KR20190020622A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of obtaining an insulating layer having a low dielectric constant and high adhesiveness to a conductor layer after a HAST test, and also being able to inhibit resin flow. The resin composition comprises: (A) an epoxy resin; (B) a curing agent; (C) rubber particles; and (D) a fluorine-based filler, wherein the amount of the component (C) is 0.1-3 mass% relative to 100 mass% of a non-volatile component in the resin composition.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition, an adhesive film, a circuit board, and a semiconductor device.

BACKGROUND ART [0002] As a manufacturing technique of a circuit board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated on an inner layer substrate is known. The insulating layer is generally formed by obtaining a resin composition layer as a coating film of a resin varnish containing a resin composition and curing the resin composition layer. For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, and a fluorine resin filler, wherein the content of the fluorine resin filler is 50 to 85% by mass with respect to the solid content of the resin composition A resin composition is described.

Japanese Laid-Open 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 insulation performance. As the thermosetting resin, an epoxy resin or a curing agent thereof was generally used. It is also known to use an inorganic filler as a filler to lower the thermal expansion rate of the cured product of the resin composition. On the contrary, the present inventors have studied using 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. Among them, the adhesiveness of the insulating layer was particularly low after the ultra-accelerated high temperature and high humidity life test (HAST test). In order to increase 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 is produced using a resin composition containing a fluorine-based filler, the resin film tends to have a large resin flow during lamination with the inner layer substrate. Here, the resin flow refers to a phenomenon in which the resin composition flows out at 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 empties outward beyond the rim of the support of the adhesive film. When the resin flow occurs, the thickness of the resin composition layer at the end portion of the adhesive film tends to be thinner by the amount of the resin composition discharged. As a result, when a large resin flow occurs, the thickness of the resin composition layer becomes uneven and it becomes difficult to control the thickness.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a resin composition capable of obtaining an insulating layer having a low dielectric constant and high adhesion to a conductor layer after HAST test, An adhesive film having a layer containing the resin composition; And a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

The inventor of the present invention has conducted intensive studies to solve the above problems and found that the above problems can be solved by combining (A) an epoxy resin, (B) a curing agent, a predetermined amount of (C) rubber particles and (D) And completed the present invention.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler, wherein the amount of the component (C) By mass to 0.1% by mass to 3% by mass.

[2] The resin composition according to [1], wherein the component (D) is a fluorine-based polymer particle.

[3] The resin composition according to [2], wherein the component (D) is a polytetrafluoroethylene particle.

[4] The resin composition according to any one of [1] to [3], which contains (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 to 70 mass% relative to 100 mass% of the nonvolatile component in the resin composition.

[7] The resin composition according to any one of [1] to [6], wherein the amount of the component (D) is 10 to 80 mass% with respect to 100 mass% of the nonvolatile component in the resin composition.

[8] The positive resist composition as described in [8], wherein the component (A) is at least one compound selected from the group consisting of a bisphenol A epoxy resin, a biquileneol epoxy resin, a biphenylaralkyl epoxy resin, a naphthylene ether epoxy resin, a naphthalene type tetrafunctional epoxy resin and a naphthol epoxy resin (1) to (7), wherein the epoxy resin is at least one epoxy resin selected from epoxy resins.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer of a circuit board.

[10] An adhesive film comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [9], which is provided on the support.

[11] A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].

[12] A semiconductor device comprising the circuit board according to [11].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an insulating layer having a low dielectric constant and high adhesion to a conductor layer after HAST test, and capable of inhibiting resin flow; An adhesive film having a layer containing the resin composition; A circuit board and a semiconductor device including the insulating layer made of the cured product of the resin composition can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a top view schematically showing the periphery of an end portion of an adhesive film laminated on an inner layer substrate in the embodiment. FIG.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. It should be noted, however, that the present invention is not limited to the embodiments and examples described below, and can be arbitrarily changed without departing from the scope of the present invention and its equivalent scope.

In the following description, the amount of each component in the resin composition is a value relative to 100 mass% of the nonvolatile component in the resin composition unless otherwise specified.

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

[One. 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 a fluorine-containing compound. The term " fluorine-based filler " refers to a filler containing a fluorine-containing compound as a material. In this resin composition, the amount of the rubber particles (C) is in a predetermined range.

With such a resin composition, it is possible to obtain a desired effect of the present invention that an insulating layer having a low dielectric constant and high adhesiveness to a conductor layer after HAST test can be obtained and resin flow can be suppressed.

[2. (A) epoxy resin]

Examples of the epoxy resin as the component (A) include epoxy resins such as a bicyclanol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin , Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type Epoxy resins, glycidyl ester type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, A resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether Epoxy resins, there may be mentioned trimethyl olhyeong epoxy resin, tetraphenyl ethane epoxy resin. The epoxy resin may be used singly or in combination of two or more kinds.

As the epoxy resin (A), an aromatic epoxy resin is preferable from the viewpoint of lowering the average linear heat expansion coefficient of the insulating layer. Here, the aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. The aromatic skeleton is a chemical structure generally defined as an aromatic group, 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 obtaining the desired effect of the present invention remarkably, the epoxy resin (A) is preferably at least one selected from the group consisting of bisphenol A epoxy resin, biquileneol epoxy resin, biphenylaralkyl epoxy resin, naphthylene ether epoxy resin, Type tetrafunctional epoxy resin and naphthol-type epoxy resin, and bisphenol A-type epoxy resin, biquilene-type epoxy resin and naphthol-type epoxy resin are particularly preferable.

The resin composition preferably contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effect of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule to (A) 100% by mass of the nonvolatile component of the epoxy resin is preferably 50% by mass or more, More preferably not less than 60% by mass, particularly preferably not less than 70% by mass.

The epoxy resin includes epoxy resin (hereinafter sometimes referred to as " liquid epoxy resin ") which is in a liquid state at a temperature of 20 캜 and epoxy resin which is solid at a temperature of 20 캜 (sometimes referred to as " solid epoxy resin "). The resin composition may contain only (A) the liquid epoxy resin as the epoxy resin, or may contain only the solid epoxy resin, but it is preferable that the resin composition contains a combination of the liquid epoxy resin and the solid epoxy resin. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, the flexibility of the resin composition layer can be improved, or 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 novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine- , A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin and a naphthalene type epoxy resin are more preferable, and a bisphenol A type epoxy resin is particularly preferable.

Specific examples of the liquid epoxy resin include " HP4032 ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828US", "jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; 630 ", " 630LSD " (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ZX1059 " (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; EX-721 " (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "SEROCIDE 2021P" (an alicyclic epoxy resin having an ester skeleton) manufactured by DICEL Corporation; &Quot; PB-3600 " (epoxy resin having a butadiene structure) manufactured by Daicel Company; ZX1658 " and " ZX1658GS " (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., and the like. These may be used singly or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in a 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 epoxy resins such as bicalcylenol type epoxy resins, biphenylaralkyl type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, A bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenyl ethane type epoxy resin are preferable, and a biscylenol type epoxy resin, a biphenyl type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, Epoxy resin, biphenylaralkyl 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 Corporation; HP-4700 ", " HP-4710 " (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; HP-7200 " (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; EXA-7311-G4 "," EXA-7311-G4S ", and" HP6000 "(manufactured by DIC Corporation," HP-7200HH "," HP-7200H "," EXA-7311 " Naphthylene ether type epoxy resin); EPPN-502H " (trisphenol type epoxy resin) manufactured by Nihon Kayakusa; NC7000L " (naphthol novolak type epoxy resin) manufactured by Nihon Kayakusa; Quot; NC3000H ", " NC3000 ", " NC3000L ", and " NC3100 " (biphenylaralkyl type epoxy resin) manufactured by Nihon Kayakusa; "ESN475V" (naphthol type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; "ESN485" (naphthol novolak type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YX4000HK " (biquileneol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YX8800 " (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "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 Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; jER1010 " (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Quot; jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used singly or in combination of two or more.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:15, more preferably 1 : 0.5 to 1:10, particularly preferably 1: 1 to 1: 8. When the mass ratio of the liquid epoxy resin to the solid epoxy resin is in the above range, favorable tackiness can be obtained when used in the form of an adhesive film. In addition, when used in the form of an adhesive film, sufficient flexibility is obtained and handling properties 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, still more preferably 110 to 1000. When the epoxy equivalent of the epoxy resin (A) is within the above range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is a mass of a resin containing one equivalent of an epoxy group, and can be measured in accordance with JIS K7236.

The weight average molecular weight of the epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500 from the viewpoint of obtaining the desired effect of the present invention. The weight average molecular weight of a resin such as an epoxy resin is a weight average molecular weight in terms of polystyrene 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, more preferably 5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability Is not less than 8% by mass, particularly preferably not less than 10% by mass, preferably not more than 70% by mass, more preferably not more than 50% by mass, particularly preferably not more than 30% by mass.

[3. (B) Curing agent]

The curing agent as the component (B) generally has a function of reacting with the epoxy resin (A) to cure the resin composition. Examples of the curing agent (B) include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. The curing agent may be used singly or in combination of two or more kinds.

As the active ester type curing agent, a compound having at least one active ester group in one molecule can be used. Among them, examples of the active ester-based curing agent include esters having two or more ester groups having high reactivity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds Compounds are preferred. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly, 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 and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specific preferred examples of the active ester curing agent include active ester compounds containing a dicyclopentadiene type phenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolak, benzoylphenol novolak And an active ester compound containing a cargo. Among them, an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T ", and" HPC-8000-65T "as active ester compounds containing a dicyclopentadiene type diphenol structure as commercial products of the active ester- 8000H-65TM "," EXB-8000L-65TM "and" EXB-8150-65T "(manufactured by DIC); EXB9416-70BK " (manufactured by DIC) as an active ester compound containing a naphthalene structure; &Quot; DC808 " (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing acetylated phenol novolak; &Quot; YLH1026 " (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing benzoylated phenol novolak; &Quot; DC808 " (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is acetylated phenol novolak; YLH1026 " (manufactured by Mitsubishi Chemical Corporation), " YLH1030 " (manufactured by Mitsubishi Chemical Corp.), and " YLH1048 " (manufactured by Mitsubishi Chemical Corporation), which are benzoylates of phenol novolak.

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

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Showa Kasei; "NHN", "CBN", "GPH" manufactured by Nihon Kayakusa; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" and "SN375" manufactured by Shinnitsu Tetsu Sumikin Kagaku Co., TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Kokohoshi Co., Ltd., "P-d" manufactured by Shikoku Chemicals, and "F-a".

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins such as bis (4-cyanate phenyl) ether, and the like; Polyfunctional cyanate resins derived from phenol novolak and cresol novolak; And prepolymerized prepolymers of these cyanate resins. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230 , &Quot; BA230S75 " (a prepolymer obtained by trimerizing a part or all of bisphenol A dicyanate to form a trimer), and the like.

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

Among the above, from the viewpoint of obtaining the desired effect of the present invention remarkably, as the curing agent (B), at least one curing agent selected from the group consisting of an active ester curing agent, a phenol curing agent and a naphthol curing agent is preferable. From the viewpoint of effectively lowering the dielectric constant of the cured product of the resin composition, an active ester type curing agent is particularly preferable. Therefore, the curing agent (B) used in the resin composition preferably contains an active ester curing agent.

When the active ester type curing agent is used, the amount of the active ester type curing agent relative to 100 mass% of the (B) curing agent is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% , Preferably not more than 80 mass%, more preferably not more than 70 mass%, further preferably not more than 60 mass%. When the amount of the active ester type curing agent is within the above range, the desired effect of the present invention can be obtained remarkably, and 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, more preferably 0.5% by mass or more, and most preferably 0.5% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining the desired effect of the present invention. , More preferably not less than 1 mass%, preferably not more than 40 mass%, more preferably not more than 30 mass%, further preferably not more than 20 mass%.

When the number of epoxy groups in the epoxy resin (A) is 1, the number of active groups in the curing agent (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, Preferably 1.2 or less, more preferably 1 or less, particularly preferably 0.8 or less. Here, the "epoxy group number of the epoxy resin (A)" is a value obtained by adding up the values obtained by dividing the mass of the nonvolatile component (A) of the epoxy resin present in the resin composition by the epoxy equivalent. The term "(B) the number of active groups of the curing agent" is a value obtained by summing the values obtained by dividing the mass of the non-volatile component of the curing agent (B) present in the resin composition by the active group equivalent. When the number of active groups of the curing agent (B) in the case where the number of epoxy groups in the epoxy resin (A) is 1, the desired effect of the present invention can be obtained remarkably, and the heat resistance .

[4. (C) Rubber Particles]

The rubber particle as the component (C) is a rubber-containing particle and generally functions 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 to improve the adhesiveness 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 mass% or more, preferably 0.3 mass% or more, particularly preferably 0.5 mass% or more, relative to 100 mass% of the nonvolatile component in the resin composition, 3 mass% or less, preferably 2.6 mass% or less, particularly preferably 2.2 mass% or less.

As the rubber particles (C), for example, rubber particles which are not soluble in an organic solvent to be described later and which are not compatible with (A) the epoxy resin and (B) the curing agent are used. Such (C) rubber particles may exist in a resin varnish and in a dispersed state in 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. Of these, core-shell type rubber particles are preferred from the viewpoint of obtaining a desired effect of the present invention remarkably.

The core-shell-type rubber particles are rubber particles comprising a shell layer on the surface of the particle and a core layer inside the shell layer. For example, core-shell type rubber particles comprising 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. 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. Such core-shell type rubber particles can suppress the agglomeration of the rubber particles by the shell layer or increase the dispersibility of the rubber particles to resin components such as (A) the epoxy resin and (B) the curing agent, and , Excellent rubber elasticity can be exhibited.

The core-shell-type rubber particles may have a two-layer structure including only the shell layer and the core layer, but may also have a three-layer structure or more including any layer. For example, the core-shell-type rubber particle may include an arbitrary layer between the shell layer and the core layer, or may include an arbitrary layer in the core layer. Specifically, for example, the core-shell-type rubber particles may have a three-layer structure including a shell layer formed of a glassy polymer, a core layer formed of a rubbery polymer, and an optional layer formed of a glassy polymer inside the core layer.

In the core-shell type rubber particle, examples of the glassy polymer include acrylic polymers such as polymethyl methacrylate; Styrene polymers such as polystyrene, styrene-divinylbenzene copolymer and the like. Of these, an acrylic polymer is preferable, and polymethyl methacrylate is particularly preferable. On the other hand, examples of the rubber-like polymer include acrylic rubbers such as homopolymers or copolymers of acrylic monomers 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. Herein, the term " acrylic monomers " includes acrylic acid esters, methacrylic acid esters, and combinations thereof.

Specific examples of the core-shell type rubber particles include star filloids "AC3832", "AC3816N", "IM401-7-17" manufactured by AIKAGO Co., Ltd.; "Metablen KW-4426" manufactured by Mitsubishi Chemical Corporation; &Quot; EXL-2655 " manufactured by Dow Chemical Co., Ltd., and the like.

Specific examples of crosslinked acrylonitrile butadiene rubber (NBR) particles include "XER-91" (average particle diameter 0.5 μm) manufactured by JSR Corporation.

Specific examples of the crosslinked styrene-butadiene rubber (SBR) particles include "XSK-500" (average particle diameter 0.5 μm) manufactured by JSR Corporation.

Specific examples of the acrylic rubber particles include Metablen "W300A" (average particle diameter 0.1 μm) manufactured by Mitsubishi Chemical Corporation; And " W450A " (average particle diameter 0.2 mu m).

The rubber particles (C) may be used singly or in combination of two or more kinds.

The rubber particles (C) generally have an action 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 (C) rubber particles has excellent mechanical strength. The rubber particles (C) usually have a stress relaxation function. 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 rubber particles (C). Therefore, since the residual stress of the insulating layer can be reduced, the mechanical strength of the insulating layer can be increased.

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

The average particle diameter of the rubber particles (C) is preferably 0.005 탆 or more, more preferably 0.2 탆 or more, preferably 1 탆 or less, and more preferably 0.6 탆 or less. The average particle diameter of the (C) rubber particles can be measured using a dynamic light scattering method. Specifically, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic wave or the like, and the particle diameter distribution of the rubber particles is measured by using a dense particle diameter analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) And the median diameter can be measured as the average particle diameter.

[5. (D) Fluorine-based filler]

The fluorine-based filler as the component (D) is a filler containing a fluorine atom-containing compound as a material. The fluorine-based filler is generally in the form of particles. Therefore, as the fluorine-based filler (D), particles containing a fluorine atom-containing compound are usually used.

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

Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE) Polytetrafluoroethylene-perfluorodioxole copolymers (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE) And vinyl fluoride (PVF). These may be used singly or in combination of two or more.

Of 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 fluorine-based filler (D), 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 4,000,000 or less, and particularly preferably 3,000,000 or less, from the viewpoint of obtaining the desired result of the present invention remarkably.

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

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

Examples of commercially available products of the fluorine-based filler (D) include "Lubron L-2", "Lubron L-5" and "Lubron L-5F" manufactured by Daikin Corporation; "FluonPTFEL-170JE", "FluonPTFEL-172JE" and "FluonPTFEL-173JE" manufactured by Asahi Shosha; "KTL-500F", "KTL-2N" and "KTL-1N" manufactured by Kitamura Co., Ltd.; And " TLP10F-1 " manufactured by Mitsui " DuPont Fluorochemicals ".

The fluorine-based filler (D) may be surface-treated. For example, the fluorine-based filler (D) may be surface-treated with an optional 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. As the fluorine-based surfactant, a non-particulate fluorine-based polymer and a fluorine-based oligomer may be used. Specific examples of the fluorine-based surfactant include " SAFLON S-243 " (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seiyam Chemical Co., Ltd., " Megapak F- 477 "," Mega Park F-553 "," Mega Park R-40 "," Mega Park R-43 "," Mega Park R-94 "; &Quot; FTX-218 " and " Pptant 610FM " manufactured by NEOS Corporation; .

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

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

[6. (E) inorganic filler]

The resin composition may contain (E) an inorganic filler as an optional component in addition to the above components. As the material of the inorganic filler as the component (E), for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, , Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, Barium titanate, barium zirconate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable in view of obtaining the desired effect of the present invention remarkably. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Of these, spherical silica is preferred. The inorganic filler (E) may be used singly or in combination of two or more kinds.

Usually, the inorganic filler (E) is contained in the resin composition in the form of particles. The average particle diameter of the inorganic filler (E) is preferably not less than 0.01 탆, more preferably not less than 0.05 탆, particularly preferably not less than 0.1 탆, from the viewpoint of obtaining the desired effect of the present invention remarkably, More preferably not more than 5.0 mu m, further preferably not more than 2.0 mu m, further preferably not more than 1.0 mu m. When the average particle diameter of the inorganic filler (E) is in the above range, it is usually possible to improve the circuit embedding property of the resin composition layer or reduce the surface roughness of the insulating layer.

Examples of commercial products of the inorganic filler (E) include "SP60-05" and "SP507-05" manufactured by Shinnitetsu Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE" and "YA010C" manufactured by Adomatex Co., "UFP-30" manufactured by Denka Corporation; "Silphil NSS-3N", "Silphil NSS-4N" and "Silpil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Adomatex Co., Ltd. The average particle diameter of the inorganic filler (E) is the same as that of the fluorine-based filler (D), and can be measured by a laser diffraction / scattering method based on the Mie scattering theory.

The specific surface area of the inorganic filler (E) is preferably not less than 1 m 2 / g, more preferably not less than 2 m 2 / g, particularly preferably not less than 3 m 2 / g, from the viewpoint of obtaining a desired effect of the present invention to be. The upper limit is not particularly limited, but is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountain Tex) according to the BET method and calculating the specific surface area using the BET multi-point method.

The inorganic filler (E) may be surface-treated with any surface-treating agent. Examples of the surface treatment agent include coupling agents such as amino silane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents and titanate coupling agents; Alkoxysilane compounds; Organosilazane compounds, and the like. By the surface treatment with these surface treatment agents, the moisture resistance and dispersibility of the inorganic filler (E) can be enhanced.

Examples of commercial products of surface treatment agents include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxy silane manufactured by Shin- Silane), KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin- KBM-4803 " manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type, manufactured by Shin-Etsu Chemical Co., Silane coupling agents). The surface treatment agent may be used singly or in combination of two or more kinds.

The degree of the surface treatment by the surface treatment agent can be evaluated by the carbon amount per unit surface area of (E) the inorganic filler. The amount of carbon per unit surface area of the inorganic filler (E) is preferably not less than 0.02 mg / m 2, more preferably not less than 0.1 mg / m 2, and particularly preferably not less than 0.2 from the viewpoint of improving the dispersibility of the inorganic filler (E) Mg / m 2 or more. On the other hand, the amount of carbon is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less from the viewpoint of suppressing the melt viscosity of the resin varnish and the increase of the melt viscosity in the sheet form, 0.5 mg / m 2 or less.

The amount of carbon per unit surface area of the inorganic filler (E) is determined by cleaning the surface-treated inorganic filler (E) with a solvent (for example, methyl ethyl ketone (hereinafter may be abbreviated as "MEK" Can be measured. Specifically, a sufficient amount of MEK and inorganic filler (E) surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 占 폚 for 5 minutes. Subsequently, the non-volatile components are dried by removing the supernatant, and then the amount of carbon per unit surface area of the inorganic filler (E) can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

The amount of the inorganic filler (E) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, relative to 100% by mass of the nonvolatile component in the resin composition , More preferably not less than 20 mass%, preferably not more than 70 mass%, more preferably not more than 60 mass%, further preferably not more than 50 mass%, particularly preferably not more than 40 mass%. If the amount of the inorganic filler (E) is not lower than the lower limit of the above range, the thermal expansion rate of the cured product of the resin composition can be lowered, thereby suppressing the warping of the insulating layer. If the amount of the inorganic filler (E) 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 particularly the resistance to stretching can be increased.

[7. (F) Thermoplastic resin]

The resin composition may contain (F) a thermoplastic resin as an optional component in addition to the above components. Examples of the thermoplastic resin as the component (F) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, Resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Among them, a phenoxy resin is preferable from the viewpoint of obtaining a desired effect of the present invention remarkably. The thermoplastic resin may be used singly or in combination of two or more kinds.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include " 1256 " and " 4250 " (both phenol resin containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; FX280 " and " FX293 " manufactured by Shinnitetsu Sumikin Kagaku; "YX6954BH30", "YX7553", "YX7553BH30", "YL7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482" manufactured by Mitsubishi Chemical Co.,

The weight average molecular weight of the thermoplastic resin (F) in terms of polystyrene is preferably 8,000 or more, more preferably 10000 or more, particularly preferably 20,000 or more, from the viewpoint of obtaining the desired effect of the present invention remarkably, More preferably not more than 60000, particularly preferably not more than 50000. (F) The weight average molecular weight of the thermoplastic resin in terms of polystyrene can be measured by gel permeation chromatography (GPC).

When (F) a thermoplastic resin is used, the amount of the thermoplastic resin (F) in the resin composition is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, , More preferably not less than 0.7 mass%, preferably not more than 15 mass%, more preferably not more than 12 mass%, further preferably not more than 10 mass%.

[8. (G) Curing accelerator]

The resin composition may contain a curing accelerator (G) as an optional component in addition to the above components. By using the (G) curing accelerator, curing can be promoted when the resin composition is cured.

Examples of the (G) curing accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators and peroxide hardening accelerators. Of these, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable, and amine-based curing accelerators are particularly preferable. The amine-based curing accelerator is preferably an amine curing accelerator, an amine curing accelerator, an imidazole curing accelerator, desirable. The (G) curing accelerator may be used singly or in combination of two or more kinds.

Examples of phosphorus hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenyl Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Among them, 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) - diazabicyclo (5,4,0) undecene. Of these, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- Water, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 2-phenylimidazoline, Imidazole compounds; And adducts of an imidazole compound and an epoxy resin. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimazole are preferable.

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

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [ 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1- (o-tolyl) biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferred.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc An organic iron complex such as an organic zinc complex and iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex 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-butylperoxy benzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di- Propylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

As the peroxide-based curing accelerator, a commercially available product can be used. For example, " Percumyl D "

When the (G) curing accelerator is used, the amount of the (C) curing accelerator in the resin composition is preferably in the range of from 100 mass% to 100 mass% in the resin composition in view of obtaining the desired effect of the present invention More preferably not less than 0.01 mass%, more preferably not less than 0.03 mass%, particularly preferably not less than 0.05 mass%, preferably not more than 3 mass%, more preferably not more than 2 mass%, particularly preferably not more than 1 mass% .

[9. (H) fluorine-based polymer or fluorine-based oligomer]

The resin composition may contain a non-particulate (H) fluoropolymer or a fluoric oligomer as an optional component in addition to the above components. As the fluorine-based polymer and the fluorine-based oligomer as the component (H), only a fluorine-based polymer may be used, only a fluorine-based oligomer may be used, or a fluorine-based polymer and a fluorine-based oligomer may be used in combination. The component (H) is a component which can be a non-particulate phase in the resin composition and is generally excellent in compatibility with a resin component such as (A) an epoxy resin. The component (H) has a high affinity for the fluorine-based filler (D) because it contains fluorine atoms in the molecule. Therefore, the component (H) functions as a surfactant at the interface between the fluorine-based filler and the resin component (D), and the dispersibility of the fluorine-based filler (D) can be enhanced. And, as the dispersibility of the fluorine-based filler (D) is increased, the surface roughness of the insulating layer after the roughening treatment can be reduced. Therefore, by using the component (H), the dielectric constant of the cured product of the resin composition can be generally lowered.

As the fluorine-based polymer, for example, "LE-605" manufactured by Kyowa Chemical Industry Co., Ltd. and the like can be mentioned. Examples of the fluorine oligomer include Megapak® F-556, F-558, F-561, F-563, F-569, DS- R-40 ", " R-41 ", and the like. The component (H) may be used singly 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 or more, Particularly preferably not less than 1.0% by mass, preferably not more than 10% by mass, more preferably not more than 5% by mass, particularly preferably not more than 3% by mass. 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 or the dielectric constant of the cured product of the resin composition can be effectively lowered.

[10. (I) coupling agent]

The resin composition may contain (I) a coupling agent as an arbitrary component in addition to the above components. (I) coupling agent, the dispersibility of the inorganic filler (E) can be increased, so that the surface roughness of the insulating layer after the roughening treatment can be reduced.

Examples of the coupling agent (I) include the same ones as those listed as examples of the surface treating agent for the inorganic filler (E). The coupling agent (I) may be used singly or in combination of two or more.

(I) coupling agent is used, the amount of the coupling agent (I) in the resin composition is preferably 0.1% by mass or more, more preferably 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, particularly preferably 1% by mass or less. When the amount of the (I) coupling agent is in the above range, the surface roughness of the insulating layer after the roughening treatment can be reduced.

[11. (J) Additive]

The resin composition may further contain an additive as an optional component in addition to the above components. Examples of such additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; Thickener; Defoamer; Leveling agents; An adhesion imparting agent; coloring agent; Flame retardants and the like. The additives may be used singly or in a combination of two or more.

[12. Method of producing resin composition]

The resin composition can be produced, for example, by mixing the compounding ingredients with a solvent as required and stirring by using a stirring device such as a rotary mixer. When the component (H) is used, the fluorine-containing filler (D) and the component (H) are separately added to the fluorine-based filler and the component (H) It is preferable to mix it with other components. Thereby, the resin flow of the resin composition can be particularly effectively suppressed.

[13. Characteristics of Resin Composition]

The cured product of the resin composition described above can lower its dielectric constant. Therefore, an insulating layer having a low dielectric constant can be obtained by the cured product of the resin composition. For example, when a cured product is obtained by curing the resin composition by the method described in the examples, the dielectric constant of the cured product is preferably 3.00 or less, more preferably 2.98 or less, particularly preferably 2.97 or less . Here, the dielectric constant of the cured product can be measured by the method described in the examples.

The above resin composition can reduce the resin flow. Therefore, when the adhesive film produced by using the 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, thereby suppressing the unexpected change in the thickness of the resin composition layer . For example, when an adhesive film comprising a resin composition layer having a thickness of 50 mu m formed by the resin composition is laminated on the inner layer substrate by the method described in the embodiment, the resin flow amount is preferably set to 3 mm or less . By using such a resin composition, it is possible to easily control the thickness of the insulating layer.

When the conductive layer is formed on the layer of the cured product of the resin composition, adhesion between the layer of the cured product and the conductive layer can be increased even after the HAST test. Therefore, the cured product of the resin composition described above can provide an insulating layer having high adhesion to the conductor layer after the HAST test. For example, an insulating layer is formed by a cured product of a resin composition by the method described in the embodiment, and a conductor layer is formed on the insulating layer by plating. In this case, the peel strength after the HAST test 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 the examples. By this insulating layer, the adhesion between the insulating layer and the conductor layer can be improved over a long period of time.

The inventors of the present invention conjecture that the above-mentioned effect can be obtained by the above-mentioned resin composition. However, the technical scope of the present invention is not limited by the structure described below.

The fluorine-based filler (D) has an effect of lowering the dielectric constant of the cured product of the resin composition when it is combined with the epoxy resin (A) and the curing agent (B).

However, the fluorine-based filler (D) generally has a low affinity with a resin component such as (A) an epoxy resin. Therefore, when the fluorine-based filler (D) is contained in the resin composition in combination with the resin component, the fluidity of the resin composition increases because the interaction between the fluorine-based filler and the resin component is small. Therefore, when the fluorine-based filler (D) is used, the resin flow of the resin composition is increased. On the other hand, when the resin composition contains (C) rubber particles, (C) the rubber particles have high affinity for the resin component, the tie plasticity of the resin composition can be increased. As a result, the flowability of the resin composition at the time of lamination can be suppressed, and resin flow can be suppressed.

Generally, (D) the fluorine-based filler has a large expansion and shrinkage due to a temperature change. Therefore, during the HAST test, the fluorine-containing filler (D) expands, and after that (D), the fluorine-containing filler shrinks. Thus, in the cured product of the resin composition, (D) stress due to the expansion and contraction of the fluorine-based filler is generated. Further, in general, the interface between the fluorine-based filler and the resin component (D) is poor in adhesion property because (D) the affinity between the fluorine-based filler and the resin component is low. Therefore, when stress is applied to the cured product of the resin composition, the interface between the fluorine-containing filler and the resin component (D) tends to be peeled off easily and tends to be a starting point of cracking. Therefore, after the HAST test, there is a tendency that peeling occurs at the interface between the fluorine-based filler and the resin component (D), or a minute crack occurs from the interface between the fluorine-based filler and the resin component (D) And the conductor layer accompanying destruction in the vicinity of the surface of the insulating layer tends to be easily peeled off. On the other hand, when the rubber particles (C) are used, (C) the rubber particles can absorb the stress caused by the expansion and contraction of the fluorine-based filler (D) Therefore, deterioration of the mechanical strength of the insulating layer due to the HAST test can be suppressed. 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 lowering of the mechanical strength can be compensated by (C) the action of improving the toughness by the rubber particles. Therefore, when the cured product of the resin composition is used, an insulating layer having high adhesion to the conductor layer after the HAST test can be obtained.

[14. Use 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. The insulating layer includes an insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer. Therefore, the resin composition may be used as a resin composition for forming an insulating layer for forming a conductor layer. Among them, the resin composition is preferably used as a resin composition for forming a build-up insulating layer for forming an insulating layer in the production of a circuit board by a build-up method.

In particular, taking advantage of the fact that an insulating layer with a low dielectric constant can be obtained, the resin composition is preferably used as a resin composition (resin composition for forming an insulating layer of a high frequency circuit substrate) for forming an insulating layer of a high frequency circuit board . Among them, the resin composition can be more suitably used as a resin composition (a resin composition for forming an interlayer insulating layer of a high-frequency circuit board) for forming an interlayer insulating layer of a high-frequency circuit board. Here, the " high frequency circuit board " means a circuit board capable of operating even an electric signal of a high frequency band. The " high frequency band " means a band of 1 GHz or more, and the resin composition is particularly effective in a band of 28 to 80 GHz.

Further, the insulating layer having a low dielectric constant can contribute to a reduction in height of the circuit board, which is suitable for applications requiring a thin circuit board. Further, the insulating layer having a low dielectric constant facilitates impedance control of the circuit board, and is therefore suitable for increasing the degree of design freedom of the circuit board. From such a viewpoint, suitable examples of the resin composition include circuit boards such as a mother board, an IC package substrate, a camera module substrate, and a substrate for a fingerprint authentication sensor, which are used in portable equipment. As 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, the authentication of the fingerprint is performed by using the capacitance value of the condenser formed by the finger, the electrode and the insulating film placed on the insulating film different from each other in the concave portion and the convex portion of the fingerprint. In such a fingerprint authentication sensor, if the insulating layer can be made thinner, the size of the sensor itself can be reduced.

The resin composition of the present invention can be applied to a wide variety of resin compositions, such as a laminate material of a sheet such as an adhesive film and a prepreg, a resin composition such as a solder resistor, an underfill material, a die bonding material, a semiconductor encapsulant, Can be used for applications.

[15. Adhesive film]

The resin composition may be applied in a varnish state to form an insulating layer. However, industrially, it is preferable to use an adhesive film having a resin composition layer containing the 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 resin composition described above and may be referred to as an " adhesive layer ".

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

As the support, for example, a film made of a plastic material, a metal foil, and a release paper can be given. As the support, a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN") Of polyester; Polycarbonate (hereinafter sometimes referred to as " PC "); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes referred to as " PMMA "); Cyclic polyolefin; Triacetyl cellulose (hereinafter sometimes referred to as " TAC "); Polyether sulfide (hereinafter sometimes referred to as " PES "); Polyether ketones; Polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and excellent in water availability.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil. Of these, copper foil is preferred. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, good.

The support may be subjected to a treatment such as a mat treatment, a corona treatment, and an antistatic treatment on the surface to be bonded with the resin composition layer.

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent that can be used for the release layer of the release layer-adhered support include one or more types of release agents selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. Examples of commercially available products of the release agent include "SK-1", "AL-5", and "AL-7" manufactured by Lin Tec Corporation, which is an alkyd resin type release agent. As the releasing agent-adherend, for example, "Lumirra T-60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Co., Ltd.; And " UNIPHIL " manufactured by UniCasa.

The thickness of the support is preferably in the range of 5 to 75 탆, more preferably in the range of 10 to 60 탆. When a release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The adhesive film is prepared, for example, by preparing a resin varnish containing an organic solvent and a resin composition, applying the resin varnish to a support using a coating device such as a die coater, and further drying the resin varnish to form a resin composition layer By weight.

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; Carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; And amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

The drying can be carried out by a known method such as heating, hot air blowing or the like. The drying conditions are set so that the content of the organic solvent in the resin composition layer is usually 10 mass% or less, preferably 5 mass% or less. When a resin varnish containing, for example, 30 to 60 mass% of an organic solvent is used, the resin varnish is dried at 50 to 150 ° C for 3 to 10 minutes to form a resin composition layer . Usually, the resin composition layer is obtained as a film obtained by partially curing a resin varnish coating film.

The adhesive film may contain any layer other than the support and the resin composition layer, if necessary. For example, a protective film according to a support may be provided on the surface of the adhesive film which is not bonded to the support of the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 to 40 mu m. By the protective film, adhesion and scratches of dust or the like to the surface of the resin composition layer can be suppressed. When the adhesive film has a protective film, the adhesive film can usually be used by peeling the protective film. Further, the adhesive film can be rolled up and stored.

[16. Prepreg]

The insulating layer may be formed using a prepreg instead of the adhesive film. The prepreg can be formed by impregnating a sheet-like fiber substrate with a resin composition.

The sheet-like fibrous substrate used in the prepreg is not particularly limited. As the sheet-like fiber base material, any fiber base material used as a base material for a prepreg such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 占 퐉 or less, more preferably 800 占 퐉 or less, further preferably 700 占 퐉 or less, particularly preferably 600 占 퐉 or less. The thickness of the sheet-like fiber base material is preferably 30 占 퐉 or less, more preferably 20 占 퐉 or less, and particularly preferably 10 占 퐉 or less, from the viewpoint of suppressing the depth of penetration of the plating for forming the conductor layer. The lower limit of the thickness of the sheet-like fibrous substrate is usually 1 占 퐉 or more, 1.5 占 퐉 or more, or 2 占 퐉 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 may be the same as that of the resin composition layer in the adhesive film.

[17. Circuit board]

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

The " inner layer substrate " Examples of the inner-layer substrate include 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 has a conductor layer formed directly or indirectly on one surface or both surfaces of the core substrate. The conductor layer may be patterned to function as, for example, an electric circuit. An inner-layer substrate on which a conductor layer is formed as a circuit on one surface or both surfaces of the core substrate is sometimes referred to as an " inner-layer circuit substrate ". An intermediate product, in which at least one of the insulating layer and the conductor layer is further formed to manufacture a circuit board, is also included in the term " inner layer substrate ". In the case where the circuit board incorporates a component, an inner-layer board containing components may be used.

The thickness of the inner layer substrate is usually 50 to 4000 占 퐉 and preferably 200 to 3200 占 퐉 in view of improvement of the mechanical strength of the circuit board and reduction in thickness (reduction in thickness).

The inner layer substrate may be formed with one or less through holes extending from one surface to the other surface in order to electrically connect the conductor layers on both sides thereof. Further, the inner-layer substrate may have additional components such as passive elements.

The insulating layer is a layer of a cured product of the resin composition. The insulating layer formed of the cured product is particularly suitable for circuit boards such as a mother board, an IC package substrate, a camera module substrate, and a substrate for a fingerprint authentication sensor used for a circuit board, a high frequency circuit board, It can be suitably applied to an insulating layer for a substrate.

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

The thickness of the insulating layer is usually 20 to 200 占 퐉, and preferably 50 to 150 占 퐉 in view of improvement in electrical characteristics and reduction in circuit board thickness.

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

Since the insulating layer is a layer formed by the cured product of the resin composition described above, excellent properties of the cured product of the resin composition can be exhibited. Therefore, the insulating layer of the circuit board preferably has a dielectric constant of the insulating layer, characteristics such as the peel strength of the insulating layer and the conductor layer after the HAST test, in the same range as described in the section of the properties of the resin composition Can be adjusted. These properties can also be measured by the methods described in the examples.

The circuit board can be manufactured by a manufacturing method including the following steps (I) and (II) using, for example, an adhesive film.

(I) A step of laminating an adhesive film on the inner layer substrate and a resin composition layer of the adhesive film to be bonded to the inner layer substrate.

 (II) A step of thermally curing 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 pressing step in which the adhesive film is heated while being pressed against the inner layer substrate on the support side. Examples of members (also referred to as " hot pressed members ") for a hot pressing process include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the hot press member through an elastic material such as heat resistant rubber so as to sufficiently adhere the adhesive film to the concave and convex portions of the surface of the inner layer substrate, rather than pressing the hot press member directly to the support of the adhesive film .

The lamination of the inner layer substrate and the adhesive film can be carried out, for example, by a vacuum laminating method. In the vacuum laminating method, the temperature of hot pressing is preferably 60 to 160 占 폚, more preferably 80 to 140 占 폚. The pressure of the hot pressing is preferably 0.098 to 1.77 MPa, more preferably 0.29 to 1.47 MPa. The time for hot pressing is preferably 20 to 400 seconds, and more preferably 30 to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

The lamination can be performed by a commercial vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meikisha Sakusho Co., Ltd., a burr applicator manufactured by Nikko Matrix Co., Ltd., and a batch vacuum pressurized laminator.

After lamination, the laminated resin composition layer may be subjected to smoothing treatment by pressing under atmospheric pressure (at atmospheric pressure), for example, on the support side with a hot pressing member. The pressing condition of the smoothing treatment can be set to the same conditions as the hot pressing conditions of the lamination. The smoothing process can be performed by a commercial laminator. The lamination and smoothing process may be performed continuously using the commercial vacuum laminator.

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

In the step (II), an insulating layer is formed by thermally curing the resin composition layer. The conditions of the thermosetting of the resin composition layer are not particularly limited, and the conditions employed 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 the kind of the resin composition, for example. The curing temperature of the resin composition layer is usually in the range of 120 to 240 캜 (preferably in the range of 150 to 220 캜, more preferably in the range of 170 to 200 캜). The curing time is usually in the range of 5 to 120 minutes (preferably 10 to 100 minutes, more preferably 15 to 90 minutes).

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

The manufacturing method of the circuit board may further include (III) a step of piercing the insulating layer, (IV) a step of applying a roughening treatment to the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be carried out according to a suitable method used for the production of a circuit board. When the support is removed after the step (II), the removal of the support may be carried out between the step (II) and the step (III), between the step (III) and the step (IV) ) May be performed at any point in time.

Step (III) is a step of perforating the insulating layer. Through 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 drilling, laser or plasma, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes can be appropriately determined according to the design of the circuit board.

Step (IV) is a step of applying a roughening treatment to the insulating layer. The procedure and condition of the roughening treatment are not particularly limited, and arbitrary procedures and conditions used for forming the insulating layer of the circuit board can be adopted. For example, the swelling treatment with a swelling liquid, the harmonization treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer.

The swelling liquid includes, for example, an alkali solution and a surfactant solution, and preferably an alkali solution. As the alkali solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferable. Examples of commercially available swelling liquids include Swelling Dip Sicergans P and Swelling Dip Sicergans SBU manufactured by Atotech Japan Co., Ltd. The swelling liquid may be used alone or in combination of two or more. The swelling treatment by the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling solution at 30 to 90 DEG C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 to 80 DEG C for 5 to 15 minutes.

As the oxidizing agent, there can be mentioned, for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidizing agent may be used singly or in combination of two or more kinds. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 캜 for 10 to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. and "Dozing Solution · Sekurigans P".

As the neutralizing solution, an acidic aqueous solution is preferable. As a commercially available product of the neutralizing solution, for example, "Reduction Solution · SEQUIRGAN P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The neutralizing liquid may be used singly or in combination of two or more kinds. The treatment with the neutralizing liquid can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 30 to 80 캜 for 5 to 30 minutes. It is preferable to immerse the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 캜 for 5 to 20 minutes in terms of workability and the like.

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 comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, do. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy of two or more metals selected from the group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is preferable from the viewpoints of versatility of the conductor layer formation, cost and ease of patterning. Or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy. 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; More preferably, a single metal layer of copper is more preferable.

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

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

The conductor layer can be formed, for example, by directly patterning it using a metal foil used as a support for an adhesive film. The conductor layer can be formed by, for example, plating. As a forming method by plating, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a method such as a semi-custom method or a pull-on method. Of these, from the viewpoint of simplicity of production, it is preferable to form it by the semi-specific method.

Hereinafter, an example in which the conductor layer is formed by the semi-specific method will be described. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, 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 the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The conductor layer may be formed using, for example, a metal foil. In the case of forming a conductor layer using a metal foil, it is preferable to carry out the step (V) between the step (I) and the step (II). For example, after the step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum laminating method. The lamination conditions may be the same as the lamination conditions of the inner layer substrate and the adhesive film in the step (I). Subsequently, an insulating layer is formed by carrying out the step (II). Thereafter, the metal layer on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a subtractive method, a modified semi- 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 foil, JXUT-III foil, 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Co., Ltd., manufactured by JX Kinzokusa.

In the case where the circuit board has two or more insulating layers and conductor layers (build-up layers), the above-described step of forming the insulating layer and the step of forming the conductor layer are repeated one or more times to function as a circuit A circuit board having a multilayer interconnection structure can be manufactured.

In another embodiment, 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 an adhesive film.

[18. Semiconductor device]

The semiconductor device includes the circuit board. This semiconductor device can be manufactured by using a circuit board.

Examples of the semiconductor device include various semiconductor devices provided in an electric product (such as a computer, a mobile phone, a digital camera and a television) and a vehicle (such as a motorcycle, a car, a train, have.

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

The semiconductor chip mounting method in manufacturing the semiconductor device may employ any method in which the semiconductor chip effectively functions. Examples of the semiconductor chip mounting method include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF) As shown in Fig. Here, the " mounting method using the bumpless buildup layer (BBUL) " means " mounting method in which the semiconductor chip is directly buried in the circuit board and the semiconductor chip and the wiring of the circuit board are connected.

Example

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

[Example 1]

, 20 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation), 10 parts of a beccylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) , 10 parts of a naphthol type epoxy resin (epoxy equivalent 332, "ESN475V" manufactured by Shinnitetsu Sumikin Kagaku KK), 30 parts of a phenoxy resin (solid content 30% by mass), 30 parts of an epoxy resin (epoxy equivalent 276, "NC3000" Of methyl ethyl ketone / cyclohexanone = 1/1 solution, "YL7553BH30" manufactured by Mitsubishi Chemical Corporation) were dissolved by heating in 60 parts of methyl ethyl ketone and 20 parts of cyclohexanone with stirring to obtain a resin solution.

To this resin solution were added 15 parts of an active ester curing agent (active equivalent weight 223, toluene solution of a nonvolatile component of 65% by mass, "HPC8000-65T" manufactured by DIC Corporation), cresol novolak type curing agent containing a triazine skeleton 4 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), a methyl ethyl ketone solution with a solid content of 5% by mass), 25 parts of a solution of N- (2-methoxypropanol solution of 50% by mass, LA3018-50P, ("SO-C2" manufactured by Adomatex Co., Ltd.) having an average particle diameter of 0.5 mu m and a specific surface area of 5.9 m < 2 > / g , 80 parts of polytetrafluoroethylene particles ("Lubron L-2" manufactured by Daikin Industries, Ltd., average particle diameter 3 μm), 2 parts of core-shell type rubber particles ("AC3816N" 4 parts of a particulate fluorine-containing polymer (" LE-605 " manufactured by Kyocera Corp.) was mixed, Each other and uniformly dispersed to obtain a resin varnish.

As a support, a polyethylene terephthalate film (thickness: 38 mu m, "AL5" manufactured by LINTEX Co., Ltd.) having an aliquot resin-based release layer was prepared. On the support, the resin varnish was uniformly coated using a die coater. The coated resin varnish was dried at 80 to 120 DEG C (100 DEG 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 mu m, and the amount of the residual solvent in the resin composition was about 2 mass%.

Subsequently, while the polypropylene film having a thickness of 15 占 퐉 was stuck to the surface of the resin composition layer, the adhesive film was rolled up. The wound adhesive film was slit at a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 mm x 336 mm.

[Example 2]

The amount of the core-shell type rubber particles ("AC3816N" manufactured by AIKAGO Co., Ltd.) was changed from 2 parts to 6 parts. A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Example 3]

80 parts of polytetrafluoroethylene particles ("Lubron L-2" manufactured by Daikin Industries) and 4 parts of a fluorine-containing polymer ("LE-605" manufactured by Kyocera Corp.) were mixed in advance, Respectively. A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Example 4]

30 parts of biphenylaralkyl type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.) was changed to 27 parts of naphthylene ether type epoxy resin (epoxy equivalent 260, "HP6000" manufactured by DIC Corporation).

2 parts of core-shell type rubber particles ("AC3816N" manufactured by AIKAGO Co., Ltd.) were mixed with core-shell type rubber particles ("IM401-7-17" manufactured by Aikagaku Co., Ltd., the core was polybutadiene, the shell was styrene-divinylbenzene copolymer ) Was changed to 2 copies. A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Example 5]

, 20 parts of a naphthylene ether type epoxy resin (epoxy equivalent 260, "HP6000" manufactured by DIC Corporation) and 30 parts of a naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, " HP4700 ", manufactured by DIC Corporation). A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Example 6]

15 parts of an active ester curing agent (a toluene solution of a nonvolatile component of 65 mass%, " HPC8000-65T ", manufactured by DIC Corporation) and 15 parts of a cresol novolak type curing agent containing a triazine skeleton (a solution of 2-methoxypropanol having a solid content of 50% 15 parts of a naphthol-type curing agent (hydroxyl equivalent: 215, "SN485" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.) and 25 parts of triazine-containing phenol novolak resin (hydroxyl equivalent: 125, Ketone solution, " LA7054 ", manufactured by DIC Corporation). A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Example 7]

To the resin varnish was further added 2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Comparative Example 1]

The amount of the core-shell type rubber particles ("AC3816N" manufactured by AIKAGO Co., Ltd.) was changed from 2 parts to 0 part. A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Comparative Example 2]

2 parts of core-shell type rubber particles ("AC3816N" manufactured by Aikagaku Co., Ltd.) was mixed with an epoxy resin having a polybutadiene structure capable of functioning as non-particulate rubber (epoxy equivalent 190, methyl ethyl ketone solution having a solid content of 80% Quot; PB3600M " manufactured by Kusa Co., Ltd.). A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Comparative Example 3]

The amount of core-shell type rubber particles ("AC3816N" manufactured by Aikano KK) was changed from 2 parts to 12 parts. A resin varnish and an adhesive film were prepared in exactly the same manner as in Example 1 except for the above.

[Measurement of dielectric constant]

A polyethylene terephthalate film ("PET501010" manufactured by Lintec Corp.) having a surface subjected to release treatment was prepared. On this polyethylene terephthalate film, resin varnishes obtained in Examples and Comparative Examples were uniformly coated using a die coater so that the thickness of the resin composition layer after drying became 50 占 퐉. The coated resin varnish was dried at 80 to 110 캜 (average 95 캜) for 6 minutes to obtain a resin composition layer. Thereafter, the resin composition layer was heat-treated at 200 캜 for 90 minutes to cure, and the support was peeled off to obtain a cured film formed of the cured resin composition. The cured film was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

With respect to the 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 占 폚 by a cavity resonance perturbation method using an analyzer ("HP8362B" manufactured by Agilent Technologies) Respectively. The measurement was carried out with respect to two test pieces, and the average value thereof was calculated.

[Measurement of Resin Flow Rate]

An inner layer substrate (glass clad epoxy resin double-side copper-clad laminate, copper foil thickness of 18 mu m, substrate thickness of 0.8 mm, "R5715ES" manufactured by Matsushita Electric Industries, Ltd.) was prepared. The adhesive films prepared in Examples and Comparative Examples were laminated by using a batch type vacuum pressure laminator (CVP700, a two-stage build-up laminator manufactured by Nikko Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate, Both sides of the substrate were laminated. The laminate was decompressed for 30 seconds to adjust the air pressure to 13 hPa or less, followed by compression at 100 DEG C and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100 占 폚 and a pressure of 0.5 MPa for 60 seconds.

Thereafter, the end portion of the adhesive film laminated on the inner layer substrate was observed. 1 is a top view schematically showing the periphery of an end portion of an adhesive film 100 laminated on an inner layer substrate 200 in the embodiment. 1, the resin composition layer 110 of the adhesive film 100 is outwardly projected beyond the edge 120E of the support 120 of the adhesive film 100 appear. The resin composition layer 110 is formed in such a manner that the resin composition layer 110 fluidized at the time of lamination flows out in the in-plane direction parallel to the surface 200U of the inner layer substrate 200. Thereupon, the distance W from the edge 120E of the support 120 of the adhesive film 100 to the tip 110T of the resin composition layer 110 that has been evacuated is measured, Flow rate. The amount of resin flow was 3 mm or less and the amount of resin flow was more than 3 mm.

[Measurement of Peel Strength]

(1) Treatment of inner layer substrate:

A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 mu m, substrate thickness of 0.8 mm, "R5715ES" manufactured by Matsushita Electric KK) on which an inner layer circuit was formed was prepared as an inner layer substrate. Both surfaces of this inner-layer substrate were etched with a thickness of 1 mu m with an etching agent (" CZ8100 " manufactured by Megas Co.) to perform coarsening treatment on both copper surfaces of the inner-layer substrate.

(2) Laminate of adhesive film:

The adhesive films prepared in Examples and Comparative Examples were laminated by using a batch type vacuum press laminator (CVP700, a two-stage build-up laminator manufactured by Nikko Co., Ltd.) Were laminated on both sides. The laminate was subjected to pressure reduction for 30 seconds to set the air pressure to 13 hPa or less, followed by compression at 100 DEG C and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100 占 폚 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 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes to thermally cure the resin composition layer to form an insulating layer. Thereafter, the polyethylene terephthalate film as a support was peeled off. Thus, a sample substrate having an insulating layer, an inner-layer substrate, and an insulating layer in this order was obtained.

(4) Harmonizing treatment:

The sample substrate was immersed in a swelling liquid ("Swelling Dip Sekurigans P", manufactured by Atotech Japan Co., Ltd., containing diethylene glycol monobutyl ether) at 60 ° C for 10 minutes. Next, the sample substrate was immersed in 80 占 폚 for 20 minutes in a roughening solution ("Concentrate Compact P" manufactured by Atotech Japan Co., Ltd., KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution). Next, the sample substrate was immersed in a neutralizing solution ("Reduction Sol-Sol-Gel, Sekurigansu P" manufactured by Atotech Japan Co., Ltd.) at 40 ° C for 5 minutes. Thereafter, the sample substrate was dried at 80 DEG C for 30 minutes to obtain a coherent substrate.

(5) Plating by semi-permanent method:

The coarsened substrate was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes and then immersed in electroless copper plating solution at 25 ° C for 20 minutes. Thereafter, the coarsened substrate was annealed by heating at 150 DEG C for 30 minutes. An etching resist was formed on the roughened substrate after annealing, and pattern formation was performed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 mu m on the surface of the insulating layer. Next, annealing was performed by heating at 180 DEG C for 30 minutes to obtain a circuit board having a conductor layer on the insulating layer.

(6) Measurement of Peel Strength (Peel Strength) of Plated Conductor Layer:

A notch was inserted into 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 in the longitudinal direction of this rectangular portion was peeled off and picked up with a forceps (AC-50CSL, an auto-comb type tester manufactured by TA, Ltd.). Then, a peeling test was carried out at room temperature in a direction perpendicular to the surface of the circuit board at a rate of 50 mm / min to peel off the conductor layer. The load (kgf / cm) . Cm < 3 >, and the peel strength was 0.3 kgf / cm or more. Further, it was judged that the peel strength was less than 0.3 kgf / cm and that the peeling occurred, as " poor ".

[Measurement of Peel Strength after HAST Test]

An accelerated environmental test was performed on the circuit board as an HAST test in which the substrate was exposed to an environment at a temperature of 130 DEG C and a humidity of 85% RH for 100 hours using an advanced accelerated life testing device ("PM422" manufactured by Kusumoto Chemical Industry Co., Ltd.). Thereafter, the peel strength at the time when the conductor layer of the circuit board was taken out was measured by the same operation as the step (6) " Measurement of peel strength (peel strength) of the plated conductor layer & .

Cm < 3 >, and the peel strength after the accelerated environmental test was 0.3 kgf / cm or more, and " poor "

[result]

The results of the above-described Examples and Comparative Examples are shown in the following table. In the following table, the amount of each component represents the mass part of the non-volatile component.

[Review]

As can be seen from Table 1, in the examples, a low dielectric constant is obtained. Further, in the examples, the resin flow amount is small and the peel strength after the HAST test is large. From these results, it was confirmed that the present invention can realize an insulating layer having a low dielectric constant and high adhesiveness to a conductor layer after the HAST test, and capable of suppressing the resin flow .

In order to obtain the desired effect of the present invention from the results of Comparative Example 1 in which (C) rubber particles are not contained and Comparative Example 3 in which the amount of rubber particles is excessive, (C) In the range of < / RTI > Particularly, in Comparative Example 3, since the amount of the rubber particles (C) was excessive, the mechanical strength of the resin composition was lowered, the peel strength before the HAST test was lowered, and (C) And the peel strength after the HAST test is considered to be lowered.

From the results of Comparative Example 2 using an epoxy resin ("PB-3600M" manufactured by Daicel Industries) that can function as a liquid rubber instead of the rubber particles (C), in order to obtain the desired effect of the present invention, It can be seen that particles should be used. In Comparative Example 2, by using a rubber component other than the particulate rubber, it was considered that the resin flow amount was increased because the effect of improving the tin firing was not obtained. Further, in Comparative Example 2, it was considered that the rubber component other than the particulate rubber could not sufficiently absorb the stress caused by the temperature change during the HAST test, and therefore, the peel strength after the HAST test was lowered.

Further, when Example 1 and Example 3 are compared, the resin flow amount in Example 1 is small. Therefore, in order to effectively suppress the resin flow, it is more preferable to mix the fluorine-containing filler (D) and the fluorine-based polymer (D), rather than mixing the other components after mixing the fluorine- It is preferable to separately mix the components with other components.

In the above examples, even when the components (E) and (I) are not used, it is confirmed that the results are the same as those of the above-mentioned examples although there are differences in the degree.

100 adhesive film
110 resin composition layer
120 support
200 inner layer substrate

Claims (12)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler, wherein the amount of the component (C) 3% by mass. The resin composition according to claim 1, wherein the component (D) is a fluorine-based polymer particle. The resin composition according to claim 2, wherein the component (D) is a polytetrafluoroethylene particle. The resin composition according to claim 1, which contains (E) an inorganic filler. The resin composition according to claim 4, wherein the component (E) is silica. The resin composition according to claim 4, wherein the amount of the component (E) is 5 to 70 mass% relative to 100 mass% of the nonvolatile component in the resin composition. The resin composition according to claim 1, wherein the amount of the component (D) is 10 to 80% by mass based on 100% by mass of the nonvolatile component in the resin composition. The epoxy resin composition according to claim 1, wherein the component (A) is at least one selected from the group consisting of bisphenol A epoxy resin, biquileneol epoxy resin, biphenylaralkyl epoxy resin, naphthylene ether epoxy resin, naphthalene type tetrafunctional epoxy resin and naphthol epoxy resin And at least one epoxy resin selected from the group consisting of epoxy resins. The resin composition according to claim 1, which is used for forming an insulating layer of a circuit board. An adhesive film comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 9 provided on the support. A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the circuit board according to claim 11.

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