TWI796291B - thermosetting resin composition - Google Patents

Abstract

The present invention provides a thermosetting thermosetting resin, an adhesive film, and wiring using the insulating layer that can form a bendable insulating layer with good dimensional accuracy and reflow resistance when manufacturing a wiring board with an embedded wiring layer. A method of manufacturing a board, a wiring board, and a semiconductor device.

The thermosetting resin composition of the present invention comprises (a) an epoxy resin, (b) a compound having a hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and (d) ) A thermosetting resin composition of an inorganic filler, in which part or all of at least one of the (a) component and (c) component has an alkylene structure having 2 to 20 carbon atoms and a carbon number of 2 to 20 A compound with a flexible structure of an alkylene structure of an ether bond of 20, when the non-volatile content in the thermosetting resin composition is 100 mass%, the (d) component is 30 mass% or more, so that the thermosetting resin composition The elastic modulus, breaking strength, and breaking elongation of the hardened product obtained by thermal curing at 23°C are 1GPa to 6GPa, 10MPa to 6%, and 6% to above.

Description

thermosetting resin composition

The present invention relates to a thermosetting resin composition. It further relates to an adhesive film having a thermosetting resin composition layer, a method for manufacturing a wiring board using the adhesive film, a wiring board, and a semiconductor device.

As a method of manufacturing a wiring board (printed circuit board), for example, a build-up method in which a conductive layer and an insulating layer formed with a circuit are alternately stacked is widely used, and it is known to harden a resin composition to form an insulating layer (for example, refer to Patent Document 1). .

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2015-82535

[Outline of Invention]

In recent years, the thinner, thinner and smaller electronic devices have required flexible wiring boards that can be bent and accommodated in electronic devices. To make the patch panel Further thinning requires a wiring board with an embedded wiring layer.

The insulation layer used in wiring boards with embedded wiring layers, in order to reduce the inconsistency of the average linear thermal expansion coefficient (Coefficient of Thermal Expansion: CTE, also known as thermal expansion rate) between the wiring layer or parts, Therefore, the inorganic filler is a material with high filling hardness. However, due to the hard material, it cannot be bent. In addition, when a soft material is used for bending, there are problems of dimensional accuracy and reflow resistance.

The object of the present invention is to solve the above-mentioned problems, and to provide a thermosetting resin composition that has excellent dimensional accuracy and reflow resistance and can form a bendable insulating layer when manufacturing a wiring board with a buried wiring layer. , Adhesive film, manufacturing method of wiring board using same, wiring board and semiconductor device.

That is, the present invention includes the following matters.

[1] A thermosetting resin composition comprising (a) an epoxy resin, (b) a compound having a hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and ( d) A thermosetting resin composition of an inorganic filler, wherein a part or all of at least one of the (a) component and (c) component is selected from those having an alkylene structure having 2 to 20 carbon atoms and having an ether bond. A compound with a flexible structure of an alkylene structure with 2 to 20 carbon atoms, when the non-volatile component in the thermosetting resin composition is 100% by mass When the component (d) is 30% by mass or more, the elastic modulus, breaking strength, and breaking elongation of the cured product obtained by thermosetting the thermosetting resin composition at 23°C are 1 GPa to 6 GPa, 10 MPa to 6 GPa, and 6 GPa to 6 GPa, respectively. %above.

[2] The thermosetting resin composition according to [1], wherein the flexible structure is an alkylene structure having 3 to 15 carbon atoms having an ether bond.

[3] The thermosetting resin composition according to [1] or [2], wherein when the non-volatile components in the thermosetting resin composition are 100 mass%, the content of the compound having a soft structure is 2 mass%~ 50% by mass.

[4] The thermosetting resin composition according to any one of [1] to [3], wherein when the non-volatile content in the thermosetting resin composition is 100% by mass, the content of the component (b) is 8 Mass%~50 mass%.

[5] An adhesive film comprising a support and the thermosetting resin composition layer according to any one of [1] to [4].

[6] The adhesive film according to [5], which is used in a manufacturing method of a wiring board including the steps of: (1) preparing a base with a wiring layer having a base material and a wiring layer provided on at least one side of the base material; (2) Embedding the wiring layer in the thermosetting resin composition layer, and laminating the adhesive film containing the thermosetting resin composition layer on the base material with the wiring layer, and thermosetting to form insulation layer, (3) the step of interlayer connection wiring layer and (4) the step of removing the base material.

[7] The following film as in [6], wherein step (3) is to form a conductive film on the insulating layer At least any one of a step of forming a via hole, a step of forming a conductor layer, and a step of grinding or grinding an insulating layer to expose a wiring layer.

[8] The adhesive film according to [5], which is used to manufacture a wiring board having an insulating layer and an embedded wiring layer embedded in the insulating layer.

[9] A method of manufacturing a wiring board, comprising the steps of: (1) preparing a base material having a base material and a wiring layer attached to at least one side of the base material; The layer is embedded in the thermosetting resin composition layer, and the step of laminating the adhesive film of any one of [5] to [8] on the base material with wiring layer, and thermosetting to form an insulating layer, (3 ) a step of connecting the wiring layers between layers and (4) a step of removing the base material.

[10] The method according to [9], wherein the step (3) is at least any one of the steps of forming a via hole in the insulating layer, forming a conductive layer, and grinding or grinding the insulating layer to expose the wiring layer.

[11] The method according to [9] or [10], wherein the step (3) is a step of forming a via hole in the insulating layer and forming a conductive layer, and is performed by laser irradiation.

[12] The method according to [11], which includes the step of performing a roughening treatment before forming the conductive layer.

[13] The method according to any one of [9] to [12], wherein the wiring board is a flexible wiring board.

[14] The method according to any one of [9] to [13], wherein the minimum pitch of the wiring pattern is 40 μm or less.

[15] A wiring board, which is equipped with any one of [5]~[8] The insulating layer of the cured product of the thermosetting resin composition layer of the film, and the embedded wiring layer embedded in the insulating layer.

[16] The wiring board of [15], which is a flexible wiring board.

[17] The wiring board according to [15] or [16], wherein the insulating layer has a thickness of 2 μm or more.

[18] A semiconductor device comprising the wiring board according to any one of [15] to [17].

According to the present invention, it is possible to provide a thermosetting resin composition that can form a bendable insulating layer when manufacturing a wiring board with an embedded wiring layer, excellent dimensional accuracy and reflow resistance, an adhesive film, and a combination thereof. A method of manufacturing a wiring board, a wiring board, and a semiconductor device.

1‧‧‧Watching board

10‧‧‧Substrate with wiring layer

11‧‧‧Substrate (core substrate)

12‧‧‧The first metal layer

13‧‧‧The second metal layer

14‧‧‧wiring layer (embedded wiring layer)

20‧‧‧adhering film

21‧‧‧thermosetting resin composition layer

21’‧‧‧Insulation layer

22‧‧‧Support

23‧‧‧Protective film

31‧‧‧via hole

40‧‧‧conductor layer

41‧‧‧Plating protective layer

42‧‧‧Electroplating layer

50‧‧‧Mask graphics

61‧‧‧hole filling

[FIG. 1] FIG. 1 is a schematic sectional view for explaining the manufacturing steps of a wiring board.

[ Fig. 2] Fig. 2 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 3] Fig. 3 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 4] Fig. 4 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 5] Fig. 5 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 6] Fig. 6 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 7] Fig. 7 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 8] Fig. 8 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 9] Fig. 9 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 10] Fig. 10 is a schematic cross-sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 11] Fig. 11 is a schematic sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 12] Fig. 12 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 13] Fig. 13 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 14] Fig. 14 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 15] Fig. 15 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 16] Fig. 16 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 17] Fig. 17 is a schematic sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 18] Fig. 18 is a schematic sectional view for explaining a manufacturing step of a wiring board.

[ Fig. 19] Fig. 19 is a schematic sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 20] Fig. 20 is a schematic cross-sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 21] Fig. 21 is a schematic sectional view for explaining the manufacturing steps of the wiring board.

[ Fig. 22] Fig. 22 is a schematic sectional view for explaining a wiring board.

[ Fig. 23] Fig. 23 is a schematic sectional view for explaining a wiring board.

The thermosetting resin composition, the adhesive film, the manufacturing method of the wiring board, the wiring board, and the semiconductor device of the present invention will be described in detail below.

[Thermosetting resin composition]

The thermosetting resin composition of the present invention comprises (a) an epoxy resin, (b) a compound having a hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and (d) ) Inorganic fillers. Additives such as (e) curing agent, (f) curing accelerator, (g) flame retardant and (h) organic filler may be further contained if necessary. The details will be described later, but when manufacturing a wiring board, the wiring layer Embedded in the thermosetting resin composition layer, thereby forming an embedded wiring layer. Therefore, part or all of at least one of the (a) component and (c) component has an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having 2 to 20 carbon atoms having an ether bond. The soft structure compound, when the non-volatile content in the thermosetting resin composition is 100 mass%, (d) component is 30 mass% or more, and the cured product obtained by thermosetting the thermosetting resin composition is heated at 23°C The elastic modulus, breaking strength, and breaking elongation are above 1GPa and below 6GPa, above 10MPa, and above 6%, respectively.

-(a) Epoxy resin-

The epoxy resin usable for the thermosetting resin composition of the present invention is not particularly limited as long as it is a compound having an epoxy group in its molecule. For example, compounds having a flexible structure selected from alkylene structures having 2 to 20 carbon atoms and alkylene structures having 2 to 20 carbon atoms having ether bonds (hereinafter sometimes referred to as "flexibility-containing compounds") can be cited. Structure compound"), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol 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, glycidylamine type epoxy resin with aromatic structure, glycidyl ester type epoxy resin with aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin , linear aliphatic epoxy resin with aromatic structure, epoxy resin with aromatic structure and butadiene structure, alicyclic epoxy resin with aromatic structure Epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin with aromatic structure, cyclohexanedimethanol epoxy resin with aromatic structure, naphthyl ether type epoxy resin, epoxy resin with aromatic structure Trimethylol type epoxy resin, tetraphenylethane type epoxy resin with aromatic structure, etc. An epoxy resin can be used individually by 1 type or in combination of 2 or more types.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having three or more epoxy groups in one molecule, which is solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"), or a combination of two or more epoxy groups in one molecule For epoxy groups, epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and solid epoxy resins are preferred. A resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin. In addition, the fracture strength of the cured product of the resin composition can also be increased.

The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin with aromatic structure Oxygen resin, glycidylamine type epoxy resin with aromatic structure, phenol novolak type epoxy resin, alicyclic epoxy resin with aromatic structure and ester skeleton, cyclohexanedioxide with aromatic structure Methanol type epoxy resin and epoxy resin with aromatic structure and butadiene structure, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene ring Oxygen resin, and more Preferable are bisphenol A type epoxy resin and bisphenol F type epoxy resin. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Co., Ltd., "828US" and "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), " 630", "630LSD" (glycidyl amine type epoxy resin), "ZX 1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. products), "EX-721" (glycidyl ester type epoxy resin) manufactured by nagasechemtex Co., Ltd., "CELLOXID2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL Co., Ltd., Xinri "ZX1658" and "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane) manufactured by Iron Chemical Co., Ltd. These can be used individually by 1 type or in combination of 2 or more types.

Solid epoxy resins are preferably naphthalene-type 4-functional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins with aromatic structures, triphenol-type epoxy resins, naphthol-type Epoxy resin, biphenyl type epoxy resin, pernaphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, more preferably naphthalene type tetrafunctional Epoxy resins, naphthol-type epoxy resins, and biphenyl-type epoxy resins, more preferably naphthalene ether-type epoxy resins, and more preferably naphthalene-type tetrafunctional epoxy resins, and naphthyl ether-type epoxy resins. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), " N-690」 (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (pernaphthyl ether type epoxy resin), Nippon Kayaku EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin ), "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX4000H" manufactured by Mitsubishi Chemical Co., Ltd., " YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" manufactured by Osaka Gas Chemical Co., Ltd. , "CG-500", "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (stilbene type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Co., Ltd. (solid bisphenol A type epoxy resin), "jER1031S" (Tetraphenylethane type epoxy resin), etc.

The liquid epoxy resin preferably has more than 2 epoxy groups in 1 molecule, and is a liquid aromatic epoxy resin at a temperature of 20°C, and the solid epoxy resin preferably has 3 epoxy groups in 1 molecule. Aromatic epoxy resin that has more than one epoxy group and is solid at a temperature of 20°C. Also, the aromatic epoxy resin referred to in the present invention refers to an epoxy resin having an aromatic ring structure in its molecule.

Epoxy resin is a combination of liquid epoxy resin and solid epoxy In the case of resins, their quantitative ratio (liquid epoxy resin: solid epoxy resin) is represented by a mass ratio, preferably in the range of 1:0.1 to 1:20. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in this range, it is possible to obtain i) moderate adhesiveness when used in the form of adhering to a film, and ii) use in a form of adhering to a film In some cases, sufficient flexibility can be obtained to improve operability, and iii) effects such as obtaining a cured product with sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i)~iii), the ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is represented by mass ratio, more preferably 1: The range of 0.3~1:10, and more preferably the range of 1:0.6~1:9.

The content of the epoxy resin in the thermosetting resin composition is preferably at least 4% by mass, more preferably at least 5% by mass, and still more preferably, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. 6% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention can be exerted, but it is preferably 50% by mass or less, more preferably 40% by mass or less.

In the present invention, the content of each component in the thermosetting resin composition represents the value when the non-volatile components in the thermosetting resin composition are 100% by mass unless otherwise stated.

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, more preferably 80-2000, and more preferably 110-1000. Within this range, the cured product has sufficient crosslink density and an insulating layer with low surface roughness. Moreover, epoxy equivalent can be measured based on JISK7236, and is the mass of the resin containing the epoxy group of 1 equivalent.

The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, and more preferably 400-1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

-Compounds having a flexible structure selected from alkylene structures having 2 to 20 carbon atoms and alkylene structures having 2 to 20 carbon atoms having ether bonds-

In the thermosetting resin composition of the present invention, part or all of at least one of (a) component and (c) component, that is, part or all of (a) component and/or (c) component is a A compound having a flexible structure of an alkylene structure with 2 to 20 atoms and an alkylene structure with 2 to 20 carbon atoms having an ether bond.

The alkylene structure having 2 to 20 carbon atoms is preferably the alkylene structure having 4 to 15 carbon atoms, more preferably the alkylene structure having 4 to 10 carbon atoms. The alkylene structure may be linear, branched, or cyclic, but is preferably a linear or branched alkylene structure. Such alkylene structures include, for example, methylene, ethylidene, propylidene, butylene, pentyl, hexylene, heptyl, octyl, nonenyl, decenyl, undecenyl, Carbenyl, Dodecenyl, Tridecenyl, Tetradecenyl, Pentadecenyl, Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Decalinyl group, norbornyl, adamantyl, etc., preferably methylene, ethyl, propyl, butyl, pentyl, hexyl, and may also have a halogen atom, an alkyl, an alkane Substituents such as oxy group, alkylene group, amino group, silyl group, acyl group, acyloxy group, carboxyl group, sulfo group, cyano group, nitro group, hydroxyl group, mercapto group, side oxy group, etc. exist Here, the above-mentioned number of carbon atoms does not include the number of carbon atoms of the substituent.

The alkylene structure having 2 to 20 carbon atoms having an ether bond is not particularly limited as long as it is an alkylene structure having at least one ether bond and having 2 to 20 carbon atoms in its structure. For example, oxygen An alkylene structure, an alkyleneoxy structure, an oxyalkyleneoxy structure, an alkyleneoxyalkylene structure, an alkyleneoxyalkyleneoxyalkylene structure, and the like. An alkylene structure having 2 to 20 carbon atoms having an ether bond, preferably an alkylene structure having 2 to 15 carbon atoms having an ether bond, more preferably an alkylene structure having 3 to 15 carbon atoms having an ether bond Alkyl structure. The alkylene structure can be any of linear, branched and cyclic, and is preferably a linear or branched alkylene structure. The alkylene structure having such an ether bond includes oxymethylene, oxyethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl, oxyheptyl, and oxyoctyl. Oxynonyl, Oxydecenyl, Oxyundecenyl, Oxydodecenyl, Oxytridecenyl, Oxytetradecenyl, Oxypentadecenyl, Oxycyclic Propyl, oxycyclopentyl, oxycyclopentyl, oxycyclohexyl, oxydecalinyl, oxynorbornyl, oxyadamantyl, etc., may also have oxymethylene, oxyextended Ethyl, oxypropyl, oxybutyl, oxypentyl, oxyhexyl are preferred, halogen atom, alkyl, alkoxy, alkylene, amino, silyl, acyl, acyloxy Substituents such as group, carboxyl group, sulfo group, cyano group, nitro group, hydroxyl group, mercapto group, pendant oxygen group, etc. Here, the above-mentioned number of carbon atoms does not include the number of carbon atoms of the substituent.

Specific compounds with flexible structures that can be used in the present invention include, for example, epoxy resins (k is an integer of 1 to 20, preferably an integer of 1 to 5) or phenoxy resins of their polymers with the following structures.

In addition, for example, resins with the following structures can be enumerated (h is an integer of 0 to 20, preferably an integer of 0 to 5, each of i and j is an integer of 1 to 20, preferably an integer of 1 to 5, preferably It is an integer of i+j=2~10).

and

In addition, examples include EXA-4850-150, EXA-4816, and EXA-4822 (epoxy resins containing an alkylene structure having an ether bond) manufactured by DIC Corporation; EP-4000S, EP-4000SS, EP-4003S, EP-4010S, and EP-4011S (containing ether Epoxy resins with an alkylene structure with an ether bond); BEO-60E and BPO-20E (epoxy resins with an alkylene structure having an ether bond) manufactured by Nippon Chemical Corporation; YX7105, YX7110, and YX7400 manufactured by Mitsubishi Chemical Corporation (Epoxy resin containing alkylene structure with ether bond) and YX7180 (Phenoxy resin containing alkylene structure with ether bond) etc.

When the non-volatile components in the thermosetting resin composition are 100% by mass, the content of the compound having a flexible structure is preferably 2% by mass to 50% by mass. More preferably, it is at least 5 mass %, more preferably at least 10 mass % or at least 15 mass %, more preferably at most 40 mass %.

-(b) Compounds having hydrogenated butadiene structures and phenolic hydroxyl groups-

The thermosetting resin composition of the present invention contains (b) a compound having a hydrogenated butadiene structure and a phenolic hydroxyl group. By including a soft structure such as a butadiene structure, the modulus of elasticity of the cured product of the thermosetting resin composition can be lowered, and the wiring board manufactured using the adhesive film of the present invention can be bent. Part or all of the butadiene formation can be hydrogenated.

(b) component has a phenolic hydroxyl group in order to react with (a) component. Also, the phenolic hydroxyl group refers to a hydroxyl group that exists in a form in which a hydrogen atom in an aromatic ring structure is substituted with a hydroxyl group (hydroxyl group). (b) The hydroxyl equivalent weight of the component is preferably 100-30,000, more preferably 250-20,000. In addition, the functional group equivalent means the number of grams of resin containing a functional group equivalent to 1 g.

(b) The component is preferably one or more resins selected from resins having a glass transition temperature of 25°C or lower and liquid resins at 25°C.

Glass of resin with a glass transition temperature (Tg) below 25°C The transition temperature is preferably below 20°C, more preferably below 15°C. The lower limit of the glass transition temperature is not particularly limited, but usually -15°C or higher. Moreover, the resin which is liquid at 25°C is preferably a resin which is liquid at 20°C, more preferably a resin which is liquid at 15°C.

(b) The number average molecular weight (Mn) of the component is preferably 500-100,000, more preferably 1000-50,000. Here, the number average molecular weight (Mn) of resin is the number average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography).

The component (b) of the present invention can also use compounds made of hydroxyl-terminated polybutadiene, diisocyanate compounds, tetrabasic acid anhydrides, and polyfunctional phenol compounds as raw materials.

The hydroxyl-terminated polybutadiene preferably has a number average molecular weight of 300 to 5,000. Specific examples include, for example, G-1000, G-2000, G-3000, GI-1000, GI-2000 (manufactured by Nippon Soda Co., Ltd.), R-45EPI (manufactured by Idemitsu Petrochemical Co., Ltd.), etc. . Part or all of the butadiene formation can be hydrogenated.

A diisocyanate compound is a compound having two isocyanate groups in the molecule, for example, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, diisocyanate, Diisocyanates such as phenylmethane diisocyanate and isophorone diisocyanate.

Quaternary acid dianhydride-based compounds having two acid anhydride groups in the molecule include, for example, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dicarboxylic acid anhydride, 5-(2,5-dioxytetrahydrofuranyl)-3- Methyl-cyclohexene-1,2-dicarboxylic anhydride, 3,3'-4,4'-diphenylenetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, etc.

Examples of the polyfunctional phenol compound include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, biphenol, phenol novolak resin, alkylphenol novolak resin, bisphenol A type novolak resin, diphenol-containing Phenol novolac resin with cyclopentadiene structure, phenol novolak resin with triazine structure, phenol novolac resin with biphenyl skeleton, phenol novolac resin with phenyl group, terpene-modified phenol resin, polyvinyl phenols, etc. In particular, alkylphenol novolac resins are preferred.

The details of this compound can be referred to the description in International Publication No. 2008/153208, which is incorporated in this specification.

The content of component (b) in the thermosetting resin composition is not particularly limited, but is preferably at most 50% by mass, more preferably at most 20% by mass, still more preferably at most 15% by mass or at most 11% by mass. Moreover, the lower limit is preferably at least 2% by mass, more preferably at least 3% by mass, and still more preferably at least 4% by mass.

-(c) Phenoxy resin-

The thermosetting resin composition of the present invention contains (c) a phenoxy resin.

Examples of phenoxy resins include compounds having a flexible skeleton selected from the aforementioned compounds, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol AF skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl Skeleton, Skeleton, Dicyclopentadiene Skeleton, Norbornene Skeleton, Naphthalene Skeleton A phenoxy resin having at least one skeleton of the group consisting of an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin can be any functional group such as phenolic hydroxyl group or epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Co., Ltd. (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" (a phenoxy resin containing a bisphenol S skeleton). Oxygen resin), and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), others include "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Mitsubishi Chemical Co., Ltd. "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", "YX7180", etc.

The polystyrene-equivalent weight average molecular weight of the phenoxy resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 10,000 to 100,000, and still more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the phenoxy resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight-average molecular weight of the phenoxy resin can be measured using Shimadzu Corporation LC-9A/RID-6A as a measuring device and Shodex K- For 800P/K-804L/K-804L, use chloroform as the mobile phase, measure at a column temperature of 40°C, and calculate using the standard polystyrene calibration curve.

The epoxy equivalent of phenoxy resin is preferably 6000~30000, more preferably 7000~20000, and more preferably 9000~15000. Moreover, epoxy equivalent can be measured according to JISK7236, and is the mass of the resin containing the epoxy group of 1 equivalent.

The content of the phenoxy resin is preferably 0.5% by mass to 60% by mass, more preferably 3% by mass to 50% by mass, and more preferably 5% by mass to 40% by mass.

-(d) Inorganic filler-

The material of the inorganic filler is not particularly limited, and examples include silicon dioxide, aluminum oxide, glass, smilanite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, aluminum hydrochloride Stone, 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, titanium Bismuth oxide, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly preferred. Also, silica is preferably spherical silica. The inorganic filler may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and more preferably 0.6 μm or less from the viewpoint of good embedding properties. The lower limit of the average particle diameter is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, and still more preferably at least 0.1 μm. Commercially available inorganic fillers having such an average particle size include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs, Electrochemical Industrial Co., Ltd. "UFP-30", Tokuyama Co., Ltd. "SilFile NSS-3N", "SilFile NSS-4N", "SilFile NSS-5N", Co., Ltd. admatechs "SOC4", "SOC2" , "SOC1", etc.

The average particle size of inorganic fillers can be determined by laser diffraction based on Mie scattering theory. measured by scattering. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis with a laser diffraction scattering particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. As a measurement sample, it is preferable to use an inorganic filler dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Seisakusho Co., Ltd., etc. can be used.

Inorganic fillers are preferably aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, Treated with one or more surface treatment agents such as organosilazane compounds, titanate-based coupling agents, etc. Commercially available surface treatment agents include, for example, "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-803" manufactured by Shin-Etsu Chemical Co., Ltd. "(3-mercaptopropyltrimethoxysilane), "KBE-903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd. "(N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM" manufactured by Shin-Etsu Chemical Co., Ltd. -103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m ² or ^more , still more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler ² or more. In addition, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in a flake form, it is preferably at most 1 mg/m ² , more preferably at most 0.8 mg/m ² , and still more preferably at most 0.5 mg/m ² .

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (such as methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

The content of the inorganic filler in the thermosetting resin composition is preferably at least 30% by mass, more preferably at least 40% by mass, and still more preferably at least 50% by mass, from the viewpoint of obtaining an insulating layer with a low thermal expansion rate. The upper limit of the content of the inorganic filler in the thermosetting resin composition is preferably at most 90% by mass, more preferably at most 75% by mass, from the viewpoint of the mechanical strength of the insulating layer, especially the tensile strength.

-(e) Hardener-

The curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples thereof include phenolic curing agents, naphthol-based curing agents, and active esters. Curing agent, benzoxazine curing agent, cyanate ester curing agent, carbodiimide curing agent, etc. The curing agent may be used alone or in combination of two or more. (e) The component is preferably at least one selected from phenolic curing agents, naphthol-based curing agents, active ester-based curing agents, and cyanate-based curing agents.

The phenol-based curing agent and the naphthol-based curing agent are preferably a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred. Among these, a phenol novolak hardener containing a triazine skeleton is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", " SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC- 9500", etc.

From the viewpoint of obtaining an insulating layer excellent in adhesion with the wiring layer, an active ester-based curing agent is preferred. The active ester-based hardener is not particularly limited, and it is generally preferred to use phenolic esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. A compound with two or more highly reactive ester groups. The active ester hardener is obtained through the condensation reaction of carboxylic acid compounds and/or thiocarboxylic acid compounds with hydroxyl compounds and/or thiol compounds. In particular, from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester-based hardener obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred . Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Phenol compounds or naphthol compounds include, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol Phenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, Dihydroxybenzophenone, Trihydroxybenzophenone, Tetrahydroxybenzophenone, Phloroglucinol, Glycerol, Dicyclopentadiene type diphenol compound, Phenol novolac Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensation of 2 molecules of phenol with respect to 1 molecule of dicyclopentadiene.

Specifically, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolaks, and benzoyl compounds containing phenol novolaks Active ester compounds are preferred, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentyl-phenylene.

Commercially available active ester-based hardeners, including active ester compounds containing dicyclopentadiene-type diphenol structures, include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC -8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.), active ester compounds containing a naphthalene structure, examples of which include "EXB9416-70BK" (manufactured by DIC Co., Ltd.), a phenolic novolak-containing The active ester compound of benzoyl compound includes "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), the active ester compound of benzoyl compound including phenol novolak includes "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), phenol The active ester-based hardener of acetylated novolaks includes "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), and the active ester-based hardener of benzoylated phenol novolacs includes "YLH1026" (Mitsubishi Chemical Co., Ltd. (stock)), "YLH1030" (Mitsubishi Chemical Co., Ltd.), "YLH1048" (Mitsubishi Chemical Co., Ltd.), etc.

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

Cyanate-based hardeners include, for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'- Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis( 4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3- 2 of bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether Functional cyanate ester resin, derived from phenol novolac and cresol novolac Multifunctional cyanate resins, prepolymers in which part of these cyanate resins are triazinated, and the like. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" manufactured by Lonza Japan Co., Ltd. (prepolymer of bisphenol A dicyanate partially or fully triazinated trimer), etc.

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

The ratio of epoxy resin to hardener is represented by the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactive groups of hardener], preferably in the range of 1:0.01~1:2. More preferably, it is 1:0.015 to 1:1.5, and more preferably, it is 1:0.02 to 1:1. Here, the reactive group of the curing agent refers to an active hydroxyl group, an active ester group, etc., and varies depending on the type of the curing agent. Also, the total number of epoxy groups in the epoxy resin refers to the total value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the hardener refers to For all hardeners, divide the mass of the solid content of each hardener by the total value of the reactive group equivalent. By setting the molar ratio between the epoxy resin and the curing agent in this range, the heat resistance of the cured product of the resin composition can be further improved.

In one embodiment, the thermosetting resin composition includes the aforementioned (a) epoxy resin, (b) a compound having a hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and (d) Inorganic filler and (e) curing agent. The thermosetting resin composition contains solid epoxy resin as (a) epoxy resin alone or a mixture of liquid epoxy resin and solid epoxy resin The mass ratio of matter (liquid epoxy resin:solid epoxy resin is preferably 1:0.1~1:20, more preferably 1:0.3~1:10, and more preferably 1:0.6~1:9 ), and (e) the hardener preferably contains one or more selected from the group consisting of phenolic hardeners, naphthol hardeners, active ester hardeners, and cyanate ester hardeners. In this case, the preferable examples of (b) component, (c) component, and (d) component are also as above-mentioned.

The content of the curing agent in the thermosetting resin composition is not particularly limited, but is preferably at most 30% by mass, more preferably at most 25% by mass, and still more preferably at most 20% by mass. Also, the lower limit is not particularly limited, but is preferably 2% by mass or more.

-(f) Hardening Accelerator-

Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Phosphorus-based hardening accelerators and amine-based hardening accelerators are preferred. agent, imidazole-based hardening accelerator, metal-based hardening accelerator, more preferably amine-based hardening accelerator, imidazole-based hardening accelerator, metal-based hardening accelerator. The hardening accelerator may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine and tetrabutylphosphonium Decanoate.

Examples of amine hardening accelerators include triethylamine and tributylamine Other trialkylamines; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-paraffin (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5 ,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undecene.

Imidazole-based hardening accelerators include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole Base-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotriazine Polycyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzyl imidazolium chloride, 2-methyl Imidazole compounds such as imidazoline and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

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

Guanidine hardening accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethyl Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1 , 1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably Dicyandiamide, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, etc. Organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, manganese (II) acetylacetonate ) and other organomanganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc decalinate, cobalt decalinate, tin stearate, and zinc stearate.

The content of the hardening accelerator in the thermosetting resin composition is not particularly limited, but when the total amount of non-volatile components of the epoxy resin and hardener is 100% by mass, it is preferably 0.01% by mass to 3% by mass.

-(g) Flame retardant-

Examples of flame retardants include organophosphorus-based flame retardants, organic nitrogen-containing Phosphorus compounds, nitrogen compounds, silicon oxide flame retardants, metal hydroxides, etc. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As a flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ-HST" manufactured by Sanko Co., Ltd., and the like.

When the thermosetting resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and more preferably 0.5% by mass %~10% by mass.

-(h) Organic filler-

As the organic filler, any organic filler that can be used when forming an insulating layer of a printed circuit board can be used, and examples thereof include rubber particles, polyamide microparticles, and silicon oxide particles.

Commercially available items may also be used for the rubber particles, and examples thereof include "EXL-2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3816N" manufactured by Aica Kogyo Co., Ltd., and the like.

When the thermosetting resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and more preferably 0.3% by mass to 5% by mass. % by mass, or 0.5% by mass to 3% by mass.

-Other ingredients-

The thermosetting resin composition may further contain other additives if necessary, such as organic copper compounds, organic zinc compounds, etc. Organometallic compounds such as organic cobalt compounds, and resin additives such as binders, tackifiers, defoamers, leveling agents, adhesion imparting agents, and colorants.

The cured product obtained by thermosetting the thermosetting resin composition of the present invention (for example, the cured product obtained by curing at 190°C for 90 minutes (thermosetting resin composition after thermosetting)) exhibits a good elastic modulus (23°C ). That is, an insulating layer exhibiting good elastic modulus is brought about. The elastic modulus at 23°C of the cured thermosetting resin composition is not less than 1 GPa and not more than 6 GPa, preferably not more than 5 GPa. The measuring method of the modulus of elasticity can be measured according to the method described in <<measurement of modulus of elasticity, breaking strength and elongation at break> mentioned later.

The cured product obtained by thermosetting the thermosetting resin composition of the present invention (for example, the cured product obtained by curing at 190°C for 90 minutes (thermosetting resin composition after thermosetting)) exhibits good breaking strength (23°C ). That is, an insulating layer exhibiting good breaking strength is brought about. The fracture strength of the cured thermosetting resin composition at 23° C. is not less than 10 MPa, preferably not less than 20 MPa. There is no particular limitation on the upper limit, but it is 500 MPa or less. The method of measuring the breaking strength can be measured according to the method described in <<measurement of elastic modulus, breaking strength and breaking elongation> mentioned later.

A cured product obtained by thermosetting the thermosetting resin composition of the present invention (for example, a cured product obtained by curing at 190°C for 90 minutes (thermosetting resin composition after thermosetting)) exhibits a good tensile strength at break (23 ℃). That is, an insulating layer exhibiting good elongation at break results. The elongation at break of the cured thermosetting resin composition at 23°C is 6% or less On, preferably more than 6.5%. The upper limit is not particularly limited and is 30% by mass or less. The measurement method of breaking elongation can be measured according to the method described in <<measurement of elastic modulus, breaking strength and breaking elongation> mentioned later.

[adhesion film]

The adhesive film of the present invention includes a support and a layer of a thermosetting resin composition (only referred to as a "thermosetting resin composition layer"). In one embodiment, the adhesive film includes a support and a layer bonded to the support. The thermosetting resin composition layer is composed of the thermosetting resin composition of the present invention. Each layer constituting the adhesive film will be described in detail below.

<support>

The adhesive film of the present invention contains a support. The support can be, for example, a film, metal foil, or release paper made of plastic materials, preferably a film or metal foil made of plastic materials.

When a film made of plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"). ") such as polyester, polyolefin such as polyethylene and polypropylene, polycarbonate (hereinafter referred to as "PC"), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, Acyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate, polyethylene naphthalate, and polypropylene are preferred, and cheap polyethylene terephthalate is particularly preferred. Ethylene formate.

When metal foil is used as a support body, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferred. Copper foil can also be made of a single metal of copper, or an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). Moreover, what laminated|stacked plural metal foils can also be used for metal foil.

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

Moreover, the support body with a mold release layer which has a mold release layer on the surface bonded to a thermosetting resin composition layer can also be used for a support body. The release agent used for the release layer of the support with release layer includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins release agent. A commercially available product can be used as the support with a release layer, for example, a PET film having a release layer mainly composed of an alkyd resin release agent, namely "SK-1" and "SK-1" manufactured by Lintec Co., Ltd. AL-5", "AL-7", Toray Co., Ltd. "Lumirror T6AM", etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the thickness of the support body with a release layer as a whole is the said range.

The thickness of the thermosetting resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably 40 μm or less, or 20 μm or less from the viewpoint of thinning the wiring board. The lower limit of the thickness of the thermosetting resin composition layer is not particularly limited, Preferably it is 2 μm or more, more preferably 5 μm or more.

Next, the film may contain other layers in addition to the support body and the thermosetting resin composition layer. For example, the adhesive film may have a protective film layer described later on the outermost surface.

The adhesive film of the present invention is used in a manufacturing method of a wiring board comprising the following steps: (1) the step of preparing a base material having a base material and a wiring layer attached to at least one side of the base material, ( 2) A step of embedding the wiring layer in the thermosetting resin composition layer, laminating an adhesive film containing the thermosetting resin composition layer on the substrate with the wiring layer, and thermosetting to form an insulating layer, ( 3) Step of connecting wiring layers between layers, and (4) Step of removing base material.

In another aspect, the adhesive film of the present invention is used to manufacture a wiring board having an insulating layer and a buried wiring layer embedded in the insulating layer.

<Manufacturing method of adhesive film>

The production method of the adhesive film is not particularly limited as long as the adhesive film including the support body and the thermosetting resin composition layer can be produced. Next, for example, a resin varnish prepared by dissolving a thermosetting resin composition in an organic solvent is prepared as a film, and the resin varnish is coated on a support using a die coater or the like, and dried to form a thermosetting resin composition. layer to manufacture.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol Acetate esters such as acetate, carbitols such as cellosolve and butyl carbitol, aromatics such as toluene and xylene Amide-based solvents such as aromatic hydrocarbons, dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone, etc. An organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but the content of the organic solvent in the thermosetting resin composition layer is 10% by mass or less, preferably 5% by mass or less for drying. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, heat can be formed by drying at 50°C to 150°C for 3 minutes to 15 minutes. curable resin composition layer.

In the adhesive film, a protective film according to the support may be further laminated on the surface not bonded to the support of the thermosetting resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent adhesion of dust or the like to the surface of the thermosetting resin composition layer or scratches. The film can then be wound into a roll for storage. Next, when the film has a protective film, it can be used by peeling off the protective film.

The protective film is preferably a film made of plastic material.

Moreover, the support body with a mold release layer which has a mold release layer on the surface bonded to a thermosetting resin composition layer can also be used for a protective film. The release agent used for the release layer of the support with release layer includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins release agent.

A commercially available product can be used as the supporting body with a release layer, examples of which can be cited For example, PET film with a release layer mainly composed of alkyd resin release agent, that is, "SK-1", "AL-5", "AL-7" manufactured by Lintec Co., Ltd., Toray Co., Ltd. ) "Lumirror T6AM" etc.

The thickness of the protective film is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the thickness of the support body with a release layer as a whole is in the said range.

[Manufacturing method of wiring board]

The manufacturing method of the wiring board of the present invention comprises the following steps: (1) the step of preparing a base material with a wiring layer with a base material and a wiring layer disposed on at least one side of the base material, (2) making the wiring layer Embedding in the thermosetting resin composition layer, laminating the adhesive film of the present invention on the base material with the wiring layer, making the thermosetting step to form an insulating layer, (3) the step of connecting the wiring layer between layers, and ( 4) The step of removing the substrate.

Wherein the step (3) is not particularly limited as long as the wiring layer can be connected between layers, preferably at least one of the steps of forming a via hole in the insulating layer, forming a conductor layer, and grinding or grinding the insulating layer to expose the wiring layer Either step.

Hereinafter, the case where step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer will be described as the first embodiment, and the case where step (3) is a step of grinding or grinding the insulating layer to expose the wiring layer will be taken as the first embodiment. 2 Embodiments will be described.

1. The first embodiment <step (1)>

Step (1) is a step of preparing a base material having a wiring layer with a base material and a wiring layer provided on at least one side of the base material. As an example shown in Figure 1, the base material 10 with the wiring layer has a first metal layer 12 and a second metal layer 13 which are part of the base material 11 on both sides of the base material 11, and the second metal layer 13 in one of them is The exposed surface of 13 (the surface opposite to the substrate 11 side) has a wiring layer 14 .

The detail of step (1) is to laminate the dry film (photosensitive resist film) on the substrate, use a photomask to expose and develop under specific conditions, and form a patterned dry film. The patterned dry film after development is used as a plating mask, and after the wiring layer is formed by electroplating, the patterned dry film is peeled off.

The materials used for the first and second metal layers are not particularly limited. In a preferred embodiment, the first and second metal layers are preferably chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, more preferably for copper.

When steps (1) to (4) can be implemented as a base material, it is not particularly limited. Substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. can also be used to form metal layers such as copper foil on the surface of the substrate .

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, for example, novolak resin, acrylic Dry film of acrylic resin etc. A commercial item can be used for a dry film, for example, "ALPHO 20A263" by nikko-materials Co., Ltd. of the dry film with a PET film can be used. The dry film may be laminated on one side of the substrate, or may be laminated on both sides of the substrate as in the second embodiment described later.

The lamination conditions of the base material and the dry film are the same as that of embedding the adhesive film of the step (2) described later in the wiring layer for lamination, and the preferred range is also the same.

After the dry film is laminated on the substrate, the dry film is exposed and developed under specific conditions using a photomask in order to form the desired pattern.

The line width (circuit width)/spacing (width between circuits) ratio of the wiring layer is not particularly limited, preferably 20/20 μm or less (that is, the spacing is 40 μm or less), more preferably 18/18 μm or less (the spacing is 36 μm or less) ), and more preferably 15/15 μm or less (pitch 30 μm or less). The lower limit of the line width/space ratio of the wiring layer is not particularly limited, but it is preferably 0.5/0.5 μm or more, more preferably 1/1 μm or more. The pitch does not need to be the same over the entire wiring layer.

The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

After forming the pattern of the dry film, the wiring layer is formed, and the dry film is peeled off. Here, the formation of the wiring layer can be performed by a plating method using a dry film formed with a desired pattern as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer contains one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. above metal. The wiring layer can be a single metal layer or an alloy layer, and the alloy layer can be formed by, for example, an alloy of two or more metals selected from the above group (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) By. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a single metal layer of nickel is preferable from the viewpoint of versatility of wiring layer formation, cost, and ease of patterning. ． Chrome alloy, copper. Nickel alloy, copper. The alloy layer of titanium alloy is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel. The alloy layer of chromium alloy is more preferably a single metal layer of copper.

The thickness of the wiring layer varies according to the desired wiring board design, preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, more preferably 10 to 20 μm, or 15 μm.

After the wiring layer is formed, the dry film is peeled off. The stripping of the dry film can be carried out using an alkaline stripping solution such as sodium hydroxide solution, for example. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern. The pitch of the formed wiring layers is as described above.

<step (2)>

Step (2) is a step of embedding the wiring layer in the thermosetting resin composition layer, laminating the adhesive film of the present invention on the substrate with the wiring layer, and thermosetting to form an insulating layer. The thermosetting resin composition layer in the present invention exhibits good embedding properties, so when it is laminated on a substrate with a wiring layer, it can be laminated without voids. As an example shown in Figure 2, the wiring layer 14 of the base material with wiring layer obtained in the aforementioned step (1) is laminated in a state where the thermosetting resin composition layer 21 of the adhesive film 20 is embedded, so that the adhesive layer The thermosetting resin composition layer 21 of the film 20 is thermally cured. Next, the film 20 is laminated in the order of the thermosetting resin composition layer 21 and the support body 22 .

First, as an example shown in FIG. 2 , the thermosetting resin composition layer 21 of the adhesive film 20 is laminated on the substrate with the wiring layer in a state where the wiring layer 14 is embedded.

The lamination of the wiring layer and the adhesive film can be carried out by, for example, bonding the adhesive film to the wiring layer by thermocompression from the side of the support after removing the protective film of the adhesive film. The member for thermocompression bonding the adhesive film to the wiring layer (hereinafter also referred to as "thermocompression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of directly pressing the thermocompression bonding member on the adhesive film, it is preferable to press the adhesive film to sufficiently follow the surface irregularities of the wiring layer through an elastic material such as heat-resistant rubber.

The lamination of the wiring layer and the adhesive film can be carried out by vacuum lamination after removing the protective film of the adhesive film. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C~160°C, more preferably in the range of 80°C~140°C, and the heating and pressing pressure is preferably 0.098MPa~1.77MPa, more preferably 0.29MPa~ In the range of 1.47MPa, the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 13 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, vacuum pressure laminators manufactured by Nikko-Materials Co., Ltd., vacuum pressure laminators manufactured by Meiki Seisakusho, Vacuum coating machine manufactured by nichigo-morton Co., Ltd., etc.

After lamination, the adhesive film after lamination may be smoothed by pressing, for example, a thermocompression bonding member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment may be the same conditions as the above-mentioned thermocompression bonding conditions for lamination. The smoothing treatment can be performed with a commercially available laminator. In addition, lamination and smoothing can also be performed continuously using the above-mentioned commercially available vacuum laminator.

After the wiring layer is buried, the thermosetting resin composition layer is laminated on the wiring layer-attached substrate, and then the thermosetting resin composition layer is thermoset to form an insulating layer. The thermosetting conditions of the thermosetting resin composition layer are not particularly limited, and conditions generally employed when forming an insulating layer of a wiring board can be used.

For example, the thermosetting conditions of the thermosetting resin composition layer vary depending on the type of thermosetting resin composition, etc., but the curing temperature can be in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, More preferably in the range of 170°C to 200°C), the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermosetting the thermosetting resin composition layer, the thermosetting resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermosetting the thermosetting resin composition layer, the thermosetting resin composition layer can be cured at a temperature of not less than 50°C and not more than 120°C (preferably not less than 60°C and not more than 110°C, more preferably not less than 70°C and not more than 100°C). The resin composition layer is preliminarily heated for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The supporting body of the following film may be peeled off after the film is laminated on the base material with wiring layer, or the support body may be peeled off before the film is laminated on the base material with wiring layer. In the case of peeling after the film is laminated on the substrate with wiring layer, the peeling may be performed before thermosetting the thermosetting resin composition layer, or after thermosetting the thermosetting resin composition layer. peel off. In addition, the support may be peeled off before the roughening treatment step described later.

The thickness of the insulating layer is the same as that of the thermosetting resin composition layer, and the preferred range is also the same.

<Step (3)>

Step (3) in the first embodiment is a step of forming a via hole in the insulating layer and forming a conductive layer. The stage of forming a via hole in the insulating layer (hereinafter also referred to as "step (3-1)") and the stage of forming a conductive layer (hereinafter also referred to as "step (3-2)") will be described separately below.

-Step (3-1)-

The formation of the via hole is not particularly limited, and examples include laser irradiation, etching, mechanical drilling, etc., but it is preferably performed by laser irradiation. As an example shown in Figure 3 in detail, step (3) is before the support 22 is peeled off (under the state where the support 22 is attached), the laser is irradiated from the surface side of the adhesive film 20, and the support 22 and the insulating layer 21' are penetrated. Via holes 31 exposing the wiring layer 14 are formed.

For this laser irradiation, any preferable laser processing machine using a carbon dioxide laser, a YAG laser, an excimer laser, etc. as a light source can be used. Usable laser processing machines include, for example, CO ₂ laser processing machine "LC-2k212/2C" manufactured by ViaMechanics Co., Ltd., 605GTWIII(-P) manufactured by Mitsubishi Electric Co., Ltd., and Panasonic Welding Systems Co., Ltd. The laser processing machine.

The conditions of laser irradiation are not particularly limited, and laser irradiation can be implemented by any preferred procedure according to a common method of the selected means.

The shape of the via hole, that is, the shape of the opening when viewed from the extending direction, is not particularly limited, and is generally circular (slightly circular). Hereinafter, the "diameter" of the via hole refers to the diameter (diameter) of the opening when viewed from the extending direction. In this specification, the top (top) diameter r1 refers to the diameter of the rim on the insulating layer 21' side of the through hole, and the bottom diameter r2 refers to the diameter of the rim on the wiring layer 14 side of the through hole (refer to FIG. 3 and FIG. 4 ) .

The top diameter r1 of the via hole is preferably 120 μm or less, preferably 90 μm or less to form the via hole.

As an example shown in FIG. 4, the via hole 31 can be formed with r1 greater than r2. As an example shown in FIG.

In this way, the embedding property of the via hole becomes good, and the occurrence of voids can be suppressed. As a result, the reliability of electrical connection can be improved by filling the hole described later.

After the via hole is formed, a step of removing residue in the via hole, a so-called desmear step, may also be performed. The following step (3-2) is a plating step In the case of step (3-2), for the via hole, for example, wet desmear treatment can be carried out. When step (3-2) is carried out by sputtering step, for example, dry desmear treatment such as plasma treatment step can be carried out. Slag step. Also, the step of desmearing can be combined with the step of roughening.

Before the step (3-2), a step of roughening may be included. The roughening treatment is performed on the via hole and the insulating layer. The procedures and conditions of the roughening treatment are not particularly limited. For example, the known sequence and conditions commonly used when forming the insulating layer of a multilayer printed circuit board can be used. Examples of dry roughening treatment include plasma treatment, and examples of wet roughening treatment include swelling treatment with swelling liquid, roughening treatment with oxidizing agent, and neutralization treatment with neutralizing solution. method.

The wet roughening treatment, for example, can be performed sequentially by swelling treatment with swelling liquid, roughening treatment with oxidizing agent, and neutralization treatment with neutralizing solution to roughen the insulating layer 21'. The swelling solution is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, etc., preferably alkali solutions, more preferably sodium hydroxide solutions, and potassium hydroxide solutions. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., and the like.

The swelling treatment by swelling liquid is not particularly limited, for example, it can be performed by immersing the insulating layer 21' in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer 21' to an appropriate level, it is preferable to immerse the insulating layer 21' in a swelling solution at 40°C to 80°C for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include potassium permanganate or sodium permanganate dissolved in an aqueous solution of sodium hydroxide Alkaline permanganate solution. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer 21' in an oxidizing solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Also, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact P" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. Also, the neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof includes "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., for example.

The treatment with the neutralizing solution can be carried out by immersing the surface roughened with the oxidizing agent solution in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability, etc., a method of immersing the object roughened with an oxidizing agent solution in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferred.

-Step (3-2)-

The conductive material constituting the conductive layer is not particularly limited. In a preferred embodiment, it can be formed of the same material as the conductor material used in the wiring pattern, preferably copper.

The conductor layer may be a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer is a multi-layer structure, the layer adjacent to the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or nickel. Alloy layer of chromium alloy.

The thickness of the conductor layer, although it also depends on the desired printed circuit board The design varies, but generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

The conductive layer can be formed by any conventionally known preferred method such as plating, sputtering, and vapor deposition, and is preferably formed by plating. In a preferred embodiment, for example, the surface of the insulating layer can be plated by conventionally known techniques such as semi-additive method and full-additive method to form a conductor layer having a desired wiring pattern. Also, when the support in the subsequent film is a metal foil, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as subtractive processes.

More specifically, a shield layer is formed on the surface of the insulating layer 21' by electroless plating. Then, on the formed plating protection layer, a mask pattern corresponding to a desired wiring pattern is formed to expose a part of the plating protection layer. On the exposed plating protective layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, unnecessary plating resist is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

As an example shown in Fig. 5, a plating resist 41 is formed to be bonded to the surface of the exposed insulating layer 21'. First, surface cleaning of the insulating layer 21' and alkali cleaning for charge adjustment are performed. Next, in order to clean the inside of the via hole 31, a soft etching step is performed. Specifically, what is necessary is just to process under arbitrary preferable conditions using etchant, such as sulfuric-acid sodium persulfate aqueous solution. Next, in order to impart Pd (palladium) to the surface of the insulating layer 21', a pre-dipping step for adjusting the surface charge of the insulating layer 21' is performed. Next, Pd of an activator (Activator) is provided to the surface, and the Pd provided to the insulating layer 21' is reduced. Next, copper (Cu) is precipitated on the surface of the insulating layer 21' to form a plated A protective layer 41 is applied. At this time, the wiring layer 14 exposed from the inside of the via hole 31 , that is, the sidewall and the via hole 31 , is covered to form a plating protection layer 41 .

As an example shown in FIG. 6, after the plating resist layer 41 is formed, a mask pattern 50 for exposing a part of the plating resist layer 41 is formed. The mask pattern 50 can be formed, for example, by bonding a dry film to the plating protection layer 41, exposing, developing and cleaning under specific conditions.

The dry film that can be used in the step (3-2) is, for example, the same as the above-mentioned dry film, and the preferable range is also the same.

As an example shown in FIG. 7 , on the exposed plating protection layer 41 , under the condition that the via hole 31 is filled, the plating layer 42 is formed by electroplating, and at the same time, the via hole is buried by electroplating to form the filled hole 61 .

As an example shown in FIG. 8 , then, the mask pattern is stripped and removed, and flash etching is performed under any preferred conditions to remove only the exposed plating protection layer 41 to form the patterned conductor layer 40 .

The conductor layer is not limited to linear wiring, but may include, for example, electrode pads (lands) on which external terminals can be mounted. Also, the conductive layer may be composed of electrode pads only.

In addition, the conductive layer can be formed by forming a plating layer and filling holes without using a mask pattern after forming a plating resist layer, and then patterning by etching.

<Step (4)>

Step (4) is a step of removing the base material and forming the wiring board of the present invention as an example shown in FIG. 9 . The method of removing the substrate is not particularly limited. one of the best In an embodiment, at the interface between the first and second metal layers, the base material is peeled off from the wiring board, and the second metal layer is removed by etching with, for example, an aqueous copper chloride solution.

If necessary, the substrate may be peeled off in a state where the protective film protective conductor layer 40 is protected. This protective film is the same as the protective film used next to the film, and the preferred range is also the same.

According to such a manufacturing method of the present invention, it is possible to manufacture a wiring board in which the wiring layer 14 is embedded in the insulating layer 21'. Also, since at least one insulating layer 21' is included, a flexible wiring board can be formed. Also, if necessary, the steps (2) to (3) of forming insulating layers and conductor layers can be repeated to form a multilayer wiring board. When manufacturing a multilayer wiring board, at least one adhesive film of the present invention may be used. Also, when step (3) is repeated, in addition to the step of forming via holes in the insulating layer and forming the conductive layer, the step of grinding or grinding the insulating layer to expose the wiring layer may also be performed. Flexibility means that the wiring board can be bent at least once without cracks or changes in resistance value.

2. The second embodiment

The first embodiment is in the case of step (3) forming a via hole in the insulating layer to form a conductor layer, but the second embodiment is in addition to the step (3) of grinding or grinding the insulating layer to expose the wiring layer, It is the same as that of the first embodiment. In each of the drawings used in the following description, the same components are assigned the same reference numerals, and overlapping descriptions may be omitted.

Step (1) A step of preparing a base material having a base material and a wiring layer with a wiring layer provided on both surfaces of the base material. The formation method of the wiring layer 14 is the same as that of the first embodiment. Each wiring layer 14 in the second embodiment The thickness can be the same or different. As an example shown in FIG. 10, it is preferable that the thicknesses of the wiring layers 14 in the second embodiment are different.

Among the wiring layers, the thickness of the wiring layer (conductive pillar) having the thickest thickness varies depending on the desired wiring board design, but is preferably 100 μm or less, more preferably 80 μm or less, and More preferably, it is 60 μm or less, and more preferably 40 μm or less, or 20 μm or less. The lower limit is not particularly limited, but is preferably 2 μm or more, more preferably 5 μm or more. The thickness of the wiring layers other than the thickest wiring layer is the same as that of the wiring layer in the first embodiment, and the preferable range is also the same.

Step (2) As an example shown in Figure 11, the wiring layer is embedded in the thermosetting resin composition layer, and the adhesive film of the present invention is laminated on the substrate with the wiring layer, and the step of thermosetting to form an insulating layer , as in the first embodiment, and the preferred range is also the same.

Step (3) is a step of grinding or grinding the insulating layer to expose the wiring layer. Unlike the step (3) in the first embodiment, no via hole is formed, so the cost of forming the via hole can be significantly reduced.

As mentioned above, the wiring layer in the second embodiment is shown in FIG. 1 as an example, and each wiring layer may have a uniform thickness. As shown in FIG. 10, each wiring layer 14 may have a different thickness. In step (3), it is not necessary to expose the entire wiring layer, and a part of the wiring layer 14 may be exposed, for example, as shown in FIG. 12 .

The grinding method or grinding method of the insulating layer is not particularly limited as long as the wiring layer can be exposed, and the grinding or grinding surface is horizontal, and conventionally known grinding methods or grinding methods can be used. Learn chemical mechanical grinding methods of mechanical grinding devices, etc.

After step (3), if necessary, a residue removal step and a roughening treatment step may be performed in the same manner as in the first embodiment. Also, if necessary, a conductor layer may be formed as in the above step (3-2).

Step (4) As shown in FIG. 13 as an example, the step of removing the base material to form the wiring board of the present invention. The method of removing the substrate is not particularly limited. In a preferred embodiment, at the interface between the first and second metal layers, the substrate is peeled off from the wiring board, and the second metal layer is removed by etching with, for example, an aqueous copper chloride solution.

3. The third embodiment

In the first embodiment, a wiring board is manufactured from a base material with a wiring layer attached to one side, but in the third embodiment, the wiring board is produced from a base material with a wiring layer attached to a wiring layer on both sides of the base material. 1 Embodiment is the same. In each of the drawings used in the following description, the same components are assigned the same reference numerals, and overlapping descriptions may be omitted.

Step (1) As an example shown in FIG. 14 , a step of preparing a base material having a wiring layer with a base material and wiring layers provided on both surfaces of the base material. The formation method of the wiring layer 14 is the same as that of the first embodiment. The wiring layers provided on both sides of the base material can be formed at the same time. The base material with the wiring layer is prepared, and one of the wiring layers can be formed, and then the other wiring can be formed. Layer, prepare the base material with wiring layer. In addition, each wiring layer may be of the same pattern or may be of a different pattern. Also, the thickness of each wiring layer may be different as shown in FIG. 10 .

Step (2) As an example shown in Figure 15, for both sides of the base material with wiring layer, the wiring layer is embedded in the thermosetting resin composition layer, The step of laminating the adhesive film on the base material with the wiring layer respectively, and curing by heat. The two kinds of adhesive films used may be the same adhesive film or different adhesive films.

Step (3) As an example shown in FIG. 16, it is preferable to irradiate laser light from the side of the thermally hardened adhesive film on both sides of the base material with wiring layer, and form via holes in the thermally hardened adhesive film. The via holes can be formed at the same time, or one of the via holes can be formed before the other via hole is formed.

Before forming the conductor layer, a step of roughening the both surfaces of the base material with wiring layer may be included, and the surface of the two insulating layers 21' may be roughened. The roughening treatment may be performed at the same time, or the other roughening treatment may be performed after one of the roughening treatments.

After the via holes are formed, conductor layers are formed on both sides of the substrate with wiring layers. As an example shown in Fig. 17, a plating protection layer 41 is formed on the insulating layer 21' after the roughening treatment. After forming the plating protection layer 41, as an example shown in Figure 18, form the mask pattern 50 that a part of the plating protection layer 41 is exposed, as an example shown in Figure 19, form electroplating on the plating protection layer 41 that exposes. layer 42, and at the same time bury the via hole by electroplating to form the filling hole 61. As an example shown in FIG. 20, the mask pattern is removed to form the conductor layer 40. As shown in FIG. The details of the formation of the conductor layer 40 can be described in the same manner as in the first embodiment. Also, two conductive layers provided on both surfaces of the substrate may be formed simultaneously, or one conductive layer may be formed and then the other conductive layer may be formed.

The step (3) in the third embodiment will be described as a step of forming a via hole in the insulating layer and forming a conductive layer, but a step of grinding or grinding the insulating layer to expose the wiring layer may also be performed. again, yes On one side of the base material with wiring layer, the steps of forming via holes in the insulating layer and forming the conductor layer can be carried out. For the other side, the step of grinding or grinding the insulating layer to expose the wiring layer can also be carried out.

Step (4) As an example shown in FIG. 21, the base material is removed to form the wiring board of the present invention. In the third embodiment, two types of wiring boards can be manufactured at the same time.

[wiring board]

The wiring board of the present invention is characterized by comprising an insulating layer of a cured product of the thermosetting resin composition layer adhering to the film of the present invention, and an embedded wiring layer embedded in the insulating layer. In addition, descriptions that overlap with those described above may be omitted.

The wiring board of the present invention, for example, includes the steps of (1) to (4) above, and can be manufactured by the manufacturing method of the wiring board of the present invention. As an example of the wiring board 1 of the present invention as shown in Fig. 9, a buried wiring layer 14 and an insulating layer 21' are laminated in this order. A conductor layer 40 is provided on the surface of the insulating layer 21' that is not bonded to the buried wiring layer 14 (that is, the surface opposite to the buried wiring layer 14). The embedded wiring layer 14 is joined to the conductor layer 40 via the filled hole 61 .

The buried type wiring layer refers to a wiring layer (wiring layer 14) buried in the insulating layer 21' when it can be connected to a conductor of a component such as a semiconductor chip. The embedded wiring layer is usually embedded in the insulating layer with its protruding height substantially zero, generally -1 μm to +1 μm, on the side opposite to the side where the adhesive film is laminated.

The wiring board of the present invention may also be a multilayer wiring board as shown in Fig. 22 and Fig. 23 as an example. The thermosetting resin composition constituting the thermosetting resin composition layer forming each insulating layer in the wiring board as an example shown in FIG. 22 and FIG. 23 may have the same composition or different compositions. Also, as shown in FIG. 22, the top diameter and bottom diameter of the filled hole 61 can be slightly the same. As shown in FIG. 23, the top diameter of the filled hole 61 can be larger than the bottom diameter.

[semiconductor device]

The semiconductor device of the present invention is characterized by comprising the wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes, etc.).

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on the conductive portions of the printed circuit board. "Conductive place" refers to "the place where the electrical signal is transmitted on the printed circuit board". The place can be a surface or a buried place. Also, the semiconductor wafer is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can effectively function. Specifically, a wire bonding mounting method, a flip chip mounting method, and The mounting method of bumpless build-up layer (BBUL), the mounting method of anisotropic conductive film (ACF), the mounting method of non-conductive film (NCF), etc. Here, "Bumpless Build-up Layer (BBUL) Mounting Method" refers to Refers to "a mounting method in which a semiconductor chip is directly buried in a concave portion of a printed circuit board, and the semiconductor chip is connected to the wiring on the printed circuit board."

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, in the description below, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Preparation of Evaluation Board> (1) Step of preparing a base material with a wiring layer attached to a base material and a wiring layer provided on at least one side of the base material (1-1) Lamination of dry film to substrate (core substrate)

Prepare the glass cloth substrate epoxy resin double-sided copper laminated board as the core substrate (Layer composition: Mitsui Metal Mining Co., Ltd. MicroThin MT-Ex copper foil (copper foil with a thickness of 3 μm / carrier foil with a thickness of 18 μm) / panasonic ( Co., Ltd. "R1515A" substrate (thickness 0.2 mm)/Mitsui Metal Mining Co., Ltd. MicroThinMT-Ex copper foil (18 μm thick carrier foil/3 μm thick copper foil)) 170×125 mm. Using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by nikko-materials Co., Ltd.), the dry film with PET film (nikko- "ALPHO 20A263" manufactured by Materials Co., Ltd., the thickness of the dry film is 20 μm) was laminated on both sides of the mat surface side of the 3 μm copper foil of the laminated board. The lamination of the dry film is carried out by depressurizing for 30 seconds, and the air pressure is above 13hPa After pressing, press-bonding was carried out at a temperature of 70° C. and a pressure of 0.1 MPa for 20 seconds.

(1-2) Formation of graphics

A glass mask (mask) formed with the wiring pattern shown below was placed on the PET film of the protective layer of the dry film, and UV was irradiated with a UV lamp at an irradiation intensity of 150 mJ/cm ² . After UV irradiation, the PET film of the dry film was peeled off, and a 1% sodium carbonate aqueous solution at 30°C was sprayed at a spray pressure of 0.15 MPa for 30 seconds. Then, the dry film is developed (patterned) by washing with water.

Wiring pattern of glass cover:

Form a comb-tooth pattern with L/S=15μm/15μm at 10mm intervals, that is, a wiring pitch of 30μm (wiring length 15mm, 16 lines, 10mm square conductor leads).

(1-3) Formation of wiring layer

After developing the dry film, electroplate copper with a thickness of 15 μm to form a wiring layer. Next, a 3% sodium hydroxide solution at 50°C was sprayed at a spray pressure of 0.2 MPa, and after the dry film was peeled off, it was washed with water and dried at 150°C for 30 minutes.

(2) The step of embedding the wiring layer in the thermosetting resin composition layer, laminating the adhesive film on the base material with the wiring layer, and thermosetting to form an insulating layer (2-1) Lamination of adhesive film

Using the resin varnish produced in Examples and Comparative Examples, peel off the protective film of each adhesive film (167mm x 122mm) prepared as described in <Preparation of Adhesive Film>, and use a batch-type vacuum pressure laminator (nikko -Materials Co., Ltd. 2-stage build-up laminator "CVP700"), the state where the thermosetting resin composition layer and the wiring layer are joined, is embedded in both sides of the wiring layer and laminated. Lamination was performed by pressure-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds after reducing the pressure to 13 hPa or less for 30 seconds. Next, the laminated adhesive film was smoothed by hot pressing for 60 seconds at 100° C. and a pressure of 0.5 MPa under atmospheric pressure.

(2-2) Thermosetting of thermosetting resin composition layer

After lamination of the films, the support (PET film) was peeled off, and the thermosetting resin composition layer was thermally cured at 190°C for 90 minutes to form insulating layers on both sides of the wiring layer. After cooling to room temperature, heat treatment was performed at 130° C. for 30 minutes to relax stress by thermal hardening.

(3) The step of forming a punching hole for length measurement on the substrate

The 15mm portion from the four corners of the obtained substrate (170×125mm) was punched to form 4 through holes (about 6mm in diameter) (the holes are temporarily called A, B, C, and D in a clockwise direction), and then After the support of the film was peeled off, measure the diagonal length L (L _AC , L _BD ).

(4) The step of removing the substrate

Then, the blade of the dicing knife was inserted into the interface between the 3 μm thick copper foil and the 18 μm thick carrier foil of the MicroThin MT-Ex copper foil on the core substrate, and the core substrate was peeled off and separated. Next, the copper foil of 3 μm was removed by etching with an aqueous copper chloride solution, washed with water, and dried at 110° C. for 30 minutes. The thus-obtained wiring board with a comb tooth pattern of L/S=15/15 μm embedded in one side is referred to as "evaluation board A".

<Evaluation of Dimensional Accuracy>

Regarding the obtained two evaluation substrates A, measure the length L'(L' _AC , L' _BD ) between the centers of the holes formed in (3) after hardening with a non-contact image measuring device in the same way as L . Any one of the dimensional changes (L' _AC - L _AC ) and (L' _BD - L _BD ) exceeding 2 mm was rated as x, 1 to 2 mm was rated as Δ, and all of them were 1 mm or less were rated as ○.

<Evaluation of Reflow Resistance>

Regarding the evaluation board A of 2 pieces after the dimensional accuracy evaluation, the reflow device ("HAS-6116" manufactured by Japan Antom Co., Ltd.) that reproduces the soldering reflow temperature with a peak temperature of 260°C was passed 3 times (the reflow temperature graph is based on IPC/JEDEC J-STD-020C). Then, by visual observation, even if there was an abnormality such as peeling in a part of the conductor pattern, it was evaluated as x, and those without any abnormality were evaluated as ○.

<Measurement of elastic modulus, breaking strength and breaking elongation>

The untreated surface of the release PET film ("501010" manufactured by Lintec Co., Ltd., thickness 38 μm, angle 240 mm) was brought into contact with the glass cloth substrate epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Co., Ltd., thickness 0.7mm, 250mm angle), set it on the glass cloth substrate epoxy resin double-sided copper laminated board, and fix the four sides of the release film with polyimide adhesive tape (width 10mm).

Using the resin varnish produced in Examples and Comparative Examples, each adhesive film (230 mm square) prepared as described in <Preparation of Adhesive Film> was used a batch-type vacuum pressure laminator (manufactured by Nikko-Materials Co., Ltd.) 2-stage build-up laminator "CVP700") performs lamination at the center with the thermosetting resin composition layer in contact with the release surface of the release PET film. The lamination process was carried out by pressure-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds after reducing the pressure to 13 hPa or less for 30 seconds.

Next, the support was peeled off, and the thermosetting resin composition layer was thermally cured under the curing conditions of 190° C. and 90 minutes.

After thermosetting, the polyimide adhesive tape was peeled off, and the thermosetting resin composition layer was peeled off from the glass cloth base epoxy resin double-sided laminated board. In addition, the release PET film was peeled off from the thermosetting resin composition layer to obtain a cured product in the form of a sheet. The flake-shaped cured product is called the cured product for evaluation. The obtained cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The tensile strength of the test piece was measured using a tensile testing machine "RTC-1250A" manufactured by Orientec Co., Ltd., and the modulus of elasticity, breaking strength and breaking elongation at 23°C were determined. The measurement system is based on JIS K7127 apply. This operation is carried out 5 times, and the average value of the upper 3 points is shown in the table.

<Evaluation of seam folding resistance>

Fold the seam at the center of the same dumbbell-shaped No. 1 shape as above, and place a 1kg load for 5 seconds. Then, the seam folded portion was restored, and a load of 1 kg was placed for 5 seconds. Repeat the above operation 5 times, and visually observe whether the folded part of the seam is cut or not. Regarding the 3 cured products for evaluation, if all the seam folds are not cut, it is evaluated as resistant (○), and even if one of the cured products is partly or completely cut at the seam folds, it is evaluated as Impatient (×).

<Measurement of melt viscosity of resin layer>

From the resin varnish produced in Examples and Comparative Examples, only the resin composition layer was peeled off from the release PET (support) of each adhesive film prepared as described in <Preparation of Adhesive Film>, and compressed with a mold, Prepare pellets for measurement (diameter 18mm, 1.2~1.3g). Then, using a dynamic viscoelasticity measurement device ("Rheosol-G3000" manufactured by UBM), for 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, from the initial temperature of 60 ° C to 200 ° C, at a heating rate of 5 ° C / Heating up in minutes, measuring temperature interval 2.5°C, vibration frequency 1Hz, deformation 1deg, measuring dynamic viscoelasticity, and calculating the minimum melt viscosity (poise), as shown in Table 1.

[Manufacture of Hardener A with Butadiene Structure and Phenolic Hydroxyl]

In the reaction vessel, 45 g of G-1000 (bifunctional hydroxyl-terminated polybutadiene, number average molecular weight = 1400, hydroxyl equivalent = 770 g/eq., manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 (aromatic hydrocarbon-based mixed solvent) were mixed : Idemitsu Petrochemical Co., Ltd.) 40 g, and 0.005 g of dibutyltin laurate were uniformly dissolved. When it became uniform, the temperature was raised to 50° C., and further, 15 g of isophorone diisocyanate (isocyanate group equivalent=113 g/eq., IPDI manufactured by Evonik Degussa Japan Co., Ltd.) was added while stirring, and the reaction was carried out for about 3 hours. Next, the reactant was cooled to room temperature, and 40 g of cresol novolac resin KA-1160 (hydroxyl equivalent = 117 g/eq., manufactured by DIC Co., Ltd.) and ethyldiethylene glycol acetic acid were added thereto. 60 g of ester (manufactured by DAICEL) was heated up to 80° C. while stirring, and reacted for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. The end of the reaction was confirmed by the disappearance of the NCO peak. After cooling the reactant to room temperature, it was filtered through a 100 mesh filter cloth to obtain Hardener A (non-volatile matter 50% by mass) having a butadiene structure and phenolic hydroxyl groups.

Number average molecular weight: 2900

[Manufacture of hardener B having hydrogenated butadiene structure and phenolic hydroxyl group]

In a reaction vessel, 46 g of GI-1000 (difunctional hydroxyl-terminated hydrogenated polybutadiene, number average molecular weight = 1500, hydroxyl equivalent = 830 g/eq., manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 (aromatic hydrocarbon system) were mixed Solvent: Idemitsu Petrochemical Co., Ltd. product) 40 g, 0.005 g of dibutyltin laurate, and made to dissolve uniformly. When it became uniform, the temperature was raised to 50°C, and further, 14 g of isophorone diisocyanate (isocyanate group equivalent = 113 g/eq., IPDI manufactured by Evonik Degussa Japan Co., Ltd.) was added while stirring, and the reaction was carried out for about 3 hours. . Next, the reactant was cooled to room temperature, and 40 g of cresol novolak resin KA-1160 (hydroxyl equivalent = 117 g/eq., manufactured by DIC Co., Ltd.) and ethyldiethylene glycol acetic acid were added thereto. 60 g of ester (manufactured by DAICEL) was heated up to 80° C. while stirring, and reacted for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. The end of the reaction was confirmed by the disappearance of the NCO peak. After the reactant was cooled to room temperature, it was filtered through a 100 mesh filter cloth to obtain Hardener B (non-volatile matter 50% by mass) having a hydrogenated butadiene structure and phenolic hydroxyl groups.

Number average molecular weight: 3000

[Manufacture of Hardener C with Butadiene Structure and Phenolic Hydroxyl]

In a reaction vessel, 69 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number average molecular weight = 3000, hydroxyl equivalent = 1800 g/eq., manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 (aromatic hydrocarbon-based Solvent: Idemitsu Petrochemical Co., Ltd. product) 40 g, 0.005 g of dibutyltin laurate, and made to dissolve uniformly. When it became uniform, the temperature was raised to 50°C, and further, 8 g of isophorone diisocyanate (isocyanate group equivalent = 113 g/eq., IPDI manufactured by Evonik Degussa Japan Co., Ltd.) was added while stirring, and the reaction was carried out for about 3 hours. . Next, the reactant was cooled to room temperature, and 23 g of cresol novolac resin KA-1160 (hydroxyl equivalent = 117 g/eq., manufactured by DIC Co., Ltd.) and ethyldiethylene glycol acetic acid were added thereto. 60 g of ester (manufactured by DAICEL) was heated up to 80° C. while stirring, and reacted for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. The disappearance of the NCO peak was regarded as the end point of the reaction. After cooling the reactant to room temperature, it was filtered through a 100 mesh filter cloth to obtain Hardener C (non-volatile matter 50% by mass) having a butadiene structure and phenolic hydroxyl groups.

Number average molecular weight: 5500

<Example 1>

5.1 parts of epoxy resin containing a flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy equivalent 406), biphenyl type epoxy resin ("NC3100" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 258) 1.5 parts, phenoxy resin containing a flexible structure ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) with a solid content of 40% by mass) 10 Parts, phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone: MEK with a solid content of 30% by mass) 6 parts, Ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu Petrochemical ( Stock) System) 1 part was heated and dissolved while stirring. Cool the heated solution to room temperature, and then mix 10 parts of hardening agent A solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 1 part, and hydroxyphenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM103") surface-treated spherical silica (average particle size 0.1 μm, Denka ) "UFP-30", carbon content per unit surface area 0.19 mg/m ² ) 8 parts, uniformly dispersed using a high-speed rotary mixer, and filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare resin varnish 1.

<Example 2>

8.5 parts of epoxy resin containing flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy equivalent 406), bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 238) 3 parts, 8 parts of phenoxy resin containing a flexible structure ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone: MEK with a solid content of 40% by mass), 8 parts of phenoxy resin ( "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 10 parts of cyclohexanone with a solid content of 30% by mass: MEK 1:1 solution), 1.5 parts of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) Heat to dissolve while stirring. Cool the heated solution to room temperature, then mix 10 parts of hardener B solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 0.8 parts, flame retardant ("HCA-HQ-HST" manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10 - Phosphaphenanthrene-10-oxide, average particle size 1.5 μm) 2.5 parts, and spherical silica ((stock) )admatechs "SO-C2", average particle size 0.5μm, carbon content per unit surface area 0.38mg/m ² ) 20 parts, use a high-speed rotary mixer to uniformly disperse, through a cartridge filter (ROKITECHNO "SHP050") Filter to make resin varnish 2.

<Example 3>

1 part of epoxy resin containing flexible structure ("YX7400" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 440), 1 part of epoxy resin containing flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy Equivalent weight 406) 6.8 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone: MEK with a solid content of 30% by mass) 12 parts, Ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu Petrochemical Co., Ltd.) 1.5 parts were heated and dissolved while stirring. Cool the heated solution to room temperature, then mix 10 parts of hardener B solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 1 part, and spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. 24 parts of average particle diameter 0.5 μm, carbon content per unit surface area 0.38 mg/m ² ) were uniformly dispersed using a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare resin varnish 3.

<Example 4>

6 parts of bisphenol AF type epoxy resin (Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent 238), dicyclopentadiene type epoxy resin DIC Co., Ltd. "HP-7200", epoxy equivalent 258) 2 parts, 8 parts of phenoxy resin with flexible structure ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone: MEK with a solid content of 40% by mass), 8 parts of MEK and 4 parts while stirring Allow to heat to dissolve. Cool the heated solution to room temperature, and then mix 20 parts of hardening agent C solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 1 part, flame retardant ("HCA-HQ-HST" manufactured by Sanko Co., Ltd.), 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10 -Phosphaphenanthrene-10- oxide, average particle size 1.5 μm) 2.5 parts, and spherical silica (average particle size Diameter 0.1 μm, "UFP-30" manufactured by Denki Kogyo Co., Ltd., carbon content per unit surface area 0.19 mg/m ² ) 8 parts, via aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573" ) 8 parts of surface-treated spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm, carbon content per unit surface area 0.38mg/m ² ), uniformly dispersed using a high-speed rotary mixer, Resin varnish 4 was prepared by filtering with a cartridge filter ("SHP050" manufactured by ROKITECHNO).

<Example 5>

2 parts of epoxy resin containing flexible structure ("YX7400" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 440), epoxy resin containing flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy Equivalent weight 406) 10.2 parts, phenoxy resin with flexible structure ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone:MEK with a solid content of 40% by mass) 8 parts, phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of cyclohexanone:MEK with a solid content of 30% by mass) 8 parts, 1.8 parts of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) Heat to dissolve while stirring. Cool the heated solution to room temperature, then mix 12 parts of hardening agent A solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 2 parts and spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., average 15 parts of particle size 0.5 μm, carbon content per unit surface area 0.38 mg/m ² ) were uniformly dispersed using a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare resin varnish 5.

<Comparative example 1>

8 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 238), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., cyclohexane with a solid content of 30% by mass) Ketone: 1:1 solution of MEK) and 1.5 parts of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) were heated and dissolved while stirring. Cool the heated solution to room temperature, then mix 10 parts of hardener B solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 0.8 parts, flame retardant ("HCA-HQ-HST" manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10 - Phosphaphenanthrene-10-oxide, average particle size 1.5μm) 2.5 parts and spherical silica ((share) 20 parts of "SO-C2" manufactured by admatechs, average particle size 0.5 μm, carbon content per unit surface area 0.38 mg/m ² ), uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) Make resin varnish6.

<Comparative example 2>

5.1 parts of epoxy resin containing a flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy equivalent 406), biphenyl type epoxy resin ("NC3100" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 258) 1.5 parts, and 1.5 parts of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), were heated and dissolved while stirring. Cool the heated solution to room temperature, and then mix 10 parts of hardening agent A solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 2 parts and spherical silica (average particle size 0.1 μm, Denki Kogyo Co., Ltd.) surface-treated with phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. 8 parts of "UFP-30" (carbon content per unit surface area: 0.19 mg/m ² ) were uniformly dispersed using a high-speed rotary mixer, and filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare resin varnish 7.

<Comparative example 3>

5.1 parts of epoxy resin containing a flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy equivalent 406), biphenyl type epoxy resin ("NC3100" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 258) 1.5 parts, phenoxy resin having a flexible structure ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 40% by mass) 15 1 part, 1 part of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), was dissolved by heating while stirring. Cool the heated solution to room temperature, and then mix 10 parts of hardening agent A solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass MEK solution) 1.5 parts and spherical silica (average particle size 0.1 μm, Denki Kogyo Co., Ltd.) surface-treated with phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM103") Prepare 4 parts of "UFP-30" (carbon content per unit surface area: 0.19 mg/m ² ), uniformly disperse using a high-speed rotary mixer, and filter with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare resin varnish 8.

<Comparative example 4>

6.8 parts of epoxy resin containing flexible structure ("EXA-4816" manufactured by DIC Co., Ltd., epoxy equivalent 406), phenoxy resin containing flexible structure ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., solid Composition 40% by mass of cyclohexanone: MEK 1:1 solution) 6 parts, Ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu Petrochemical Co., Ltd.) 10 parts, heated and dissolved while stirring. Cool the heated solution to room temperature, then mix 10 parts of hardener B solution, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass of MEK solution) 0.8 parts and spherical silica ("SO-C2" manufactured by Admatechs, average 50 parts of particle size 0.5 μm, carbon content per unit surface area 0.38 mg/m ² ) were uniformly dispersed using a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare resin varnish 9.

<Production of Adhesive Film>

Prepare an alkyd resin-based release agent (manufactured by Lintec Co., Ltd.) as a support "AL-5") PET film ("lumirror R80" manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130° C., "release PET") subjected to release treatment. Resin varnishes 1 to 9 were uniformly coated on the release surface, and each resin varnish was dried at 80 to 120°C (average 100°C) for 5 minutes, and the thickness of the dried thermosetting resin composition layer was 40 μm. The rough surface of a polypropylene film ("alphan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film was bonded to the thermosetting resin composition layer to prepare an adhesive film.

1‧‧‧Watching board

14‧‧‧wiring layer (embedded wiring layer)

40‧‧‧conductor layer

41‧‧‧Plating protective layer

42‧‧‧Electroplating layer

61‧‧‧hole filling

21’‧‧‧Insulation layer

Claims (19)

A thermosetting resin composition comprising (a) an epoxy resin, (b) a compound having a hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and (d) an inorganic In the thermosetting resin composition of the filler, a part or all of at least one of the (a) component and (c) component has a carbon number selected from an alkylene structure having 2 to 20 carbon atoms and an ether bond. A compound with a soft structure of an alkylene structure of 2 to 20, when the non-volatile content in the thermosetting resin composition is 100 mass%, the (d) component is 30 mass% or more, and the thermosetting resin composition is heated. The elastic modulus, breaking strength, and breaking elongation of the cured product obtained by curing at 23°C are 1GPa to 6GPa, 10MPa to 6%, and 6% to above, respectively. The thermosetting resin composition as claimed in claim 1, wherein the flexible structure is an alkylene structure having ether bonds and having 3 to 15 carbon atoms. The thermosetting resin composition according to claim 1, wherein when the non-volatile components in the thermosetting resin composition are 100 mass%, the content of the compound having a soft structure is 2 mass% to 50 mass%. The thermosetting resin composition according to claim 1, wherein when the non-volatile components in the resin composition are 100% by mass, the content of component (a) is 19.25% by mass or more. The thermosetting resin composition according to claim 1, wherein when the non-volatile components in the thermosetting resin composition are 100 mass%, the content of component (b) is 8 mass% to 50 mass%. An adhesive film comprising a support and the thermosetting resin composition layer of claim 1. The adhesive film according to claim 6, which is used in a manufacturing method of a wiring board comprising the following steps: (1) The step of preparing a base material having a base material and a wiring layer attached to at least one side of the base material , (2) Embedding the wiring layer in the thermosetting resin composition layer, laminating the adhesive film containing the thermosetting resin composition layer on the substrate with the wiring layer, and thermosetting to form an insulating layer , (3) the step of connecting the wiring layers between layers, and (4) the step of removing the base material. The adhesive film according to claim 7, wherein step (3) is at least any one of the steps of forming a via hole in the insulating layer, forming a conductor layer, and grinding or grinding the insulating layer to expose the wiring layer. The adhesive film of claim 6 is used to manufacture a wiring board with an insulating layer and a buried wiring layer embedded in the insulating layer. A method for manufacturing a wiring board, comprising the following steps: (1) preparing a base material with a wiring layer and a wiring layer provided on at least one side of the base material, (2) embedding the wiring layer On the thermosetting resin composition layer, the step of laminating the adhesive film according to any one of claims 7 to 10 on the base material with wiring layer, and thermally hardening to form an insulating layer, (3) interlayer connection wiring layer step, and (4) the step of removing the substrate. The method according to claim 10, wherein step (3) is at least any one of the steps of forming a via hole in the insulating layer, forming a conductor layer, and grinding or grinding the insulating layer to expose the wiring layer. The method according to claim 10, wherein step (3) is a step of forming via holes in the insulating layer and forming a conductor layer, and is performed by laser irradiation. The method according to claim 12, which includes the step of roughening before forming the conductor layer. The method according to claim 10, wherein the wiring board is a flexible wiring board. The method according to claim 10, wherein the minimum pitch of the wiring pattern is 40 μm or less. A wiring board comprising an insulating layer of a cured product of a thermosetting resin composition layer attached to a thin film according to any one of claims 6 to 9, and an embedded wiring layer embedded in the insulating layer. As the wiring board of Claim 16, it is a flexible wiring board. The wiring board according to claim 16, wherein the insulating layer has a thickness of 2 μm or more. A semiconductor device comprising the wiring board of claim 16.

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