WO2007097209A1 - Epoxy resin composition - Google Patents

Abstract

An epoxy resin composition suitable for use as an insulating layer of multilayer printed wiring board, which epoxy resin composition attains satisfactory flame retardation without relying upon halogen flame retardants and phosphorus flame retardants and excels in storage stability and strength of adhesion of the insulating layer to plated conductor. There is provided an epoxy resin composition characterized by containing (A) aromatic epoxy resin having two or more epoxy groups in each molecule, (B) naphthol curing agent, (C) thioalkyl-containing phenolic curing agent and (D) inorganic filler.

Description

 Specification

 Epoxy resin composition

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition suitable for forming an insulating layer of a multilayer printed wiring board.

 Background art

 In recent years, electronic devices have become smaller and higher in performance, and the miniaturization and higher density of wiring have progressed even on multilayer printed wiring boards. Conductive layer formation methods suitable for forming high-density wiring include the additive method of forming a conductive layer by electroless plating after roughening the surface of the insulating layer, and conductive layers by electroless plating and electrolytic plating. The semi-additive method of forming is known. Therefore, the epoxy resin composition used for forming the insulating layer of the multilayer printed wiring board is required to have high adhesion with the plating conductor layer.

 [0003] On the other hand, halogen-based compounds such as brominated epoxy resins have been widely used for the flame retardancy of epoxy resin compositions. However, environmental problems represented by dioxin in recent years have been widely used. As such, it is becoming difficult to use. In the epoxy resin composition for multilayer printed wiring boards, as a flame retardant method that does not use a halogen compound, for example, as shown in Patent Document 1, Patent Document 2, etc. A method of using a flame retardant is known. Patent Document 3 discloses a method of using a phenol resin having a thioalkyl group as a curing agent in a resin sealing resin composition.

 Patent Document 1: Japanese Patent Laid-Open No. 2001-214037

 Patent Document 2: Japanese Patent No. 3108412

 Patent Document 3: Japanese Patent Laid-Open No. 2004-339277

 Disclosure of the invention

 Problems to be solved by the invention

[0004] However, the use of phosphorus-based flame retardants is also being suppressed due to environmental problems and the like. Further, according to the knowledge of the present inventor, thioalkyl group-containing phenol resin has a tendency to reduce the storage stability of the resin composition. Furthermore, according to the knowledge of the present inventor, The flame retardant effect of thioalkyl group-containing phenol resin is not always sufficient, for example

As in Patent Document 3, the content of inorganic fillers such as silica is 70 to 95% by mass. In the epoxy resin composition for wiring boards, the reduction of flame retardancy becomes a significant problem.

[0005] The present invention has been made in view of the above circumstances, and a problem to be solved is an epoxy resin composition suitable for use as an insulating layer of a multilayer printed wiring board, Epoxy that can achieve sufficient flame retardancy without depending on the rogen flame retardant and phosphorus flame retardant, and has excellent storage stability and adhesion strength of the insulating layer (interlayer insulating layer) to the plating conductor The object is to provide a fat composition.

 Means for solving the problem

 [0006] As a result of diligent research to solve the above problems, the present invention has the following results. (A) Aromatic epoxy resin having two or more epoxy groups in one molecule, (B) a naphthol curing agent, (C An epoxy resin composition comprising a phenolic curing agent containing a thioalkyl group and (D) an inorganic filler is an insulative layer (interlayer insulation layer) for flame retardancy, storage stability, and a metallic conductor. ), The present invention was completed.

 That is, the present invention includes the following contents.

 [1] (A) Aromatic epoxy resin having two or more epoxy groups in the molecule, (B) naphthol curing agent, (C) thioalkyl group-containing phenol curing agent, and (D) inorganic filling An epoxy resin composition comprising a material.

 [2] The epoxy resin composition according to [1] above, containing 20 to 60% by mass of the inorganic filler of component (D) when the nonvolatile component of the epoxy resin composition is 100% by mass.

 [3] The epoxy resin composition according to [1] above, containing 30 to 50% by mass of the inorganic filler of component (D) when the nonvolatile component of the epoxy resin composition is 100% by mass.

 [4] The epoxy resin composition according to any one of [1] to [3] above, wherein the inorganic filler of component (D) is silica.

 [5] The above-mentioned [1] to [1], wherein the mixing ratio of components (B) and (C) is from 1: 0.1 to 1: 1.5 by mass ratio

4] V, epoxy resin composition according to any of the above.

[6] The naphthol-based curing agent of component (B) is represented by the following formula (1): [0008] [Chemical 1]

[Wherein, R1 to R4 each independently represent a hydrogen atom or an alkyl group, XI may be each substituted with an alkyl group, may represent a naphthalene ring, and Y may each be substituted with an alkyl group. A benzene ring, a hydroxybenzene ring, a biphenyl ring or a naphthalene ring, each of which may be an integer, and j and k each represent an average value of 1 to 15.)

 A naphthol type hardener represented by the formula (2):

 [0010] [Chemical 2]

[Wherein, R5 represents a hydrogen atom or an alkyl group, R6 represents a thioalkyl group, X2 is each substituted with an alkyl group, and represents a benzene ring or a naphthalene ring, and j and k are Each represents an average value of 1 to 15, and m represents an integer of 1 to 5. The above-mentioned [1] to [5], which is a thioalkyl group-containing phenolic hardener represented by The epoxy resin composition described.

[7] The naphthol-based curing agent of component (B) is represented by the following formula (1 ') _:

( 1，) [0012] [Chemical 3]

(1,)

(Wherein R1 to R4 each independently represent a hydrogen atom or an alkyl group, XI may be each substituted with an alkyl group, may represent a naphthalene ring, and Y represents each substituted with an alkyl group. A benzene ring, a hydroxybenzene ring, a biphenyl ring or a naphthalene ring, which may be used, n represents an average value of 1 to 15.)

A thioalkyl group-containing phenolic curing agent of component (C) represented by the following formula (2 ') _:

[0014] [Chemical 4]

(In the formula, R5 represents a hydrogen atom or an alkyl group, R6 represents a thioalkyl group, X2 is each substituted with an alkyl group, and represents a benzene ring or a naphthalene ring, and n represents an average value. Represents a number from 1 to 15, and m represents an integer from 1 to 5.)

 The epoxy resin composition according to any one of [1] to [5] above, which is a thioalkyl group-containing phenol hardener represented by the formula:

 [8] The aromatic epoxy resin of component (A) is an aromatic epoxy resin that has two or more epoxy groups in the (Al) 1 molecule and is liquid at a temperature of 20 ° C. And (A2) a second epoxy resin that has 3 or more epoxy groups in one molecule and is a solid aromatic epoxy resin at a temperature of 20 ° C. The epoxy resin composition according to any one of [1] to [7] above.

[9] The epoxy equivalent of the second epoxy resin of component (A2) is 230 or less, [8] The epoxy resin composition described.

 [10] The epoxy resin composition according to [8] above, wherein the epoxy equivalent of the second epoxy resin of component (A2) is in the range of 150 to 230.

 [11] Mixing ratio of the first epoxy resin (A1) and the second epoxy resin (A2) (A1: A2) force The mass ratio ranges from 1: 0.3 to 1: 2, The epoxy resin composition according to any one of 8] to [10].

 [12] When the nonvolatile component of the epoxy resin composition is 100% by mass, the content of the aromatic epoxy resin of component (A) is 10 to 50% by mass, and the epoxy resin composition contains The ratio of phenolic hydroxyl groups in the naphthol-based curing agent of component (B) and the thioalkyl group-containing phenolic curing agent of component (C) to the existing epoxy groups is 1: 0.5 to 1: 1.5. [1] to [11], the epoxy resin composition according to any one of the above.

[13] The epoxy resin composition according to the above [1] to [12], wherein the epoxy resin composition further contains a polyvinyl acetal resin.

 [14] The epoxy resin composition according to the above [13], wherein the content of the polybulacetal resin is 2 to 20% by mass when the nonvolatile component of the epoxy resin composition is 100% by mass.

[15] An adhesive film in which the epoxy resin composition according to any one of [1] to [14] above is layered on a support film.

 [16] A pre-preda, wherein the epoxy resin composition according to any one of [1] to [14] is impregnated in a sheet-like reinforcing base material having a fiber strength.

[17] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the epoxy resin composition according to any one of [1] to [14] above.

 [18] A method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer comprises the above [1] to [ 14] It is formed by thermosetting the epoxy resin composition according to any one of the above, and the conductor layer is formed by copper plating on a rough surface obtained by roughing the surface of the insulating layer. A method for producing a multilayer printed wiring board.

[19] A method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is the above [15] The adhesive film is laminated on the inner circuit board, and the epoxy resin composition is heat-cured with or without peeling off the support film, and the support film is peeled off when the support film is present after curing. The method for producing a multilayer printed wiring board, wherein the conductor layer is formed by copper plating on a rough surface obtained by roughening the surface of the insulating layer.

 [20] A method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is the pre-preda The conductive layer is formed by copper plating on a roughened surface obtained by roughening the surface of the insulating layer. The manufacturing method of a multilayer printed wiring board.

 The invention's effect

 [0016] According to the present invention, sufficient flame retardancy can be achieved regardless of the halogen-based flame retardant and the phosphorus-based flame retardant, the storage stability is excellent, and the adhesion strength with the conductive layer formed by plating An epoxy resin composition capable of forming an excellent insulating layer can be provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0017] Hereinafter, the present invention will be described in more detail.

 [0018] [Epoxy resin of component (A)]

 The “aromatic epoxy resin having two or more epoxy groups in one molecule” of the component (A) in the present invention is not particularly limited, and examples thereof include a cresol novolac type epoxy resin and a phenol novolac type. Epoxy resin, tert-butyl-catechol type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidylamine type Examples include epoxy resin. Those containing a halogen atom are not preferred. In addition, the aromatic epoxy resin referred to in the present invention means an epoxy resin having an aromatic ring skeleton in the molecule.

 [0019] The epoxy resin of component (A) may be used alone or in combination of two or more.

(Al) 1st epoxy resin that has 2 or more epoxy groups in one molecule and is liquid aromatic epoxy resin at a temperature of 20 ° C and (A2) 3 or more in 1 molecule An embodiment in which a “second epoxy resin” having an epoxy group and being a solid aromatic epoxy resin at a temperature of 20 ° C. is used in combination is preferable. The second epoxy resin has an epoxy equivalent of 230 or less Particularly preferred are those having a more preferred epoxy equivalent weight in the range of 150-230.

[0020] When the first epoxy resin (A1) and the second epoxy resin (A2) are used as the epoxy resin (A), the resin composition is used in the form of an adhesive film. In addition, an adhesive film exhibiting sufficient flexibility (excellent in handling and properties) can be formed, and at the same time, the breaking strength of the cured resin composition is improved, and the durability of the multilayer printed wiring board is improved.

In the present invention, the “(A1) first epoxy resin having two or more epoxy groups in one molecule and being an aromatic epoxy resin that is liquid at a temperature of 20 ° C.” Examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, and glycidylamine type epoxy resin. In the present invention, the first epoxy resin (A1) may be used alone or in combination of two or more. The first epoxy resin (A1) may be liquid at a temperature of less than 20 ° C.

[0022] Specific examples of such epoxy resins include HP4032 (Dainippon Ink Chemical Co., Ltd.), HP4032D (Dainippon Ink Chemical Co., Ltd.), jER807 (Epicoat 807) For example, Japan Epoxy Resin Co., Ltd.), jER828EL (Epicoat 828EL) (Japan Epoxy Resin Co., Ltd.), jER152 (Epicoat 152) (Japan Epoxy Resin Co., Ltd.), and the like.

On the other hand, (A2) “second epoxy resin having 3 or more epoxy groups in one molecule and being a solid aromatic epoxy resin at a temperature of 20 ° C.” includes, for example, naphthalene Type epoxy resin, epoxy resin (trisphenol type epoxy resin) of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group. In addition, the second epoxy resin (A2) has an epoxy equivalent of 150 to 230, preferably having an epoxy equivalent of 230 or less in order to improve physical properties such as glass transition temperature of the resin composition. Those in the range are more preferred. Therefore, in the present invention, the second epoxy resin (A2) has the following meaning: “A molecule having 3 or more epoxy groups, an epoxy equivalent of 230 or less, and a solid aromatic compound at a temperature of 20 ° C. "Epoxy resin" that has 3 or more epoxy groups in one molecule, and has an epoxy equivalent of 150-230 and is a solid aromatic epoxy resin that is solid at a temperature of 20 ° C. It is more preferable that Even if one second epoxy resin (A2) is used, two or more A combination of the above may be used. The second epoxy resin (A2) may be in a solid state at a temperature exceeding 20 ° C.

 [0024] Specific examples of such epoxy resins include HP 4700 (EXA4700) (tetrafunctional naphthalene type epoxy resin, epoxy equivalent 163, solid) manufactured by Dainippon Ink & Chemicals, Inc., N— 690 (Crezo novolac epoxy resin, epoxy equivalent 208, solid), N—695 (Crezo novolac epoxy resin, epoxy equivalent 208, solid), EPP N— 502H (Trisphenol) from Nippon Kayaku Co., Ltd. Epoxy resin, epoxy equivalent 168, solid), NC7000L (naphthol novolac epoxy resin, epoxy equivalent 228, solid), NC3000H (biphenyl epoxy resin, epoxy equivalent 290, solid), manufactured by Tohto Kasei Co., Ltd. ESN185 (naphtholene novolak type epoxy resin, epoxy equivalent 275, solid), ESN475 (naphthol nopolac type epoxy resin, epoxy equivalent 350, solid) and the like.

 [0025] When the first epoxy resin (A1) and the second epoxy resin (A 2) are used in combination as the epoxy resin (A), the first epoxy resin (A1) and the second epoxy resin (A1) The blend ratio (A1: A2) of the epoxy resin (A2) is preferably in the range of 1: 0.3 to 2 in terms of mass ratio, more preferably in the range of 1: 0.5 to 1. If the ratio of the first epoxy resin (A1) is too large beyond the range, it will increase the tackiness of the resin composition and, when used in the form of an adhesive film, deaeration during vacuum lamination Tends to decrease and voids tend to occur. In addition, the peelability of the protective film and the support film during vacuum lamination tends to decrease, and the heat resistance after curing tends to decrease. In addition, a sufficient breaking strength tends to be hardly obtained in the cured product of the resin composition. On the other hand, if the ratio of the second epoxy resin (A2) is too large beyond the range where force is applied, sufficient flexibility cannot be obtained when the adhesive film is used in the form of an adhesive film, resulting in poor handling. There is a tendency that it is difficult to obtain sufficient fluidity when laminating.

[0026] In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by mass, the epoxy resin content of the component (A) is 10 to 50% by mass. More preferably, it is 20 to 40% by mass, and particularly preferably 20 to 35% by mass. Content power of epoxy resin (A) S If this range power is also removed, the curability of the resin composition tends to decrease. In addition, the epoxy resin composition of the present invention has a range in which the effect of the present invention is exhibited (usually 50% when the nonvolatile component of the epoxy resin composition is 100% by mass). In addition to component (A), other epoxy resins may be included.

 [0027] [Naphthol-based curing agent of component (B)]

 The “naphthol curing agent” in the present invention means a compound having two or more naphthol structures in one molecule and acting as a curing agent for epoxy resin (A).

 [0028] As the naphthol-based curing agent, the naphthol-based curing agent represented by the following formula (1 ') is particularly preferable, and the naphthol-based curing agent represented by the following formula (1) is particularly preferable.

 [0029] [Chemical 5]

(Wherein R1 to R4 each independently represents a hydrogen atom or an alkyl group, XI may be each substituted with an alkyl group, may represent a naphthalene ring, and Y represents each substituted with an alkyl group. A benzene ring, a hydroxybenzene ring, a biphenyl ring or a naphthalene ring, each of which may be an integer, and j and k each represent an average value of 1 to 15.)

 [0031] [Chemical 6]

 (1,)

 (Wherein R1 to R4 each independently represent a hydrogen atom or an alkyl group, XI may be each substituted with an alkyl group, may represent a naphthalene ring, and Y represents each substituted with an alkyl group. A benzene ring, a hydroxybenzene ring, a biphenyl ring or a naphthalene ring, which may be used, n represents an average value of 1 to 15.)

 [0033] In the formula (1) and the formula (1 '), the alkyl group in the formula is preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

[0034] [Thioalkyl group-containing phenolic curing agent of component (C)] The “thioalkyl group-containing phenolic curing agent” in the present invention has one or more thioalkyl groups in one molecule and one or more phenol and / or naphthol structures in one molecule, and is a curing agent for epoxy resin (A). Means a compound that acts as

 [0035] As the thioalkyl group-containing phenolic curing agent, a thioalkyl group-containing phenolic agent represented by the following formula (2 '), which is preferably a thioalkyl group-containing phenolic curing agent represented by the following formula (2): A curing agent is particularly preferred.

 [0036] [Chemical 7]

 (In the formula, R5 represents a hydrogen atom or an alkyl group, R6 represents a thioalkyl group, X2 is each substituted with an alkyl group, and represents a benzene ring or a naphthalene ring, and j and k are Each represents an average value of 1 to 15, and m represents an integer of 1 to 5.)

 [0038] [Chemical 8]

 (2,)

 (In the formula, R5 represents a hydrogen atom or an alkyl group, R6 represents a thioalkyl group, X2 is each substituted with an alkyl group, and may represent a benzene ring or a naphthalene ring, and n represents an average value. Represents a number from 1 to 15, and m represents an integer from 1 to 5.)

[0040] In the formulas (2) and (2 '), when m is 2 to 5, a plurality of R6 need not be the same, each independently selected from a hydrogen atom, an alkyl group, or a thioalkyl group. It may be a group. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable. As the thioalkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. In particular, a thiomethyl group is preferred.

 In the present invention, the average hydroxyl group content P ((total number of hydroxyl groups) in one molecule as represented by the above formula (1), formula (1 ′), formula (2) and formula (2 ′). By employing a phenol-based curing agent having an average value of Z total benzene ring number) of 0 <P <1, a coarse product obtained by subjecting the cured product of the epoxy resin composition of the present invention to a rough treatment. The surface can be made finer and more suitable for high-density wiring.

 [0042] The naphthol curing agent of component (B) is more preferably represented by the following formula (3).

[0043] [Chemical 9]

(In the formula, R7 represents a hydrogen atom or a methyl group, Z represents a naphthalene ring, and n represents an average value of 1 to 15.)

 [0045] Specific examples of the naphthol-based curing agent represented by the powerful formula (3) include NHN (Z: naphthalene ring, R7: methyl group, average hydroxyl group content: 3Z5 to 2Z3 manufactured by Nippon Kayaku Co., Ltd. And CBN (Z: naphthalene ring, R7: methyl group, average hydroxyl group content: 3Z5 to 2Z3, see the figure below).

[0046] [Chemical 10]

[0047] The thioalkyl group-containing phenolic curing agent of component (C) is more preferably one represented by the following formula (4).

[0048] [Chemical 11]

(Wherein R11 represents a thiomethyl group, and n represents an average value of 1 to 15)

 Specific examples of the thioalkyl group-containing phenolic curing agent represented by the formula (4) include YLH1110L (average hydroxyl group content: 1Z2 to 2Z3) manufactured by Japan Epoxy Resin Co., Ltd.

 [0050] The mixing ratio of the components) and (C) is preferably in the range of 1: 0.1 to 1: 1.5 in terms of mass ratio, in the range of 1: 0.1 to 1: 1. More preferably. If the proportion of the phenolic curing agent containing a thioalkyl group as the component (C) is too small, the adhesion between the insulating layer formed by the epoxy resin composition and the conductive conductor layer tends to decrease. There is a tendency for the storage stability of rosin to decrease.

[0051] The epoxy resin composition of the present invention includes a phenol other than component (B) and component (C). A system curing agent may be blended. In this case, it is preferable that 50% by mass or more of the total phenolic hardener in the composition is the component (B) and the component (C) in order to sufficiently exhibit the effects of the present invention. More preferably, 70% by mass or more, particularly 90% by mass or more is preferably component (B) and component (C).

[0052] In the present invention, the amount of the phenolic curing agent in the epoxy resin composition (the total amount when only the component (B) and the component (C) are used, or the component (B) and the component (C) The total amount of those used in combination with other phenolic curing agents is usually the total number of epoxy groups present in the epoxy resin composition and the phenolic hydroxyl groups of the phenolic curing agent. It is preferable to set the ratio so that the ratio of the total number is 1: 0.1 to 1: 1.5, and it is more preferable to set the ratio so that the ratio is 1: 0.3 to 1: 1. The total number of epoxy groups present in the epoxy resin composition is the total value of all epoxy resins obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent. Yes, the total number of phenolic hydroxyl groups in the phenolic hardener is the total number of phenolic hardeners obtained by dividing the solid mass of each phenolic hardener by its phenolic hydroxyl group equivalent. Is the total value of. If the content of the phenol-based curing agent is outside the preferable range, the heat resistance of the cured product obtained by curing the resin composition may be insufficient.

[0053] In the present invention, the inorganic filler of component (D) increases the flame retardancy of the epoxy resin composition and contributes to a decrease in the coefficient of thermal expansion. Examples of inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanium. Examples thereof include barium oxide, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and among these, silica is particularly preferable. The average particle size of the inorganic filler is preferably 1 μm or less, more preferably 0.8 m or less, and particularly preferably 0.7 μm or less. When the average grain size exceeds 1 μm, it tends to be disadvantageous for the formation of fine wiring. If the average particle size force of the inorganic filler becomes too small, the viscosity of the varnish tends to increase and the handleability tends to decrease when the epoxy resin composition is made into a resin varnish. The diameter is preferably 0.05 m or more. Inorganic filler is moisture resistant In order to improve this, what is surface-treated with a surface treatment agent such as a silane coupling agent is preferable.

 [0054] The average particle size of the inorganic filler can be measured by a laser diffraction 'scattering method based on Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of an inorganic filler on a volume basis with a laser diffraction particle size distribution measuring device and setting its median diameter as an average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

 [0055] When the inorganic filler is blended, the content ratio with respect to the resin composition (non-volatile content: 100% by mass) varies depending on the properties required for the resin composition. Formation of interlayer insulating layer of multilayer printed wiring board When used in the above, it is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, and particularly preferably 30 to 45% by mass. If the amount of the inorganic filler is too large, the adhesion strength between the insulating layer and the conductive conductor layer tends to decrease, and the cured product of the epoxy resin composition tends to become brittle. On the other hand, if the amount is too small, the flame retardancy of the cured product tends to decrease and the coefficient of thermal expansion tends to increase.

 [0056] The epoxy resin composition of the present invention may contain poly (bullacetal) resin for the purpose of increasing the adhesion strength of the metallic conductor. The polyvinyl acetal resin is not particularly limited, but a polyvinyl butyral resin is preferable. Specific examples of polyvinylacetal resin include: Electric Chemical Industry Co., Ltd., Electric Butyral 4000-2, 5000—A, 600 0—C, 6000—EP, Sekisui Chemical Co., Ltd. ESREC BH series, BX Series, KS series, BL series, BM series etc.

 [0057] The polyvinyl acetal particularly preferably has a glass transition temperature of 80 ° C or higher. The “glass transition temperature” here is determined in accordance with the method described in IS K 7197. When the glass transition temperature is higher than the decomposition temperature and no glass transition temperature is actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention. The decomposition temperature is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.

[0058] In the epoxy resin composition of the present invention, the non-volatile component of the epoxy resin composition is 10%. When the content is 0% by mass, the content ratio of polybutelacetal is preferably 2 to 20% by mass.

 [0059] The epoxy resin composition of the present invention may contain phenoxy resin for the purpose of improving the flexibility of the adhesive film. The phenoxy resin is not particularly limited, and a known phenoxy resin can be used. When the nonvolatile component of the epoxy resin composition is 100% by mass, the content of the phenoxy resin is preferably in the range of 3 to 30% by mass. Specific examples of phenoxy resin include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YL6954 and YL6974 manufactured by Japan Epoxy Resin Co., Ltd.

[0060] The epoxy resin composition of the present invention may contain rubber particles for the purpose of increasing the mechanical strength of the cured product. Preferable examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, acrylic rubber particles and the like. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer, or an outer layer. And a three-layer structure in which the shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (Ganz Kasei Co., Ltd. trade name), Metaprene KW-4426 (Mitsubishi Rayon Co., Ltd. trade name). Specific examples of Atariguchi-tolyl butadiene rubber (NBR) particles include: 尺 -91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0, manufactured by Co., Ltd.). Specific examples of the acrylic rubber particles include Metapuren W300A (average particle size 0. 1 m), W450A (flat Hitoshitsubu径_0. 2 μ ΐ η) (manufactured by Mitsubishi Rayon Co., Ltd.).

 [0061] When the rubber particles are blended, the content ratio with respect to the resin composition (non-volatile content: 100% by mass) is a force of 1 to 10% by mass, which varies depending on the properties required for the resin composition. Furthermore, 2 to 5% by mass is more preferable.

[0062] The epoxy resin composition of the present invention may contain a curing accelerator for the purpose of adjusting the curing time. Examples of the curing accelerator include organic phosphine compounds and imidazoles. Compounds, amine adduct compounds, tertiary amine compounds and the like. Specific examples of organic phosphine compounds include TPP, ΤΡΡ—Κ, ΤΡΡ—S, TPTP—S (Hokuko Chemical Industries).

(Trade name)). Specific examples of imidazole compounds include cure azole

2MZ, 2E4MZ, C11Z, C11Z—CN, C11Z—CNS, C11Z—A, 2MZ—OK, 2 MA—OK, 2PHZ (trade names of Shikoku Kasei Kogyo Co., Ltd.). Specific examples of the amine amine compound include Novaki Yua (trade name of Asahi Kasei Kogyo Co., Ltd.) and Fuji Cure (trade name of Fuji Kasei Kogyo Co., Ltd.). Specific examples of the tertiary amine compound include DBU (1,8-diazabicyclo [5,4,0] undec-7-ene). In the epoxy resin composition of the present invention, the content of the curing accelerator is usually when the total amount of epoxy resin and phenolic curing agent contained in the epoxy resin composition is 100% by mass (solid content). 0.1 Used in the range of 1-5% by mass.

 [0063] The epoxy resin composition of the present invention may contain a flame retardant as long as the effects of the present invention are exhibited. However, the use of halogen-based flame retardants is becoming difficult due to environmental problems such as dioxin in recent years, and the use of phosphorus-based flame retardants, such as the impact on the environment, is being suppressed. It is preferable to contain no flame retardant or as little as possible. Since the epoxy resin composition of the present invention can achieve sufficient flame retardancy without containing a halogen element and a phosphorus element, it can be an epoxy resin composition that is excellent in terms of environment.

 [0064] The epoxy resin composition of the present invention may contain other resin additives other than those described above as long as the effects of the present invention are exhibited. Examples of the oil additives include silicone powders, organic fillers such as nylon powder and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based and polymer-based antifoaming agents or leveling agents. , Imidazole series, thiazole series, triazole series, adhesion imparting agents such as silane coupling agents, and coloring pigments.

[0065] The epoxy resin composition of the present invention is applied to a support film to form a resin composition layer to form an adhesive film for a multilayer printed wiring board, or a sheet-like reinforcing substrate that also has fiber strength. The resin composition can be impregnated into a prepreg for an interlayer insulating layer of a multilayer printed wiring board. The epoxy resin composition of the present invention is applied to a circuit board to form an insulating layer. However, industrially, it is generally used for forming an insulating layer in the form of an adhesive film or a pre-preda.

 [0066] The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, and applying this resin varnish using the support film as a support. Further, the organic solvent can be dried by heating or blowing hot air to form a resin composition layer.

 [0067] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Carbitols such as cellosolve and butyral carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents may be used in combination.

 [0068] The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Different forces depending on the amount of organic solvent in the varnish For example, a varnish containing 30 to 60% by mass of an organic solvent can be dried at 50 to 150 ° C. for about 3 to 10 minutes. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

 [0069] The thickness of the resin composition layer formed in the adhesive film is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 m, the thickness of the resin composition layer is preferably 10 to: LOO m. The resin composition layer may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer.

[0070] Examples of the support film and protective film in the present invention include polyolefins such as polyethylene, polypropylene, and polychlorinated butyl, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyesters such as polyethylene naphthalate, and polycarbonate. Examples thereof include polyimide, and metal foil such as release paper, copper foil, and aluminum foil. The support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment. [0071] The thickness of the support film is not particularly limited, but is usually 10 to 150 µm, and preferably 25 to 50 / ζ πι. The thickness of the protective film is not particularly limited, but is usually 1 to 40 / ζ πι, preferably 10 to 30 / ζ πι. As will be described later, the support film used as the support in the production process of the adhesive film can also be used as a protective film for protecting the surface of the resin composition layer.

 [0072] The support film in the present invention is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heated and cured, adhesion of dust and the like in the curing process can be prevented, and the surface smoothness of the insulating layer after curing can be improved. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance. The resin composition layer formed on the support film is preferably formed so that the area of the layer is smaller than the area of the support film. The adhesive film can be wound up in a roll shape and stored and stored.

 [0073] Next, a method for producing the multilayer printed wiring board of the present invention using the adhesive film of the present invention will be described. When the resin composition layer is protected by a protective film, after peeling off, the resin composition layer is laminated on one or both sides of the circuit board so that the resin composition layer is in direct contact with the circuit board. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating method may be batch or continuous with rolls. In addition, the adhesive film and circuit board may be heated (preheated) as necessary before lamination.

[0074] The laminating conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressure bonding pressure is preferably 1 to: L lkgf / cm ² (9.8 x 10 ^{4 to} 109.9 x 10 ⁴ N / m ² ) and laminating under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

 [0075] Vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include: -Chigoichi 'Morton Co., Ltd. vacuum applicator 1; Meiki Seisakusho Co., Ltd. vacuum pressurizing laminator; Hitachi Industries roll dry coater; Hitachi Air Examples include vacuum laminators manufactured by EC Co., Ltd.

[0076] The circuit board in the present invention is mainly glass epoxy, metal board, polyester. This refers to a substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like on which one or both surfaces of a patterned conductor layer (circuit) are formed. A multilayer printed wiring board having a conductor layer (circuit) in which conductor layers and insulating layers are alternately formed and patterned on one or both sides is also included in the circuit board referred to in the present invention. The surface of the conductor circuit layer is preferably roughened by blackening or the like in advance from the viewpoint of adhesion of the insulating layer to the circuit board.

 [0077] After laminating the adhesive film on the circuit board in this way, when the support film is peeled off, the insulating film can be formed on the circuit board by peeling off and thermosetting. Heat curing conditions are selected in the range of 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably 160 ° C. C ~ 200. C for 30-120 minutes.

 [0078] After the insulating layer is formed, if the support film is peeled off before being cured, it is peeled off here. Next, a hole is made in the insulating layer formed on the circuit board to form a via hole and a through hole. Drilling force is a force that can be performed by a known method such as drilling, laser, or plasma, and a combination of these methods, if necessary, and is the most common method of drilling force by a laser such as a carbon dioxide laser or YAG laser.

 Next, roughening treatment is performed on the surface of the insulating layer. The roughening treatment in the present invention is usually preferably carried out by a wet roughening method using an oxidizing agent. Oxidizing agents include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide

Z sulfuric acid, nitric acid, etc. are mentioned. Preferably, an alkaline permanganic acid solution (for example, potassium permanganate or sodium permanganate hydroxide), which is an oxidant commonly used for the roughening of insulating layers in the production of multilayer printed wiring boards by the built-up method. It is preferable to perform roughening using (sodium aqueous solution).

 [0080] The roughness of the roughened surface obtained by roughening the surface of the insulating layer is usually Ra value force greater than or equal to ^ 0.01 μm, preferably 0. It is preferable that the roughness is 1 μm or more, especially 0.15 μm or more. The upper limit of the Ra value is preferably a force of 0.5 / zm or less from the viewpoint of the fine wiring formability, more preferably 0.5 or less, and particularly preferably 0.35 m or less.

[0081] Surface roughness Ra value is a kind of numerical value representing surface roughness, and is called arithmetic average roughness. Specifically, the absolute value of the height changing in the measurement region is measured by the surface line as an average line and arithmetically averaged. For example, using WYK ON NT3300 manufactured by BEIKOTSU SUMENTSU Co., Ltd., the VSI contact mode can be obtained from the numerical value obtained with a 50 × lens with a measurement range of 121 μm Χ 92 μm.

 [0082] Next, a conductor layer is formed on the surface of the resin composition layer on which uneven anchors have been formed by roughening treatment by a method combining electroless plating and electrolytic plating. In addition, a reverse resist pattern resist can be formed from the conductor layer, and the conductor layer can be formed only by electroless plating. After forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

 [0083] Further, as a method of forming a circuit by patterning the conductor layer, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

 [0084] The pre-preda of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material made of fiber by a hot melt method or a solvent method and semi-curing by heating. it can. That is, it can be set as the pre-predator which will be in the state which impregnated the resin composition of this invention in the sheet-like reinforcement base which consists of fibers.

 [0085] As the sheet-like reinforcing substrate made of fiber fiber, for example, a glass cloth garamide fiber, which is commonly used as a fiber for pre-predators, can be used.

 [0086] In the hot melt method, the resin without dissolving the resin in an organic solvent is coated on a coated paper having good releasability from the resin and laminated on a sheet-like reinforcing substrate, or by duplication. In this method, a pre-preda is manufactured by direct coating with an equator. Also, the solvent method is a method in which a sheet-like reinforcing base material is soaked in a resinous varnish in which the resin is dissolved in an organic solvent, and then the resinous varnish is impregnated into the sheet-like reinforcing base material and then dried. It is.

Next, a method for producing the multilayer printed wiring board of the present invention using the pre-preder of the present invention will be described. One or more of the pre-preders of the present invention are stacked on a circuit board, and a metal plate is sandwiched through a release film, and press-laminated under pressure and heating conditions. The pressure is preferably 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ), and the temperature is preferably 120 to 200 ° C. Better!/,. Same as adhesive film In this way, it can also be manufactured by laminating on a circuit board by a vacuum laminating method and then curing by heating. Thereafter, in the same manner as described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

 [0088] The present invention will be described in more detail with reference to the following examples and comparative examples, but these do not limit the present invention in any way. In the following description, “part” means “part by mass”.

 Example 1

[0089] Butyral resin (glass transition temperature 105 ° C, "KS-5ZJ" made by Sekisui Chemical Co., Ltd.) in a 1: 1 mixed solvent of ethanol and toluene at 60 ° C to a solid content of 15% A liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.) 30 parts and a naphthalene type tetrafunctional epoxy resin 30 parts of fat (epoxy equivalent: 163, “HP-4700” manufactured by Dainippon Ink and Chemicals, Inc.) is dissolved in 15 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) and 15 parts of cyclohexanone with stirring. It was. Thereto, 60 parts of MEK solution with a solid content of 50% solids of naphthol-based novolak rosin (“CBN” manufactured by Nippon Kayaku Co., Ltd., phenolic hydroxyl group equivalent: 139), thiomethyl group-containing phenolic hardener 18 parts of MEK solution with 60% solid content of novolak resin (“YLH-1110LJ, phenolic hydroxyl group equivalent 168” manufactured by Japan Epoxy Resin Co., Ltd.), curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 / ζ πι, aminosilane treatment, “SOC2” manufactured by Admatechs) 70 parts, 35 parts of the above butyral resin solution are mixed and rotated at high speed Uniform dispersion was performed with a mixer to prepare a rosin varnish (inorganic filler content based on the non-volatile content of the varnish varnish, 40% by mass). Next, this varnished varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as PET) with a die coater so that the dried varnish thickness would be 40 μm. It was dried at ° C (average 100 ° C) for 6 minutes (residual solvent amount was about 1% by mass). Next, a 15 μm-thick polypropylene film was bonded to the surface of the greave composition and wound into a roll. The roll-like adhesive film was slit to a width of 507 mm, and from this, a sheet-like adhesive film having a size of 507 × 336 mm was obtained. Example 2

 [0090] Liquid bisphenol A type epoxy resin (epoxy equivalent 180, Japan epoxy resin)

 30 parts of “Epicoat 828EL” (manufactured by Co., Ltd.) and 30 parts of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 163, “HP-4700” manufactured by Dainippon Ink & Chemicals, Inc.) (Hereinafter abbreviated as MEK) 15 parts and cyclohexanone 15 parts were heated and dissolved with stirring. To that end, 60 parts of a 50% solid MEK solution of novolak rosin (“NHN”, phenolic hydroxyl group equivalent: 143 manufactured by Nippon Kayaku Co., Ltd.), a naphthol-based curing agent, and thiomethyl group-containing phenol. 18 parts of MEK solution with a solid content of 60% solids of novolac rosin (“YLH-1110L” manufactured by Japan Epoxy Resin Co., Ltd., phenolic hydroxyl group equivalent 168), a curing catalyst (Shikoku Kasei Kogyo Co., Ltd.) Manufactured by “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 / ζ πι, treated with aminosilane, “SOC2” manufactured by Admatechs) 70 parts, 35 parts of petital resin solution prepared in Example 1 Were mixed uniformly with a high-speed rotary mixer to prepare a rosin varnish (inorganic filler content based on nonvolatile content of rosin varnish, 40% by mass). Next, a sheet-like adhesive film was obtained in the same manner as in Example 1.

 Example 3

 [0091] Liquid bisphenol A type epoxy resin (epoxy equivalent 180, Japan epoxy resin

30 parts of “Epicoat 828EL” manufactured by Co., Ltd. and 30 parts of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 163, “HP-4700” manufactured by Dainippon Ink and Chemicals, Inc.) (Hereinafter abbreviated as MEK) 15 parts and cyclohexanone 15 parts were heated and dissolved with stirring. To that end, 70 parts of a 50% solid MEK solution of naphthol-based novolak resin (“CBN” manufactured by Nippon Kayaku Co., Ltd., phenolic hydroxyl group equivalent: 139), thiomethyl group-containing phenol 9 parts of MEK solution of 60% solid content of novolac rosin (“YLH-1110L” manufactured by Japan Epoxy Resin Co., Ltd., phenolic hydroxyl group equivalent 168), a curing catalyst (Shikoku Kasei Kogyo Co., Ltd.) Manufactured by “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 / ζ πι, treated with aminosilane, “SOC2” manufactured by Admatechs) 70 parts, 35 parts of petital resin solution prepared in Example 1 Were mixed uniformly with a high-speed rotary mixer to prepare a rosin varnish (inorganic filler content based on nonvolatile content of rosin varnish, 40% by mass). Next, a sheet-like adhesive film was obtained in the same manner as in Example 1. Example 4

 [0092] Liquid bisphenol A type epoxy resin (epoxy equivalent 180, Japan epoxy resin)

 30 parts of “Epicoat 828EL” (manufactured by Co., Ltd.) and 30 parts of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 163, “HP-4700” manufactured by Dainippon Ink & Chemicals, Inc.) (Hereinafter abbreviated as MEK) 15 parts and cyclohexanone 15 parts were heated and dissolved with stirring. Thereto, 60 parts of MEK solution with 50% solid content of naphthalene-structured novolac resin (“CBN”, phenolic hydroxyl group equivalent: 139), a phenolic curing agent, containing thiomethyl group Novolak resin (“YLH-1110L” manufactured by Japan Epoxy Resin Co., Ltd., phenolic hydroxyl group equivalent weight 168), 18 parts of MEK solution with 60% solid content, curing catalyst (Shikoku Chemical Industries ( Co., Ltd., “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 m, aminosilane treatment, “SOC2” manufactured by Admatex) 70 parts, butyral resin solution prepared in Example 1 17 17 parts of phenoxy resin (Japan Epoxy Resin Co., Ltd. “YX8100 ΒΗ30”, 30% solids cyclohexanone and MEK mixing solution) were mixed and dispersed uniformly with a high-speed rotary mixer. A fat varnish was prepared (inorganic to the non-volatile content of rosin varnish. Hamazai content, 39 wt%). Next, a sheet-like adhesive film was obtained in the same manner as in Example 1.

 [0093] <Comparative Example 1>

30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, Dainippon Ink & Chemicals, Inc.) 30 parts of “HP-4700”) were dissolved in 15 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) and 15 parts of cyclohexanone with stirring. To that end, a novolak resin, a phenolic curing agent (“TD2 090-60M” manufactured by Dainippon Ink & Chemicals, Inc., MEK solution with a solid content of ½0% by mass, phenolic hydroxyl group equivalent of solids 105) 50 parts, curing catalyst (Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 m, aminosilane treatment, “SOC2” manufactured by Admatechs) 60 parts, implementation 35 parts of the petital rosin solution prepared in Example 1 was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a varnish varnish (inorganic filler content relative to the non-volatile content of the varnish varnish, 39 mass%). Next, a sheet-like adhesive film was obtained in the same manner as in Example 1. [0094] <Reference Example 1>

 30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, Dainippon Ink & Chemicals, Inc.) 30 parts of “HP-4700”) were dissolved in 15 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) and 15 parts of cyclohexanone with stirring. Then, 80 parts of MEK solution with a solid content of 60%, novolak resin, a thiomethyl group-containing phenolic hardener (“YLH-1110LJ, phenolic hydroxyl group equivalent 168” manufactured by Japan Epoxy Resin Co., Ltd.), curing catalyst (Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 / ζ πι, aminosilane treatment, “SOC2” manufactured by Admatechs) 70 parts, prepared in Example 1 35 parts of the petital rosin solution was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a rosin varnish (inorganic filler content relative to the non-volatile content of the varnish varnish, 38% by mass). Next, a sheet-like adhesive film was obtained in the same manner as in Example 1.

 [0095] <Reference Example 2>

 30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, Dainippon Ink & Chemicals, Inc.) 30 parts of “HP-4700”) were dissolved in 15 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) and 15 parts of cyclohexanone with stirring. To that end, a novolak rosin as a phenol curing agent (“TD20 90-60M” manufactured by Dainippon Ink & Chemicals, Inc., MEK solution with a solid content of ½0 mass%, phenolic hydroxyl group equivalent 105) 41 parts, thiomethyl group Novolak resin, which is a hardener containing phenol (Japan Epoxy Resin Co., Ltd. “¥ 1 ^ ¾11101 ^”, phenolic hydroxyl group equivalent 168), 14 parts, curing catalyst (manufactured by Shikoku Chemicals Co., Ltd.) , “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 / ζ πι, aminosilane treatment, “SOC2” manufactured by Admatechs Co., Ltd.) 65 parts, petital resin solution prepared in Example 1 35 parts Were mixed uniformly with a high-speed rotary mixer to prepare a resin varnish (inorganic filler content based on the non-volatile content of the resin grease, 40% by mass). Next, a sheet-like adhesive film was obtained in the same manner as in Example 1.

 [0096] <Manufacture of multilayer printed wiring board>

[0097] (1) Fabrication of circuit board A circuit pattern is formed on both sides of a glass cloth base epoxy resin-coated double-sided copper-clad laminate [copper foil thickness 18 m, substrate thickness 0.8 mm, Matsushita Electric Works Ltd. R5715ES]. It was immersed in CZ8100 manufactured by Co., Ltd. and the copper surface was roughened to prepare a circuit board.

 [0098] (2) Lamination of adhesive film

 The adhesive film prepared in Example 1 was laminated on both sides of the circuit board using a notch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at a pressure of 0.74 MPa for 30 seconds.

[0099] (3) Curing of the resin composition

 The laminated adhesive film also peeled off the PET film and cured the resin composition at 180 ° C for 30 minutes.

[0100] (4) Via hole formation

 Matsushita Welding System Co., Ltd. CO laser processing machine (YB— HCS03T04)

 2

 A via hole having a diameter of 60 μm on the surface of the insulating layer was formed by observing under conditions of a wave number of 10001¾, a pulse width of 13 seconds, and a shot number of 3.

[0101] (5) Roughening treatment

 The circuit board was immersed for 5 minutes at 60 ° C in a swelling dip-sequel ligand P containing diethylene glycol monobutyl ether from Atotech Japan. Next, crude concentrate, Atotech Japan's Concentrate 'Compact P (KMnO:

 Four

60 gZL, NaOH: 40 gZL aqueous solution) at 80 ° C. for 20 minutes. Finally, it was soaked at 40 ° C for 5 minutes in the neutralization solution, Reduction Sholyshin 'Sekiyuriganto P' from Atotech Japan.

[0102] (6) Meat with semi-additive method

 In order to form a circuit on the insulating layer surface, the circuit board is used for electroless plating containing PdCl.

 2

It was immersed in a solution and then immersed in an electroless copper plating solution. After heating for 30 minutes at 150 ° C. and carrying out a char treatment, copper sulfate electrolytic plating was performed. Annealing is performed at 180 ° C for 60 minutes to form a copper layer with a thickness of about 25 m on the surface of the insulating layer to obtain a multilayer printed wiring board. It was.

 [0103] <Preparation of peel strength measurement sample>

 [0104] (1) Laminate surface treatment

 Double-sided copper-clad laminate with glass cloth substrate epoxy resin [copper foil thickness 18 m, substrate thickness 0.8 mm, R5715ES made by Matsushita Electric Works Ltd.] both sides immersed in MEC CZ8100 copper The surface was roughened.

 [0105] (2) Lamination of adhesive film

 The adhesive films prepared in Examples, Comparative Examples, and Reference Examples were laminated on both surfaces of a laminate using a notch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at a pressure of 0.74 MPa for 30 seconds.

 [0106] (3) Curing of the resin composition

 The laminated adhesive film also peeled off the PET film and cured the resin composition at 180 ° C for 30 minutes.

 [0107] (4) Roughening treatment

 The laminate is immersed in a swelling dip Sekiyu ligand p containing diethylene glycol monopropyl ether from Atotech Japan Co., Ltd. for 5 minutes at 60 ° C. ) Concentrate 'Compact P (KMn04: 60 g ZL, NaOH: 40 g ZL aqueous solution) at 80 ° C for 20 minutes, and finally, as a neutralizing solution, Atotech Japan Co., Ltd. Immerse at 40 ° C for 5 minutes.

 [0108] (5) Meat with semi-additive method

 Immerse the laminate in an electroless plating solution containing PdCl and then in an electroless copper plating solution.

 2

 Pickled. After annealing for 30 minutes at 150 ° C, copper sulfate electrolytic plating was performed to form a copper layer with a thickness of 25 ± 10 m. Next, annealing was performed at 180 ° C for 60 minutes. The peel strength of the copper plating was measured using this laminate.

[0109] [Peel strength test of peeled copper layer]

Make a notch of 10mm width and 100mm length in the copper layer of the laminate, and strip this end. The load was measured when 35mm was peeled off in the vertical direction at a speed of 50mmZ at room temperature.

 [0110] [Flame retardancy test]

 The adhesive films obtained in Examples, Comparative Examples, and Reference Examples were laminated on both sides of a 0.2 mm thick glass epoxy substrate (R1566 manufactured by Matsushita Electric Works) and regreased at 180 ° C for 90 minutes. Cured. Sample test pieces were prepared according to UL-94 for the cured product, and a flame retardancy test was conducted.

 [0111] [Storage stability (pot life) test]

 The adhesive films obtained in Examples, Comparative Examples and Reference Examples were allowed to stand at room temperature (25 ° C.) for 72 hours, and were used with a model Rheoso G3000 manufactured by UBM Co., Ltd. The dynamic viscoelasticity of the fat composition layer was measured. A tablet with a diameter of 20 mm and a thickness of about 2.3 mm (weight: about lg) is used as a measurement sample, and a measurement start temperature is set to 60 ° C using a normal plate, and the rate of temperature rise is 5 ° C. The measurement was performed under the conditions of ° CZ min, measurement interval temperature 2.5 ° C, frequency lHzZdeg, 100 g static load constant. As curing progressed, X was defined as X when the viscosity was not measurable at the start of measurement, and X was marked for viscosity measurement without overload.

 [0112] Table 1 shows the results of each test for the samples of Examples 1 to 4, Comparative Example 1 and Reference Examples 1 and 2. It can be seen that the example samples are excellent in all of flame retardancy, storage stability and peel strength.

[0113] [Table 1]

Industrial applicability

 The epoxy resin composition of the present invention, the adhesive film prepared with the resin composition, and the pre-preda form an interlayer insulating layer of a multilayer printed wiring board, particularly a multilayer printed wiring board manufactured by a build-up method. It is suitably used as a material to be used.

 This application is based on Japanese Patent Application No. 2006-045638 filed in Japan, the contents of which are incorporated herein by reference in their entirety.

Claims

The scope of the claims  [1] (A) Aromatic epoxy resin having two or more epoxy groups in one molecule, (B) naphthol curing agent, (C) thioalkyl group-containing phenol curing agent, and (D) inorganic filling An epoxy resin composition characterized by containing a material. [2] The epoxy resin composition according to claim 1, comprising 20 to 60% by mass of the inorganic filler of component (D) when the nonvolatile component of the epoxy resin composition is 100% by mass. [3] The epoxy resin composition according to claim 1, comprising 30 to 50% by mass of the inorganic filler of component (D) when the nonvolatile component of the epoxy resin composition is 100% by mass. [4] The epoxy resin composition according to any one of claims 1 to 3, wherein the inorganic filler of component (D) is silica.  [5] The epoxy resin according to any one of claims 1 to 4, wherein the blending ratio of the components (B) and (C) is 1: 0.1 to 1: 1.5 by mass ratio. Composition. [6] The naphthol curing agent of component (B) is represented by the following formula (1):  [Chemical 1]

(Wherein R1 to R4 each independently represents a hydrogen atom or an alkyl group, XI is each substituted with an alkyl group, may be a naphthalene ring, and Y is each substituted with an alkyl group. A benzene ring, a hydroxybenzene ring, a biphenyl ring or a naphthalene ring, and j and k each represent an average value of 1 to 15.)  A naphthol type hardener represented by the formula (2): [Chemical 2]

 (In the formula, R5 represents a hydrogen atom or an alkyl group, R6 represents a thioalkyl group, X2 is each substituted with an alkyl group, and represents a benzene ring or a naphthalene ring, and j and k are average values, respectively. And m represents an integer of 1 to 5. The epoxy resin composition according to any one of claims 1 to 5, which is a thioalkyl group-containing phenolic curing agent represented by: object.  [7] The naphthol-based curing agent of component (B) is represented by the following formula (1 '):  [Chemical 3]

(Wherein R1 to R4 each independently represents a hydrogen atom or an alkyl group, XI is each substituted with an alkyl group, may be a naphthalene ring, and Y is each substituted with an alkyl group. A benzene ring, a hydroxybenzene ring, a biphenyl ring, or a naphthalene ring, and n represents an average value of 1 to 15.) A thioalkyl group-containing phenolic curing agent of component (C) represented by the following formula (2 ') _: [Chemical 4]

(In the formula, R5 represents a hydrogen atom or an alkyl group, R6 represents a thioalkyl group, X2 is each substituted with an alkyl group, and may represent a benzene ring or a naphthalene ring, and n represents an average value of 1 to Represents a number of 15, m represents an integer of 1 to 5.)  The epoxy resin composition according to any one of claims 1 to 5, which is a thioalkyl group-containing phenolic curing agent represented by the formula: [8] The aromatic epoxy resin of component (A) is (Al) an aromatic epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C. And (A2) a second epoxy resin that has 3 or more epoxy groups in one molecule and is a solid aromatic epoxy resin at a temperature of 20 ° C. 8. The epoxy resin composition according to any one of 1 to 7, wherein  [9] The epoxy resin composition according to claim 8, wherein the epoxy equivalent of the second epoxy resin of component (A2) is 230 or less.  10. The epoxy resin composition according to claim 8, wherein the epoxy equivalent of the second epoxy resin of component (A2) is in the range of 150 to 230. [11] The mixing ratio (A1: A2) of the first epoxy resin (A1) and the second epoxy resin (A2) is in the range of 1: 0.3 to 1: 2 by mass ratio. Item 10. The epoxy resin composition according to any one of items 8 to 10, wherein [12] When the non-volatile component of the epoxy resin composition is 100% by mass, the content of the aromatic epoxy resin of component (A) is 10 to 50% by mass and is present in the epoxy resin composition The ratio of the phenolic hydroxyl group of the naphthol-based curing agent of component (B) and the thioalkyl group-containing phenolic curing agent of component (C) to the epoxy group is from 1: 0.5 to 1: 1.5. The epoxy resin composition according to any one of 1 to 11 above. [13] The epoxy resin composition according to any one of [1] to [12], wherein the epoxy resin composition further comprises a polybulassetal resin.  [14] The epoxy resin composition according to [13], wherein the content of the polybulacetal resin is 2 to 20% by mass when the nonvolatile component of the epoxy resin composition is 100% by mass.  [15] An adhesive film in which the epoxy resin composition according to any one of claims 1 to 14 is layered on a support film.  [16] A pre-preda, wherein the epoxy resin composition according to any one of claims 1 to 14 is impregnated in a sheet-like reinforcing base material having a fiber strength.  [17] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the epoxy resin composition according to any one of claims 1 to 14.  [18] A method for producing a multilayer printed wiring board, comprising: a step of forming an insulating layer on an inner layer circuit board; and a step of forming a conductor layer on the insulating layer, wherein the insulating layer comprises: The epoxy resin composition according to any one of claims 1 and 2 is formed by thermosetting, and the conductor layer is formed by copper plating on a rough surface obtained by roughening the surface of the insulating layer. A method for producing a multilayer printed wiring board, characterized by:  [19] The method for producing a multilayer printed wiring board, comprising a step of forming an insulating layer on the inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is the adhesive according to claim 15. The film is laminated on the inner circuit board, and the epoxy resin composition is thermally cured with or without peeling the support film, and when the support film is present after curing, the support film is peeled off and formed. A method for producing a multilayer printed wiring board, wherein the conductor layer is formed by copper plating on a roughened surface obtained by roughening the surface of the insulating layer.  [20] A method for producing a multilayer printed wiring board, comprising: a step of forming an insulating layer on an inner circuit board; and a step of forming a conductor layer on the insulating layer. It is formed by laminating a preda on an inner circuit board and thermosetting an epoxy resin composition, and the conductor layer is formed by copper plating on a roughened surface obtained by roughening the surface of the insulating layer. The manufacturing method of a multilayer printed wiring board.