ltd. 477 "," Mega Fvck F-553 "," Mega Fvck R-40 "," Mega Fvck R-43 "," Mega Fvck R-94 "; Neos" FTX-218 "," Futergent 610FM " ; Can be mentioned.

The amount of the (D) fluorine-based filler in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass, based on 100% by mass of the non-volatile component in the resin composition. The above is preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less. When the amount of the fluorine-based filler (D) is within the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced. it can.

Further, particularly when the resin composition contains (E) an inorganic filler, the amount of the (D) fluorine-based filler in the resin composition is 100 mass in total of the (D) fluorine-based filler and the (E) inorganic filler. With respect to%, it is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 35% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass. % Or less. When the amount of the fluorine-based filler (D) is within the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced. it can.

[6. (E) Inorganic filler]
In addition to the above-mentioned components, the resin composition may contain (E) an inorganic filler as an arbitrary component. Examples of the material of the inorganic filler as the component (E) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and 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, zirconate oxide, barium titanate, barium titanate titanate, barium zirconate titanate, calcium zirconate titer, zirconate zirconate, and zirconate titanate phosphate. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Of these, spherical silica is preferable. (E) The inorganic filler may be used alone or in combination of two or more.

Usually, the (E) inorganic filler is contained in the resin composition in the form of particles. The average particle size of the inorganic filler (E) 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 remarkably obtaining the desired effect of the present invention. It is preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. Further, when the average particle size of the (E) inorganic filler is in the above range, it is usually possible to improve the circuit embedding property of the resin composition layer and reduce the surface roughness of the insulating layer.

(E) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatex Co., Ltd. , "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatex. Examples thereof include "SO-C4", "SO-C2", and "SO-C1"; The average particle size of the (E) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory, as in the case of the (D) fluorine-based filler.

The inorganic filler (E) may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include coupling agents such as aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, and titanate-based coupling agents; alkoxysilane compounds; organosilazane compounds; and the like. Be done. By surface-treating with these surface-treating agents, the moisture resistance and dispersibility of the (E) inorganic filler can be enhanced.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Further, the surface treatment agent may be used alone or in combination of two or more.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (E) inorganic filler. (E) carbon content per unit surface area of the inorganic filler, (E) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, Particularly preferably, it is 0.2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. It is 0.5 mg / m ² or less.

The amount of carbon per unit surface area of the (E) inorganic filler is determined after the surface-treated (E) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter, may be abbreviated as “MEK”)). , Can be measured. Specifically, a sufficient amount of MEK and the (E) inorganic filler surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing the supernatant and drying the non-volatile component, the amount of carbon per unit surface area of the (E) inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

The amount of the (E) inorganic filler in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. It is more preferably 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and further preferably 40% by mass or less. When the amount of the inorganic filler (E) is at least the lower limit of the above range, the coefficient of thermal expansion of the cured product of the resin composition can be lowered, so that the warp of the insulating layer can be suppressed. Further, when the amount of the (E) inorganic filler is not more than the upper limit of the above range, the mechanical strength of the cured product of the resin composition can be improved, and in particular, the resistance to elongation can be improved.

[7. (F) Thermoplastic resin]
The resin composition may contain (F) a thermoplastic resin as an arbitrary component in addition to the above-mentioned components. Examples of the thermoplastic resin as the component (F) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , Polyether resin, polyether ether ketone resin, polyester resin and the like. Of these, a phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. One type of thermoplastic resin may be used alone, or two or more types may be used in combination.

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

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Corporation (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation; "YX6954BH30", "YX7553", "YX7553BH30", "YL7553BH30", manufactured by Mitsubishi Chemical Corporation. Examples thereof include "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

The polystyrene-equivalent weight average molecular weight of the (F) thermoplastic resin is preferably 8000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 70,000 from the viewpoint of significantly obtaining the desired effect of the present invention. Below, it is more preferably 60,000 or less, and particularly preferably 50,000 or less. (F) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by a gel permeation chromatography (GPC) method.

When the (F) thermoplastic resin is used, the amount of the (F) thermoplastic resin in the resin composition is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. It is 0.6% by mass or more, more preferably 0.7% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less.

[8. (G) Curing accelerator]
In addition to the above-mentioned components, the resin composition may contain (G) a curing accelerator as an arbitrary component. By using the (G) curing accelerator, curing can be accelerated when the resin composition is cured.

Examples of the (G) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators. Be done. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable, and amines are more preferable. A system curing accelerator is particularly preferable. The curing accelerator (G) may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. Of these, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 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 trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Imidazole compounds such as phenylimidazolin; and adducts of imidazole compounds and epoxy resins; Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide can be mentioned. Of these, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex 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 thereof include organic zinc 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 peroxide-based curing accelerator include cyclohexanone peroxide, tert-butylperoxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, and diisopropylbenzenehydro. Examples thereof include peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

As the peroxide-based curing accelerator, a commercially available product can be used, and examples thereof include "Park Mill D" manufactured by NOF CORPORATION.

When the (G) curing accelerator is used, the amount of the (G) curing accelerator in the resin composition is based on 100% by mass of the non-volatile component in the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably. It is 1% by mass or less.

[9. (H) Fluorine-based polymer or fluorine-based oligomer]
In addition to the above-mentioned components, the resin composition may contain a non-particle-like (H) fluorine-based polymer or a fluorine-based oligomer as an arbitrary component. As the fluorine-based polymer and the fluorine-based oligomer as the component (H), only the fluorine-based polymer may be used, only the fluorine-based oligomer may be used, or the fluorine-based polymer and the fluorine-based oligomer may be used in combination. This component (H) is a component that can be in the form of non-particles in the resin composition, and is usually excellent in compatibility with a resin component such as (A) epoxy resin. Further, since the component (H) contains a fluorine atom in its molecule, it has a high affinity for the (D) fluorine-based filler. Therefore, the component (H) functions as a surfactant at the interface between the (D) fluorine-based filler and the resin component, and the dispersibility of the (D) fluorine-based filler can be enhanced. By increasing the dispersibility of the (D) fluorine-based filler in this way, the surface roughness of the insulating layer after the roughening treatment can be reduced. Further, by using the component (H), the dielectric constant of the cured product of the resin composition can usually be lowered.

Examples of the fluorine-based polymer include "LE-605" manufactured by Kyoeisha Chemical Co., Ltd. Examples of the fluorine-based oligomer include DIC's Megafuck "F-556", "F-558", "F-561", "F-563", "F-569", "DS-21", and " Examples thereof include "R-40" and "R-41". Further, the component (H) may be used alone or in combination of two or more.

When the component (H) is used, the amount of the component (H) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass, based on 100% by mass of the non-volatile component in the resin composition. % Or more, particularly preferably 1.0% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the amount of the component (H) is in the above range, the surface roughness of the insulating layer after the roughening treatment can be reduced, and the dielectric constant of the cured product of the resin composition can be effectively lowered.

[10. (I) Coupling agent]
In addition to the above-mentioned components, the resin composition may contain (I) a coupling agent as an arbitrary component. By using the (I) coupling agent, the dispersibility of the (E) inorganic filler can be enhanced, so that the surface roughness of the insulating layer after the roughening treatment can be reduced.

Examples of the (I) coupling agent include the same ones as those mentioned as the surface treatment agent for the (E) inorganic filler. Further, (I) the coupling agent may be used alone or in combination of two or more.

When the (I) coupling agent is used, the amount of the (I) coupling agent in the resin composition is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. It is 0.2% by mass or more, particularly preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. (I) When the amount of the coupling agent is within the above range, the surface roughness of the insulating layer after the roughening treatment can be reduced.

[11. (J) Additive]
In addition to the above-mentioned components, the resin composition may further contain additives as arbitrary components. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners; defoamers; leveling agents; adhesion-imparting agents; colorants; flame retardants; etc. Can be mentioned. In addition, one type of additive may be used alone, or two types of additives may be used in any combination.

[12. Method for manufacturing resin composition]
The resin composition can be produced, for example, by mixing the compounding components with a solvent, if necessary, and stirring the mixture using a stirring device such as a rotary mixer. Further, especially when the component (H) is used, the (D) fluorine-based filler is used rather than the (D) fluorine-based filler and the (H) component mixed and then the other components are mixed. It is preferable to separately mix the component (H) with the other components. Thereby, the resin flow of the resin composition can be suppressed particularly effectively.

[13. Characteristics of resin composition]
The dielectric constant of the cured product of the above-mentioned resin composition can be lowered. Therefore, an insulating layer having a low dielectric constant can be obtained from the cured product of this resin composition. For example, when the resin composition is cured by the method described in Examples to obtain a cured product, the dielectric constant of the cured product is preferably 3.00 or less, more preferably 2.98 or less, and particularly preferably 2. It can be less than .97. Here, the dielectric constant of the cured product can be measured by the method described in Examples.

The resin composition described above can reduce the resin flow. Therefore, when the adhesive film produced by using this resin composition is laminated with the inner layer substrate, the outflow of the resin composition from the end portion of the adhesive film is suppressed and the thickness of the resin composition layer is changed unintentionally. Can be suppressed. For example, when an adhesive film having a resin composition layer having a thickness of 50 μm formed of the resin composition is laminated on the inner layer substrate by the method described in Examples, the resin flow amount can be preferably 3 mm or less. Then, by using such a resin composition, the thickness of the insulating layer can be easily controlled.

When the conductive layer is formed on the cured product layer of the resin composition described above, the adhesion between the cured product layer and the conductive layer can be improved even after the HAST test. Therefore, according to the cured product of the resin composition described above, an insulating layer having high adhesion to the conductor layer can be obtained after the HAST test. For example, by the method described in Examples, an insulating layer is formed by a cured product of a resin composition, and a conductor layer is formed on the insulating layer by plating. In this case, the peel strength after the HAST test is performed under the conditions described in the examples can be increased. Specifically, the peel strength after the HAST test can be set to 0.3 kgf / cm or more. The peel strength can be measured by the method described in Examples. Then, according to such an insulating layer, the adhesion between the insulating layer and the conductor layer can be improved for a long period of time.

The present inventor speculates the mechanism by which the above-mentioned effect is obtained by the above-mentioned resin composition as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
The (D) fluorine-based filler has an effect of lowering the dielectric constant of the cured product of the resin composition when combined with the (A) epoxy resin and (B) curing agent.
However, the (D) fluorine-based filler generally has a low affinity with a resin component such as (A) an epoxy resin. Therefore, when the (D) fluorine-based filler is contained in the resin composition in combination with the resin component, the interaction between the fluorine-based filler and the resin component is small, so that the fluidity of the resin composition is high. Therefore, when the (D) fluorine-based filler was used, the resin flow of the resin composition was increased. On the other hand, when the resin composition contains (C) rubber particles, the (C) rubber particles have a high affinity for the resin component, so that the thixotropic property of the resin composition can be enhanced. As a result, the fluidity of the resin composition at the time of laminating can be suppressed, and the resin flow can be suppressed.
In addition, the (D) fluorine-based filler usually has a large expansion and contraction due to a temperature change. Therefore, the (D) fluorine-based filler expands during the HAST test, and then the (D) fluorine-based filler shrinks when cooled. Then, in the cured product of the resin composition, stress due to expansion and contraction of the (D) fluorine-based filler is generated. Further, in general, since the affinity between the (D) fluorine-based filler and the resin component is low, the interface between the (D) fluorine-based filler and the resin component has poor binding properties. Therefore, when stress is applied to the cured product of the resin composition, the interface between the (D) fluorine-based filler and the resin component is likely to be peeled off and is likely to be a starting point of cracks. Therefore, after the HAST test, peeling may occur at the interface between the (D) fluorine-based filler and the resin component, or minute cracks may occur starting from the interface between the (D) fluorine-based filler and the resin component. As a result, the mechanical strength of the insulating layer is lowered, and the conductor layer tends to be easily peeled off due to destruction near the surface of the insulating layer. On the other hand, when the (C) rubber particles are used, the (C) rubber particles can absorb the stress generated by the expansion and contraction of the (D) fluorine-based filler due to the temperature change. Therefore, it is possible to suppress a decrease in the mechanical strength of the insulating layer due to the HAST test. Further, the rubber particles (C) have an action of increasing the toughness of the cured product of the resin composition. Therefore, even if the mechanical strength of the insulating layer is lowered by the HAST test, the decrease can be compensated for by the action of (C) improving the toughness of the rubber particles. Therefore, by using the cured product of the resin composition described above, an insulating layer having high adhesion to the conductor layer can be obtained after the HAST test.

[14. Uses of resin composition]
The resin composition of the present invention can be used as a resin composition for forming an insulating layer of a circuit board such as a printed circuit board. Among them, a build-up for forming an insulating layer in the manufacture of a circuit board by a build-up method. It is preferably used as a resin composition for forming an insulating layer.

In particular, utilizing the advantage of being able to obtain an insulating layer having a low dielectric constant, this resin composition is a resin composition for forming an insulating layer of a high-frequency circuit board (for forming an insulating layer of a high-frequency circuit board). It can be suitably used as a resin composition). Above all, this resin composition can be more preferably used as a resin composition for forming an interlayer insulating layer of a high-frequency circuit board (a resin composition for forming an interlayer insulating layer of a high-frequency circuit board). Here, the "high frequency circuit board" means a circuit board that can be operated even with an electric signal in a high frequency band. Further, the "high frequency band" usually means a band of 1 GHz or more, and the above resin composition is particularly effective in a band of 28 GHz to 80 GHz.

Further, since the insulating layer having a low dielectric constant can contribute to the reduction of the height of the circuit board, it is suitable for applications requiring a thin circuit board. Further, an insulating layer having a low dielectric constant facilitates impedance control of the circuit board, and is therefore suitable for increasing the degree of freedom in designing the circuit board. From this point of view, suitable uses of the resin composition include circuit boards such as motherboards, IC package boards, camera module boards, and fingerprint authentication sensor boards used in mobile devices. To give a specific example, the fingerprint authentication sensor may include an insulating layer included in a circuit board, a plurality of electrodes formed on the insulating layer, and an insulating coating in this order. In this fingerprint authentication sensor, fingerprint authentication is performed by utilizing the fact that the capacitance value of the capacitor formed by the finger, the electrode, and the insulating coating placed on the insulating coating differs between the concave portion and the convex portion of the fingerprint. It is said. In such a fingerprint authentication sensor, if the insulating layer can be made thin, the sensor itself can be miniaturized.

Further, as the resin composition of the present invention, resin compositions such as adhesive films, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and component embedding resins are used. Can be used for a wide range of applications.

[15. Adhesive film]
The above-mentioned resin composition can be applied in a varnish state and used for forming an insulating layer. However, industrially, it is preferable to use an adhesive film having a resin composition layer containing this resin composition for forming an insulating layer. The adhesive film includes a support and a resin composition layer provided on the support. The resin composition layer is a layer formed of the above-mentioned resin composition, and is sometimes referred to as an “adhesive layer”.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and particularly preferably 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, and the like.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern. As the support, a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN") or the like. Polyester; Polycarbonate (hereinafter sometimes referred to as "PC"); Acrylic polymer such as polymethylmethacrylate (hereinafter sometimes referred to as "PMMA"); Cyclic polyolefin; Triacetylcellulose (hereinafter sometimes referred to as "TAC"). ); Polyether sulfide (hereinafter sometimes referred to as "PES"); Polyether ketone; Polyethylene; Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and has excellent availability.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Of these, copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be subjected to a treatment such as a mat treatment, a corona treatment, or an antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent that can be used for the release layer of the support with the release layer include one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based mold release agents. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Ltd.; and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the adhesive film, for example, a resin varnish containing an organic solvent and a resin composition is prepared, the resin varnish is applied to a support using a coating device such as a die coater, and further dried to form a resin composition layer. It can be manufactured by allowing it to be produced.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol and the like. Carbitol solvent; aromatic hydrocarbon solvent such as toluene and xylene; amide solvent 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 can be carried out by a known method such as heating or blowing hot air. The drying conditions are set so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed. Usually, the resin composition layer is obtained as a film obtained by semi-curing a coating film of a resin varnish.

The adhesive film may include any layer other than the support and the resin composition layer, if necessary. For example, in the adhesive film, a protective film similar to the support may be provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust and the like from adhering to the surface of the resin composition layer and scratches. When the adhesive film has a protective film, the adhesive film can usually be used by peeling off the protective film. In addition, the adhesive film can be rolled up and stored.

[16. Prepreg]
The insulating layer may be formed by using a prepreg instead of the adhesive film. The prepreg can be formed by impregnating a sheet-shaped fiber base material with a resin composition.

The sheet-like fiber base material used for the prepreg is not particularly limited. As the sheet-shaped fiber base material, any fiber base material used as a base material for prepreg, such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and particularly preferably 600 μm or less. From the viewpoint of suppressing the depth of plating involved in the formation of the conductor layer to be small, the thickness of the sheet-shaped fiber base material is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is usually 1 μm or more, and may be 1.5 μm or more or 2 μm or more.

The prepreg can be produced by a method such as a hot melt method or a solvent method.
The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

[17. Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition described above. In one embodiment, the circuit board includes an inner layer board and an insulating layer provided on the inner layer board.

The "inner layer substrate" is a member that serves as a base material for a circuit board. Examples of the inner layer substrate include those including a core substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, usually, the inner layer substrate includes a conductor layer directly or indirectly formed on one side or both sides of the core base material. The conductor layer may be patterned, for example, to function as an electrical circuit. An inner layer substrate in which a conductor layer is formed as a circuit on one side or both sides of a core substrate is sometimes called an "inner layer circuit board". Also included in the term "inner layer substrate" is an intermediate product in which at least one of an insulating layer and a conductor layer should be further formed in order to manufacture a circuit board. When the circuit board contains components, an inner layer board containing the components may be used.

The thickness of the inner layer substrate is usually 50 μm to 4000 μm, and is preferably 200 μm to 3200 μm from the viewpoint of improving the mechanical strength of the circuit board and reducing the height (reduction of the thickness).

The inner layer substrate may be provided with one or more through holes extending from one surface to the other in order to electrically connect the conductor layers on both sides thereof. Further, the inner layer substrate may be provided with additional components such as a passive element.

The insulating layer is a layer of a cured product of the resin composition. The insulating layer formed of this cured product is used for circuits such as circuit boards by build-up method, high frequency circuit boards, and motherboards, IC package boards, camera module boards, and fingerprint authentication sensor boards used in portable devices. It can be suitably applied to an insulating layer for a substrate.

The circuit board may have only one insulating layer, or may have two or more layers. When the circuit board has two or more insulating layers, it can be provided as a build-up layer in which conductor layers and insulating layers are alternately laminated.

The thickness of the insulating layer is usually 20 μm to 200 μm, and is preferably 50 μm to 150 μm from the viewpoint of improving the electrical characteristics and reducing the height of the circuit board.

The insulating layer may be provided with one or more via holes for electrically connecting the conductor layers of the circuit board.

Since the insulating layer is a layer formed by the cured product of the resin composition described above, the excellent properties of the cured product of the resin composition described above can be exhibited. Therefore, the insulating layer of the circuit board preferably has characteristics such as the dielectric constant of the insulating layer and the peel strength between the insulating layer and the conductive layer after the HAST test in the same range as described in the section of the characteristics of the resin composition. Can be adjusted to. In addition, these characteristics can be measured by the method described in Examples.

The circuit board can be manufactured by, for example, using an adhesive film by a manufacturing method including the following steps (I) and (II).
(I) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate.
(II) A step of thermosetting the resin composition layer to form an insulating layer.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by a heat-bonding step in which the adhesive film is heated while being pressed against the inner layer substrate from the support side. Examples of the member for the heat crimping step (also referred to as “heat crimping member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It should be noted that instead of pressing the heat-bonded member directly against the support of the adhesive film, the adhesive film sufficiently follows the unevenness of the surface of the inner layer substrate through an elastic material such as heat-resistant rubber. It is preferable to press.

Lamination of the inner layer substrate and the adhesive film can be carried out by, for example, a vacuum laminating method. In the vacuum laminating method, the temperature of heat crimping is preferably 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The pressure for heat crimping is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The time of heat crimping is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After the lamination, the laminated resin composition layer may be smoothed by pressing under normal pressure (atmospheric pressure), for example, from the support side with a heat-bonding member. The press conditions for the smoothing treatment can be the same as the conditions for heat-pressing the laminate. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermoset to form an insulating layer. The conditions for thermosetting the resin composition layer are not particularly limited, and the conditions adopted when forming the insulating layer of the circuit board can be arbitrarily adopted.

The thermosetting conditions of the resin composition layer also differ depending on, for example, the type of resin composition. The curing temperature of the resin composition layer is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably in the range of 170 ° C. to 200 ° C.). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermoset, 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 usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The method for manufacturing a circuit board may further include (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be carried out according to an appropriate method used for manufacturing a circuit board. When the support is removed after the step (II), the support is removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step. It may be carried out at any time between (IV) and step (V).

Step (III) is a step of drilling holes in the insulating layer. By drilling holes, holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be carried out by, for example, a method such as a drill, a laser, or a plasma, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the circuit board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and any procedure and conditions used in forming the insulating layer of the circuit board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

Examples of the swelling solution include an alkaline solution and a surfactant solution, and preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. Further, one type of swelling liquid may be used alone, or two or more types may be used in combination. The swelling treatment with the swelling liquid is not particularly limited. The swelling treatment can be performed, 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 of 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.

Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. In addition, one type of oxidizing agent may be used alone, or two or more types may be used in combination. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. 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 Security P" manufactured by Atotech Japan.

As the neutralizing solution, an acidic aqueous solution is preferable. Examples of commercially available products of the neutralizing solution include "Reduction Solution Security P" manufactured by Atotech Japan. In addition, one type of neutralizing solution may be used alone, or two or more types may be used in combination. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer roughened with an oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the insulating layer that has been roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

Step (V) is a step of forming a conductor layer. The material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is 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. Examples of the alloy layer include a layer formed from an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. for forming the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or a nickel-chromium alloy, copper. -Alloy layers of nickel alloys and copper / titanium alloys are preferable. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of a nickel-chromium alloy; is more preferable, and a single metal layer of copper is further preferable.

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

The thickness of the conductor layer is usually 3 μm to 200 μm, preferably 10 μm to 100 μm.

The conductor layer can be formed by directly patterning the metal foil used as the support of the adhesive film, for example. Further, the conductor layer can be formed by plating, for example. As a forming method by plating, for example, the surface of the insulating layer can be plated by a method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Above all, from the viewpoint of ease of production, it is preferable to form by the semi-additive method.

Hereinafter, an example of forming the conductor layer by the semi-additive method will be described. 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 part of the plating seed layer so as to correspond to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

The conductor layer may be formed, for example, by using a metal foil. When the conductor layer is formed using the metal foil, the step (V) is preferably carried out between the steps (I) and the steps (II). For example, after step (I), the support is removed and a metal leaf is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil can be carried out by a vacuum laminating method. The laminating conditions may be the same as the laminating conditions of the inner layer substrate and the adhesive film in the step (I). Then, step (II) is carried out to form an insulating layer. After that, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a method such as a subtractive method or a modified semi-additive method. The metal foil can be produced by, for example, an electrolytic method, a rolling method, or the like. Examples of commercially available metal foils include HLP foils and JXUT-III foils manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foils and TP-III foils manufactured by Mitsui Mining & Smelting Co., Ltd.

When the circuit board includes two or more insulating layers and a conductor layer (build-up layer), the circuit can be formed by repeating the above-described insulating layer forming step and conductor layer forming step one or more times. It is possible to manufacture a circuit board having a functionable multilayer wiring structure.

In other embodiments, the circuit board can be manufactured using a prepreg instead of the adhesive film. The manufacturing method using the prepreg is basically the same as the case of using the adhesive film.

[18. Semiconductor device]
The semiconductor device includes the circuit board described above. This semiconductor device can be manufactured using a circuit board.

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

A semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a circuit board. The "conduction point" is a "place where an electric signal can be transmitted on the circuit board", and the place may be a place on the surface of the circuit board or a place embedded in the circuit board. Absent. Further, as the semiconductor chip, an electric circuit element made of a semiconductor can be arbitrarily used.

As the mounting method of the semiconductor chip when manufacturing the semiconductor device, any method in which the semiconductor chip functions effectively can be adopted. Examples of the mounting method of the semiconductor chip include a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF). ) Can be mentioned. Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the circuit board and the semiconductor chip and the wiring of the circuit board are connected".

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Example 1]
20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Co., Ltd.), 10 parts of bixilenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd.), biphenyl aralkyl type epoxy resin (epoxy) Equivalent 276, 30 parts of Nippon Kayakusha "NC3000"), 10 parts of naphthol type epoxy resin (epoxy equivalent 332, Nippon Steel & Sumitomo Metal Chemical "ESN475V"), and phenoxy resin (methyl ethyl ketone / cyclohexanone with a solid content of 30% by mass) = 1/1 solution, 20 parts of "YL7553BH30" manufactured by Mitsubishi Chemical Corporation) was heated and dissolved in 60 parts of methyl ethyl ketone and 20 parts of cyclohexanone while stirring to obtain a resin solution.

To this resin solution, 15 parts of an active ester curing agent (active group equivalent 223, toluene solution of 65% by mass of non-volatile component, "HPC8000-65T" manufactured by DIC), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, solid). 50% by mass 2-methoxypropanol solution, 25 parts of "LA3018-50P" manufactured by DIC), 4 parts of curing accelerator (4-dimethylaminopyridine (DMAP), methyl ethyl ketone solution with 5% by mass of solid content), N- 100 parts of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm) surface-treated with phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shinetsu Chemical Co., Ltd.), polytetrafluoroethylene particles (Daikin Kogyo Co., Ltd. "Lubron L-2", average particle size 3 μm) 80 parts, core-shell type rubber particles (Aika Kogyo Co., Ltd. "AC3816N") 2 parts, and non-particulate fluorine-containing polymer (Kyoeisha Chemical Co., Ltd.) "LE-605") 4 parts were mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin varnish.

As a support, a polyethylene terephthalate film (thickness 38 μm, “AL5” manufactured by Lintec Corporation) having an alkyd resin-based release layer on the surface was prepared. The resin varnish was uniformly applied onto the support using a die coater. The applied resin varnish was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 6 minutes to form a resin composition layer, and an adhesive film having a support and a resin composition layer was obtained. The thickness of the resin composition layer was 50 μm, and the amount of residual solvent in the resin composition was about 2% by mass.

Next, the adhesive film was wound into a roll while adhering a polypropylene film having a thickness of 15 μm to the surface of the resin composition layer. The wound adhesive film was slit to a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Example 2]
The amount of core-shell type rubber particles (“AC3816N” manufactured by Aica Kogyo Co., Ltd.) was changed from 2 parts to 6 parts. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 3]
80 parts of polytetrafluoroethylene particles (“Lubron L-2” manufactured by Daikin Industries, Ltd.) and 4 parts of a fluorine-containing polymer (“LE-605” manufactured by Kyoeisha Chemical Co., Ltd.) were mixed in advance and then mixed with a resin solution. .. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 4]
30 parts of biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000") was changed to 27 parts of naphthylene ether type epoxy resin (epoxy equivalent 260, DIC Corporation "HP6000").
Further, two parts of core-shell type rubber particles (“AC3816N” manufactured by Aika Kogyo Co., Ltd.), core-shell type rubber particles (“IM401-7-17” manufactured by Aika Kogyo Co., Ltd.), the core is polybutadiene, and the shell is a styrene / divinylbenzene copolymer. ) Changed to 2 copies. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 5]
30 parts of biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000"), 20 parts of naphthylene ether type epoxy resin (epoxy equivalent 260, DIC company "HP6000"), and naphthalene type tetrafunctional epoxy resin (epoxy) Equivalent 163, changed to 5 copies of "HP4700" manufactured by DIC). Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 6]
15 parts of active ester curing agent (toluene solution of 65% by mass of non-volatile component, "HPC8000-65T" manufactured by DIC) and cresol novolac type curing agent containing triazine skeleton (2-methoxypropanol solution having 50% by mass of solid content, manufactured by DIC) 25 parts of "LA3018-50P"), 15 parts of naphthol type curing agent (hydroxyl equivalent 215, "SN485" manufactured by Nippon Steel & Sumitomo Metal Corporation) and triazine-containing phenol novolac resin (hydroxyl equivalent 125, solid content 60% methyl ethyl ketone solution, DIC) Changed to 12 copies of "LA7054") manufactured by the company. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 7]
Two parts of N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) were further added to the resin varnish. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Comparative Example 1]
The amount of core-shell type rubber particles (“AC3816N” manufactured by Aica Kogyo Co., Ltd.) was changed from 2 parts to 0 parts. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Comparative Example 2]
Epoxy resin (epoxy equivalent 190, solid content 80% by weight methyl ethyl ketone solution, manufactured by Daicel Chemical Co., Ltd., in which two parts of core-shell type rubber particles (“AC3816N” manufactured by Aika Kogyo Co., Ltd.) can function as non-particle-shaped rubber. PB3600M ") Changed to 2.5 copies. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Comparative Example 3]
The amount of core-shell type rubber particles (“AC3816N” manufactured by Aica Kogyo Co., Ltd.) was changed from 2 parts to 12 parts. Except for the above items, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Measurement of permittivity]
A polyethylene terephthalate film (“PET501010” manufactured by Lintec Corporation) having a mold release treatment on its surface was prepared. The resin varnishes obtained in Examples and Comparative Examples were uniformly applied onto the polyethylene terephthalate film using a die coater so that the thickness of the resin composition layer after drying was 50 μm. The applied resin varnish was dried at 80 ° C. to 110 ° C. (average 95 ° C.) for 6 minutes to obtain a resin composition layer. Then, the resin composition layer was heat-treated at 200 ° C. for 90 minutes to be cured, and the support was peeled off to obtain a cured product film formed of the cured product of the resin composition. The cured film was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

For this evaluation sample, the dielectric constant of the cured product of the resin composition was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an analyzer (“HP8362B” manufactured by Agilent Technologies). The rate was measured. The measurement was performed on two test pieces, and the average value was calculated.

[Measurement of resin flow amount]
An inner layer substrate (glass cloth base material epoxy resin double-sided copper-clad laminate, copper foil thickness 18 μm, substrate thickness 0.8 mm, “R5715ES” manufactured by Matsushita Electric Works, Ltd.) was prepared. The adhesive film produced in Examples and Comparative Examples is brought into contact with the inner layer substrate by using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). As described above, it was laminated on both sides of the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

After that, the edge of the adhesive film laminated on the inner layer substrate was observed. FIG. 1 is a top view schematically showing the periphery of the end portion of the adhesive film 100 laminated on the inner layer substrate 200 in the embodiment. As a result of the above observation, as shown in FIG. 1, it was observed that the resin composition layer 110 of the adhesive film 100 protruded from the edge 120E of the support 120 of the adhesive film 100. The protrusion of the resin composition layer 110 is formed by the resin composition layer 110 fluidized during laminating flowing out in the in-plane direction parallel to the surface 200U of the inner layer substrate 200. Therefore, the distance W from the edge 120E of the support 120 of the adhesive film 100 to the tip 110T of the protruding resin composition layer 110 was measured, and this distance W was determined as the amount of resin flow. Then, the one having a resin flow amount of 3 mm or less was judged as "◯", and the one having a resin flow amount larger than 3 mm was judged as "x".

[Measurement of peel strength]
(1) Base treatment of inner layer substrate:
A glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R5715ES” manufactured by Matsushita Electric Works, Ltd.) on which an inner layer circuit was formed was prepared as an inner layer substrate. Both sides of the inner layer substrate were etched by 1 μm with an etching agent (“CZ8100” manufactured by MEC) to roughen both copper surfaces of the inner layer substrate.

(2) Adhesive film lamination:
The adhesive film produced in Examples and Comparative Examples was subjected to a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate. , Laminated on both sides of the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of resin composition:
The adhesive film laminated on the inner layer substrate was heated at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to thermally cure the resin composition layer to form an insulating layer. Then, the polyethylene terephthalate film as a support was peeled off. As a result, a sample substrate having an insulating layer, an inner layer substrate, and an insulating layer in this order was obtained.

(4) Roughening treatment:
The sample substrate was immersed in a swollen solution (including "Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd. and diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes. Next, the sample substrate was immersed in a roughening solution (an aqueous solution of "Concentrate Compact P" KMnO ₄ : 60 g / L and NaOH: 40 g / L manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 20 minutes. Next, the sample substrate was immersed in a neutralizing solution (“Reduction Sholysine Securigant P” manufactured by Atotech Japan) at 40 ° C. for 5 minutes. Then, the sample substrate was dried at 80 ° C. for 30 minutes to obtain a roughened substrate.

(5) Plating by semi-additive method:
The roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Then, the roughened substrate was annealed by heating at 150 ° C. for 30 minutes. An etching resist was formed on the roughened substrate after the annealing treatment, and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm on the surface of the insulating layer. Next, an annealing treatment was performed by heating at 180 ° C. for 30 minutes to obtain a circuit board having a conductor layer on the insulating layer.

(6) Measurement of peeling strength (peeling strength) of the plated conductor layer:
A notch was made in the conductor layer of the circuit board so as to surround a rectangular portion having a width of 10 mm and a length of 100 mm. One end of this rectangular portion in the length direction was peeled off and grasped with a grasping tool (autocom type testing machine "AC-50CSL" manufactured by TSE Co., Ltd.). Then, at room temperature, at a speed of 50 mm / min, a peeling test was conducted to peel off the conductor layer in the direction perpendicular to the surface of the circuit board, and the load (kgf / cm) when the length of 35 mm was peeled off was the peel strength. Was measured as. Those having a peel strength of 0.3 kgf / cm or more were judged as “◯”. Further, those having a peel strength of less than 0.3 kgf / cm and those having swelling were judged as "x".

[Measurement of peel strength after HAST test]
An accelerated environment test was conducted in which the circuit board was exposed to an environment at a temperature of 130 ° C. and a humidity of 85% RH for 100 hours using an advanced accelerated life test device (“PM422” manufactured by Kusumoto Kasei Co., Ltd.). After that, the peel strength when the conductor layer of the circuit board was peeled off was measured by the same operation as the step (6) "Measurement of the peeling strength (peeling strength) of the plated conductor layer" in the above [Measurement of peel strength]. ..
Those having a peel strength of 0.3 kgf / cm or more after the accelerated environment test were judged as "◯", and those having a peel strength of less than 0.3 kgf / cm were judged as "x".

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the amount of each component represents the mass part of the non-volatile component. In the table below, the meanings of the abbreviations are as follows.
828US: Liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation).
YX4000HK: Bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation).
NC3000: Biphenyl aralkyl type epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.).
HP6000: Naftylene ether type epoxy resin (epoxy equivalent 260, "HP6000" manufactured by DIC Corporation).
HP4700: Naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" manufactured by DIC Corporation).
ESN-475V: Naftor type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
PB3600M: Epoxy resin having a polybutadiene structure that can function as a non-particle rubber (epoxy equivalent 190, solid content 80% by weight methyl ethyl ketone solution, "PB3600M" manufactured by Daicel Chemical Co., Ltd.).
HPC8000-65T: Active ester curing agent (active group equivalent 223, non-volatile component 65% by mass toluene solution, "HPC8000-65T" manufactured by DIC).
SN485: Naftor type curing agent (hydroxyl equivalent 215, "SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
LA3018-50P: Triazine skeleton-containing cresol novolac type curing agent (2-methoxypropanol solution having a phenol equivalent of 151 and a solid content of 50% by mass, "LA3018-50P" manufactured by DIC Corporation).
LA7054: Triazine-containing phenol novolac resin (methyl ethyl ketone solution having a hydroxyl group equivalent of 125 and a solid content of 60%, "LA7054" manufactured by DIC Corporation).
AC3816N: Core-shell type rubber particles (“AC3816N” manufactured by Aica Kogyo Co., Ltd.).
IM401-Kai 7-17: Core-shell type rubber particles ("IM401-Kai 7-17" manufactured by Aica Kogyo Co., Ltd., core is polybutadiene, shell is styrene / divinylbenzene copolymer).
Lubron L-2: Polytetrafluoroethylene particles (“Lubron L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm).
SO-C2: Spherical silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatex Co., Ltd., average particle size 0.5 μm).
YL7553BH30: Phenoxy resin (methyl ethyl ketone / cyclohexanone = 1/1 solution having a solid content of 30% by mass, "YL7553BH30" manufactured by Mitsubishi Chemical Corporation).
DMAP: Curing accelerator (4-dimethylaminopyridine, methyl ethyl ketone solution having a solid content of 5% by mass).
LE605: Non-particulate fluorine-containing polymer (“LE-605” manufactured by Kyoeisha Chemical Co., Ltd.).
KBM573: N-Phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.).

[Consideration]
As can be seen from Table 1, a low dielectric constant is obtained in the examples. Further, in the examples, the resin flow amount is small and the peel strength after the HAST test is large. Therefore, from this result, according to the present invention, it is possible to obtain an insulating layer having a low dielectric constant and high adhesion to the conductor layer after the HAST test, and further to realize a resin composition capable of suppressing the resin flow. Was confirmed.

Further, from the results of (C) Comparative Example 1 containing no rubber particles and Comparative Example 3 in which the amount of rubber particles is excessive, in order to obtain the desired effect of the present invention, (C) rubber particles can be obtained. It turns out that the amount should be within a certain range. In particular, in Comparative Example 3, since the amount of (C) rubber particles was excessive, the mechanical strength of the resin composition was lowered, the peel strength before the HAST test was lowered, and (C) rubber particles were also lowered. It is considered that the influence of the expansion of the rubber was increased and the peel strength after the HAST test was lowered.

Further, from the result of Comparative Example 2 in which an epoxy resin (“PB-3600M” manufactured by Daicel Corporation) capable of functioning as a liquid rubber was used instead of (C) rubber particles, in order to obtain the desired effect of the present invention. Knows that particles should be used as the rubber component. In Comparative Example 2, it is considered that the resin flow amount was increased because the thixotropic property was not improved by using the non-particulate rubber component. Further, in Comparative Example 2, it is considered that the non-particulate rubber component could not sufficiently absorb the stress generated by the temperature change during the HAST test, so that the peel strength after the HAST test was lowered.

Further, when comparing Example 1 and Example 3, the amount of resin flow in Example 1 is smaller. Therefore, in order to effectively suppress the resin flow, it is better than mixing the (D) fluorine-based filler and the (H) fluorine-based polymer and then mixing the other components as in Example 1. , (D) It can be seen that it is preferable to mix the fluorine-based filler and (H) the fluorine-based polymer separately with other components.

It has been confirmed that even when the components (E) to (I) are not used in the above-mentioned examples, the same results as those in the above-mentioned examples are obtained, although the degree is different.

100 Adhesive film 110 Resin composition layer 120 Support 200 Inner layer substrate

Claims (11)

A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler.
The component (D) is a fluorinated polymer particle.
(C) the amount of the component with respect to 100 mass% of non-volatile components in the resin composition, Ri to 3% by mass 0.1% by mass,
Amount of the component (D), with respect to 100 wt% non-volatile components in the resin composition, Ru 20 weight% to 80% by mass, the resin composition. A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler.
The component (D) is a fluorinated polymer particle.
(C) the amount of the component with respect to 100 mass% of non-volatile components in the resin composition, Ri to 3% by mass 0.1% by mass,
The amount of the component (D) is 10% by mass to 80% by mass with respect to 100% by mass of the non-volatile component in the resin composition.
(B) A resin composition containing a compound having one or more active ester groups in one molecule, or a triazine skeleton-containing phenolic curing agent . The resin composition according to claim 1 or 2, wherein the component (D) is polytetrafluoroethylene particles. (E) The resin composition according to any one of claims 1 to 3, which contains an inorganic filler. The resin composition according to claim 4, wherein the component (E) is silica. The resin composition according to claim 4 or 5, wherein the amount of the component (E) is 5% by mass to 70% by mass with respect to 100% by mass of the non-volatile component in the resin composition. One type of component (A) selected from the group consisting of bisphenol A type epoxy resin, bixylenel type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type tetrafunctional epoxy resin and naphthol type epoxy resin. The resin composition according to any one of claims 1 to 6 , which is the above epoxy resin. The resin composition according to any one of claims 1 to 7 , which is used for forming an insulating layer of a circuit board. An adhesive film having a support and a resin composition layer containing the resin composition according to any one of claims 1 to 8 provided on the support. A circuit board including an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 8 . A semiconductor device comprising the circuit board according to claim 10 .

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