TWI738815B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition capable of imparting a thin insulating layer with excellent insulating properties; a resin sheet containing the resin composition; a printed wiring board and a semiconductor device having a thin insulating layer with excellent insulating properties.

The solution of the present invention is a resin composition containing (A) epoxy resin and (B) curing agent. The resin composition is cured at 100°C for 30 minutes and then at 180°C for 30 minutes to obtain a cured product. When the surface of the hardened product is roughened, the contact angle to water of the hardened surface is X(°), and the contact angle of the hardened surface to water after the surface of the hardened is roughened is Y (°), satisfy the relationship of XY≦0° and Y≧80°.

Description

Resin composition

The present invention relates to a resin composition. Furthermore, it relates to a resin sheet, a printed wiring board, and a semiconductor device containing this resin composition.

In recent years, in order to achieve the miniaturization of electronic devices, the thickness of printed wiring boards has been reduced, and the thickness of the inner layer substrate or the insulating layer has tended to become thinner. As a technique for reducing the thickness of the inner layer substrate or the insulating layer, for example, a resin composition for thin films described in Patent Document 1 is known.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2014-152309 A

In Patent Document 1, the inventors of the present application found that when a film is applied to an insulating layer, the thickness increases and the peel strength tends to decrease. In order to solve these problems, they proposed to make the blending amount of the thermoplastic resin into a specific amount. method. However, in this document, there is no review on the insulation performance when the thickness of the insulation layer is made thinner (hereinafter also referred to as "film insulation").

When the insulating layer is a thin film, the inorganic filler particles will come into contact with each other and the current transferred to the interface becomes easy to flow, or the thickness of the insulating layer increases the electrostatic capacitance and becomes easy to short circuit. Insulation performance has become more difficult than before.

The subject of the present invention is to provide a resin composition capable of imparting a thin insulating layer with excellent insulating properties; a resin sheet containing the resin composition; a printed wiring board and a semiconductor device having a thin insulating layer with excellent insulating properties.

The inventors of the present case have conducted an intensive review to solve the aforementioned problems and found that the contact angle of the cured product surface with water before the roughening treatment of the cured resin composition and the roughness of the cured resin composition The contact angle of the surface of the cured product after chemical treatment to water is within a specific range, and the film insulation can be improved, thereby completing the present invention.

That is, the present invention includes the following contents.

[1] A resin composition containing (A) epoxy resin and (B) curing agent. When the resin composition is cured at 100°C for 30 minutes, and then at 180°C for 30 minutes to obtain a cured product, The contact angle of the hardened surface to water before the surface roughening treatment is X(°), and the contact angle of the hardened surface to water after roughening the hardened surface is Y(°) When it meets the relationship of XY≦0° and Y≧80°.

[2] The resin composition described in [1] further containing (C) an inorganic filler.

[3] When the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 50% by mass or more of the resin composition described in [2].

[4] The resin composition described in [2] or [3] in which the average particle diameter of the component (C) is 0.05 μm to 0.35 μm.

[5] The resin composition described in any one of [1] to [4] containing a fluorine compound.

[6] The fluorine compound is the resin composition described in [5] of the fluorine-containing epoxy resin.

[7] The fluorine compound is the resin composition described in [5] or [6] of (D) fluorine-containing silane coupling agent.

[8] The component (C) is the resin composition described in [7] where the component (D) is surface-treated.

[9] The resin composition described in any one of [1] to [8] for forming an insulating layer of a printed wiring board.

[10] A resin sheet comprising a support and a resin composition layer formed of the resin composition described in any one of [1] to [9] provided on the support.

[11] The resin sheet described in [10] in which the thickness of the resin composition layer is 15 m or less.

[12] For forming the insulating layer of a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer with a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer [11] The resin sheet described.

[13] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer with a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer, and the insulating layer is [1]~ [9] A printed wiring board that is a cured product of any resin composition.

[14] A semiconductor device including the printed wiring board described in [13].

According to the present invention, it is possible to provide a resin composition capable of imparting a thin insulating layer with excellent insulating properties; a resin sheet containing the resin composition; a printed wiring board and a semiconductor device having a thin insulating layer with excellent insulating properties.

5‧‧‧The first conductor layer

51‧‧‧The main surface of the first conductor layer

6‧‧‧Second conductor layer

61‧‧‧The main surface of the second conductor layer

7‧‧‧Insulation layer

Fig. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

Hereinafter, the resin composition, resin sheet, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Resin composition]

The resin composition of the present invention contains (A) epoxy resin and (B) curing agent. When the resin composition is thermally cured at 100°C for 30 minutes and then at 180°C for 30 minutes to obtain a cured product, the The contact angle of the hardened surface to water before the surface roughening treatment is X(°), and the contact angle of the hardened surface to water after roughening the hardened surface is Y(°) ，Satisfy the relationship of XY≦0° and Y≧80°. By adjusting the contact angle X and the contact angle Y to satisfy the relationship of XY≦0° and Y≧80°, the surface of the insulating layer is hydrophobized to make it difficult for moisture to penetrate into the insulating layer. A thin insulating layer with excellent insulating properties can be provided. . Hereinafter, when the resin composition is thermally cured at 100°C for 30 minutes, and then at 180°C for 30 minutes to obtain a cured product, the contact angle of the surface of the cured product to water before the roughening treatment is called "contact Angle X" is also called the contact angle of the surface of the cured product after roughening treatment when the resin composition is cured at 100°C for 30 minutes, and then at 180°C for 30 minutes to obtain a cured product. "Contact Angle Y".

Here, the so-called contact angle refers to the angle between the liquid surface and the solid surface (the angle within the liquid) on the free surface of the stationary liquid where it is connected to the solid wall.

The resin composition, if necessary, further contains (C) inorganic filler, (D) fluorine-containing silane coupling agent, (E) thermoplastic resin, (F) hardening accelerator, (G) flame retardant and (H) organic filler Additives such as materials are also acceptable. In addition, the resin composition of the present invention preferably contains a fluorine compound from the viewpoint of adjusting the contact angle X and the contact angle Y to a desired range. The fluorine compound is a compound containing one or more fluorine atoms per molecule, and is a concept including organic compounds and inorganic compounds. In addition, the weight average molecular weight of the fluorine compound is usually 100 to 5,000. The fluorine compound preferably contains any of the components (A) to (H), and the fluorine compound preferably contains the component (A) and/or the component (D). A fluorine compound may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the fluorine compound contains the component (A), the component (A) may be used in combination with the component (A) which is a fluorine compound and a non-fluorine compound. Hereinafter, each component included in the resin composition of the present invention will be explained in detail.

<(A) Epoxy resin>

(A) Examples of epoxy resins include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins, perfluoroalkyl type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins. Resin, bisphenol S type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol Type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol phenol type ring Oxygen resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, Cyclohexanedimethanol type epoxy resin, anisole type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may be used 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 (hereinafter also referred to as "mass%"), at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups per molecule. Among them, it contains an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and has three or more epoxy groups in one molecule, An epoxy resin that is solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin") is preferred. As the epoxy resin, by using a liquid epoxy resin and a solid epoxy resin in combination, excellent flexibility can be obtained, and the breaking strength of the cured product can also be improved.

As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester epoxy resin, glycidyl amine type epoxy resin Oxygen resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with butadiene structure are Preferably, glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin are more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL" (double Phenolic A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YD-8125G" (bisphenol A type) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy resin), "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase Chemtex, "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600 ”(Epoxy resin with a butadiene structure), “ZX1658”, “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., and “630LSD” manufactured by Mitsubishi Chemical Co., Ltd. Glycidylamine type epoxy resin), "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by Daikin Industrial Co., Ltd., etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As solid epoxy resins, naphthalene type tetrafunctional epoxy resin, o-cresol type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, Benzene type epoxy resin, anisole type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthalene type tetrafunctional epoxy resin , Naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N-690" (o-cresol type epoxy resin), "N-695" (o-cresol type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" ( Dicyclopentadiene epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (anisole epoxy Resin), "EPPN-502H" (triphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd. (Biphenyl type epoxy resin), "ESN475V" (naphthol novolac epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., "ESN485" (naphthol novolac epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation ”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bisxylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG manufactured by Osaka Gas Chemical Co., Ltd. -100", "CG-500", "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (Tetraphenylethane type epoxy resin), "YL7760" (Bisphenol AF type epoxy resin), etc.

As a liquid epoxy resin, an aromatic epoxy resin having two or more epoxy groups per molecule and being liquid at a temperature of 20°C is preferable, and a solid epoxy resin having three or more epoxy groups per molecule The epoxy group is preferably an aromatic epoxy resin that is solid at a temperature of 20°C. In addition, the aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

As the component (A), from the viewpoint of adjusting the contact angle X and the contact angle Y to a desired range, a fluorine-containing epoxy resin of a fluorine compound is preferred.

When a liquid epoxy resin and a solid epoxy resin are used together as an epoxy resin, the content ratio of these (liquid epoxy resin: solid epoxy resin) is in the range of 1:0.1 to 1:15 depending on the mass ratio. Better. By setting the content ratio of the liquid epoxy resin to the solid epoxy resin in this range, it can be obtained that i) has moderate adhesion when used in the form of resin sheets, and ii) when used in the form of resin sheets Sufficient flexibility can be obtained, handleability can be improved, and iii) a cured product of the resin composition layer with sufficient breaking strength can be obtained. From the viewpoint of the effects of the aforementioned i) to iii), the content ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1:0.1 by mass ratio. The range of 1:12 is more preferable, and the range of 1:0.5 to 1:10 is even more preferable.

The content of epoxy resin in the resin composition is preferably 5 mass% or more, more preferably 9 mass% or more, from the viewpoint of obtaining an insulating layer with good tensile breaking strength and showing insulation reliability. Preferably, it is 13 mass% or more. The upper limit of the epoxy resin content is not particularly limited as long as the effects of the present invention can be exhibited, and it is preferably 50% by mass or less, and more preferably 40% by mass or less.

In addition, in the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

When the resin composition of the present invention contains two or more (A) components, when the non-volatile content in the resin composition of the fluorine-containing epoxy resin in the resin composition is 100% by mass, the mass is W _A , and the resin When the non-volatile content in the resin composition of the epoxy resin composition other than the fluorine-containing epoxy resin is 100% by mass, when the mass is W _B , W _B /W _A is preferably 1 to 10, and 1 to 5 For better, 1~3 is better.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1000. Within this range, the bridging density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be obtained. In addition, the epoxy equivalent can be measured in accordance with the Japanese Industrial Standards JIS K7236, and is the mass of the resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel penetration chromatography (GPC) method.

<(B) Hardener>

The curing agent is not particularly limited as long as it has the function of curing the epoxy resin. Examples include phenol curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanogen curing agents. Acid ester hardeners, carbodiimide hardeners, etc. The curing agent may be used singly, or two or more of them may be used in combination.

As the phenol-based curing agent and naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a phenolic structure or a naphthol-based curing agent having a phenolic structure is preferable. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer, a phenol phenol hardener containing a triazine skeleton is preferred.

Specific examples of phenol-based hardeners and naphthol-based hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. ", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumitomo Metal Corporation , "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. manufactured by DIC.

The active ester curing agent is not particularly limited, but it is generally preferable to use phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., having two in one molecule The above-mentioned ester-based compounds with high reactivity. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a sulfhydryl compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is hardened The agent is better. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, methylene succinic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. . Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol naphthalene, methylated bisphenol A, and methylated bisphenol F. , Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type Diphenol compounds, phenol phenolic aldehydes, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing phenol phenolic acetate, and an active ester compound containing phenol phenolic phenolic structure Among them, an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene- pentacyclopentadiene-phenylene.

As commercially available products of active ester hardeners, active ester compounds containing dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC- 8000H-65TM" and "EXB-8000L-65TM" (manufactured by DIC Corporation). Examples of active ester compounds containing naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation) and active ester compounds containing phenol phenolic acetaldehyde Examples include "DC808" (manufactured by Mitsubishi Chemical Corporation). Examples of active ester compounds containing phenol phenolic phenolic compounds include "YLH1026" (manufactured by Mitsubishi Chemical Corporation) and active ester hardeners containing phenolic phenolic acetaldehyde. Examples include "DC808" (manufactured by Mitsubishi Chemical Corporation), and active ester hardeners containing phenol phenolic phenate include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like.

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

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate, oligosaccharides (3-methine-1,5-phenylene cyanate), 4,4 '-Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis (4-cyanate ester) phenyl propane, 1,1-bis (4-cyanate ester phenyl methane), bis (4-cyanate ester-3,5-dimethyl phenyl) methane, 1 , 3-bis (4-cyanate phenyl-1-(methyl ethylene)) benzene, bis (4-cyanate phenyl) thioether, and bis (4-cyanate phenyl) Difunctional cyanate ester resins such as ethers, polyfunctional cyanate ester resins induced by phenol phenolic and cresol phenolic resins, and prepolymers in which a part of these cyanate ester resins are triazineized. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin) manufactured by Lonza Japan, and "ULL-950S" (polyfunctional cyanate resin). Ester resin), "BA230", "BA230S75" (part or all of bisphenol A dicyanate is triazaphenylized into a ternary prepolymer), etc.

Specific examples of carbodiimide-based hardeners include "V-03" and "V-07" manufactured by Nisshinbo Chemical.

The content ratio of epoxy resin and hardener is based on the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], preferably in the range of 1:0.01~1:2. 1: 0.015 to 1: 1.5 is more preferable, and 1: 0.02 to 1: 1 is even more preferable. Here, the reactive group of the curing agent refers to an active hydroxyl group, an active ester group, etc., and it varies with the type of the curing agent. In addition, the total number of epoxy groups of the epoxy resin refers to the total value of the total amount of epoxy resins divided by the epoxy equivalent of the solid content of each epoxy resin. The so-called total number of reactive groups of the hardener , Refers to the value obtained by dividing the mass of the solid content of each hardener by the equivalent of the reactive group for all hardeners. By setting the content ratio of the epoxy resin to the curing agent in such a range, the heat resistance of the cured product of the resin composition layer can be further improved.

In one embodiment, the resin composition includes the aforementioned epoxy resin and hardener. The resin composition is a mixture of liquid epoxy resin and solid epoxy resin each containing (A) as the epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1:0.1 ~1:15, more preferably 1:0.3~1:12, and even more preferably 1:0.6~1:10), (B) as the hardener is selected from phenol hardener, naphthol hardener, active One or more types of the group consisting of an ester type curing agent and a cyanate type curing agent (preferably one or more types selected from the group consisting of an active ester type curing agent and a cyanate type curing agent).

The content of the hardener in the resin composition is not particularly limited, and is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. In addition, the lower limit is not particularly limited, but 2% by mass or more is preferable.

<(C) Inorganic filler>

In one embodiment, the resin composition may contain inorganic fillers. The inorganic filler is not particularly limited, and examples include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite ( Aluminum magnesium carbonate), boehmite (boehmite), aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and tungsten phosphate Zirconium acid and so on. Among these, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as the silica, spherical silica is preferred. Inorganic fillers may be used singly or in combination of two or more.

The average particle size of the inorganic filler is preferably 0.35 μm or less, more preferably 0.32 μm or less, even more preferably 0.3 μm or less, and even more preferably 0.29 μm or less. From the viewpoint of improving the dispersibility in the resin composition layer, the lower limit of the average particle size is preferably 0.05 μm or more, more preferably 0.06 μm or more, and even more preferably 0.07 μm or more. As a commercially available product of an inorganic filler having such an average particle diameter, for example, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., "SPH516-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., and the like can be cited. By adjusting the average particle size of the inorganic filler within the aforementioned range, the insulation can be improved.

The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle size. For the measurement sample, it is preferable to use an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

Inorganic fillers, it is better to use surface treatment agents for surface treatment. Examples of the surface treatment agent include (D) a fluorine-containing silane coupling agent described later, and surface treatment agents other than the component (D) (hereinafter also referred to as "other surface treatment agents"). The component (C) can be surface-treated with component (D) or other surface treatment agents. From the viewpoint of adjusting contact angle X and contact angle Y, component (C) can be used as component (D) Surface treatment is better. A surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types.

As other surface treatment agents, at least one surface treatment agent among silane coupling agents, alkoxysilane compounds, and organosiloxane compounds other than the component (D) is preferable. These may also be oligomers. Examples of other surface treatment agents include aminosilane coupling agents, siloxane oxide coupling agents, mercaptosilane coupling agents, silane coupling agents, organosiloxane compounds, alkoxysilane compounds, titanic acid Salt-based coupling agent, etc. Commercial products of surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-Glycoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl-3-amine) manufactured by Shin-Etsu Chemical Co., Ltd. Propyl trimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by industrial companies, etc.

According to the degree of surface treatment of the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, for 100 parts by mass of the component (C), 0.2 to 2 parts by mass of the surface treatment agent is preferably used for surface treatment , It is more preferable to carry out the surface treatment with 0.2 parts by mass to 1 part by mass, and it is even more preferable to carry out the surface treatment with 0.3 parts by mass to 0.8 parts by mass.

According to the degree of surface treatment of the surface treatment agent, it can be evaluated based on the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² or more good. On the other hand, from the viewpoint of suppressing the melt viscosity of the varnish and the melt viscosity in the sheet form, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² The following is even more preferable.

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

From the viewpoint of improving the thickness stability of the resin composition layer, when the non-volatile content in the resin composition is 100% by mass, the content (filling amount) of the inorganic filler in the resin composition is preferably 50% by mass or more. It is more preferably 55% by mass or more, and still more preferably 60% by mass or more. The upper limit of the inorganic filler in the resin composition is preferably 85% by mass or less from the viewpoint of improving the insulation of the film and the tensile breaking strength of the insulating layer (the cured product of the resin composition layer) 80% by mass or less, more preferably 75% by mass or less.

<(D) Fluorine-containing silane coupling agent>

In one embodiment, the resin composition of the present invention contains a fluorine-containing silane coupling agent as a fluorine compound. By including fluorine-containing silane coupling agent, the contact angle X and the contact angle Y can be adjusted.

As a specific example of the component (D), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be cited. (D) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

The aspect of the (D) component contained in the resin composition of the present invention is not particularly limited, and the following aspects (i) to (iii) are preferably included in the resin composition, and (i) or (ii) It is more preferable to contain the form of) in the resin composition, and it is even more preferable to contain the form of (i) in the resin composition. That is, the (D) component is preferably contained in the resin composition as a surface treatment agent as the (C) component.

(i) The component (D) contains a surface treatment agent as the component (C).

(ii) The component (D) is contained alone in the resin composition.

(iii) The component (D) contains the surface treatment agent as the component (C), and the component (D) is contained alone in the resin composition.

"The (D) component contains the surface treatment agent as the (C) component"” means that the (C) component is surface-treated with the (D) component. In this case, the component (D) usually exists on the surface of the component (C). In addition, "the component (D) is contained in the resin composition alone" means that the component (D) does not contain the surface treatment agent as the component (C). In addition, when the component (D) does not contain the surface treatment agent as the component (C), the component (D) is released in the resin composition.

(D) The content of the component is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and even more preferably 0.2% by mass or more. The upper limit is not particularly limited, but is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less.

In the case of a surface treatment agent containing component (D) as component (C), depending on the degree of surface treatment of the surface treatment agent and from the viewpoint of improving the dispersibility of the inorganic filler, for 100 parts by mass of component (C), 0.2 to 2 parts by mass of the surface treatment agent is preferable for surface treatment, 0.2 to 1 part by mass is more preferable for surface treatment, and 0.3 to 0.8 part by mass is more preferable for surface treatment.

<(E) Thermoplastic resin>

In one embodiment, the resin composition of the present invention further contains (E) a thermoplastic resin.

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyimide resins, and polyetherimide resins. Resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, preferably phenoxy resin. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by the gel penetration chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin can be used as the measuring device LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. can be used as the column. /K-804L, use chloroform for the mobile phase, measure under the condition of a column temperature of 40°C, and calculate using the calibration curve of standard polystyrene.

Examples of phenoxy resins include those having a skeleton selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorenone skeleton, and dicyclopentane skeleton. A phenoxy resin with one or more skeletons from the group consisting of diene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton . The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. Specific examples of phenoxy resins include "1256" and "4250" made by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton), and "YX8100" (a benzene containing a bisphenol S skeleton). Oxy resin), and “YX6954” (phenoxy resin containing bisphenol acetophenone skeleton). Other examples include “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and “FX293” manufactured by Mitsubishi Chemical Co., Ltd. "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

As the polyvinyl acetal resin, for example, polyvinyl formal resin, polyvinyl butyral resin, and polyvinyl butyral resin are preferable. As specific examples of polyvinyl acetal resins, for example, "electrochemical butyral 4000-2", "electrochemical butyral 5000-A", "electrochemical butyral 5000-A" manufactured by Denki Kagaku Kogyo Co., Ltd. can be cited. 6000-C", "Electrochemical Butyral 6000-EP", S Lec BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series manufactured by Sekisui Chemical Industry Co., Ltd. .

As specific examples of polyimide resins, "RICA COAT SN20" and "RICA COAT PN20" manufactured by Nippon Rika Co., Ltd. can be cited. As a specific example of the polyimide resin, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetraprotic acid anhydride (Japanese Patent Application Publication No. 2006-37083 Denatured polyimide such as polyimide described in No. Bulletin), polyimide containing a polysiloxane skeleton (polyimide described in JP 2002-12667 and JP 2000-319386), etc. Imine.

As specific examples of polyimide imide resins, "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. can be cited. As specific examples of polyimide imide resins, there are also denatured polyamides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide imide) manufactured by Hitachi Chemical Co., Ltd. Amide.

As a specific example of the polyether sulfide resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

Specific examples of polysulfone resins include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Among them, as the thermoplastic resin, phenoxy resin and polyvinyl acetal resin are preferred. That is, in a suitable embodiment, the thermoplastic resin includes one or more selected from the group consisting of phenoxy resin and polyvinyl acetal resin.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, and more preferably 0.3% by mass to 1% by mass.

<(F) Hardening accelerator>

In one embodiment, the resin composition of the present invention further contains (F) a hardening accelerator.

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

Examples of phosphorus-based hardening accelerators include triphenyl phosphine, borate phosphorus compounds, tetraphenyl phosphate tetraphenyl borate, n-butyl phosphate tetraphenyl borate, tetrabutyl phosphate decanoate, ( 4-Methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., with triphenyl phosphine, tetrabutyl phosphonium decanoate Better.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylamine) Aminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4, 0)-Undecene is preferred.

Examples of imidazole-based hardening accelerators include 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2 ,4-Diamine-6-[2'-Methylimidazole- (1')]-Ethyl-s-Triazine, 2,4-Diamine-6-[2'-Undecylimidazole- (1'))-Ethyl-s-triazine, 2,4-diamine-6-[2'-ethyl-4'-methylimidazole-(1')]-ethyl-s- Triazine, 2,4-diamine-6-[2'-methylimidazole-(1')]-ethyl-s-triazine isocyanuric acid addend, 2-phenylimidazole Isocyanuric acid addenda, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydroxy-1H-pyrrolo [1,2-a] Benmidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole, 2-phenylimidazole and other imidazole compounds and imidazole compounds and The adduct of epoxy resin is preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, commercially available products can be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation can be cited.

Examples of guanidine-based hardening accelerators include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl )Guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7- Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl guanidine, 1-ethyl guanidine, 1-n-butyl guanidine, 1 -n-octadecyl guanidine, 1,1-dimethyl guanidine, 1,1-diethyl guanidine, 1-cyclohexyl guanidine, 1-allyl guanidine, 1 -Phenyl bisguanidine, 1-(o-tolyl) bisguanidine, etc., preferably dicyandiamine, 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 organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, and copper(II) acetylacetonate Organic copper complexes such as salt, organic zinc complexes such as zinc (II) acetypyruvate, organic iron complexes such as iron (III) acetylpyruvate, nickel (II) acetylpyruvate, etc. Organic nickel complexes, manganese (II) acetopyruvate and other organic manganese complexes, etc. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the non-volatile components of the epoxy resin and the hardener are 100% by mass, the content of the hardening accelerator in the resin composition is not particularly limited, and it is preferably 0.01% by mass to 3% by mass.

<(G) Flame Retardant>

In one embodiment, the resin composition of the present invention further contains (G) a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As the flame retardant, commercially available products can be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Dahachi Chemical Industry Co., Ltd., and the like. As a flame retardant, one that is not easily decomposed by water is preferred, for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxo-10-phosphophenanthrene-10-oxide, etc. .

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

<(H) Organic Filling Material>

In one embodiment, the resin composition of the present invention may contain (H) organic filler. By including the component (H), the tensile fracture strength of the cured product of the resin composition layer of the resin sheet can be increased. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board can also be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

As the rubber particles, commercially available products such as "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aika Industrial Co., Ltd. can be used.

As the rubber particles, it is preferable to use "AC3816N" and "AC3401N" manufactured by Aika Industrial Co., Ltd. from the viewpoint of reducing the ionicity and the conductivity of the extracted water of the cured product of the resin composition layer.

When the 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 still more preferably 0.3% by mass to 5% by mass, More preferably, it is 0.5% by mass to 3% by mass.

<(I) Arbitrary additives>

In one embodiment, the resin composition of the present invention may further include other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds and other organic metal compounds, as well as Resin additives such as adhesives, defoamers, leveling agents, adhesion imparting agents, and coloring agents.

<Physical properties of resin composition>

When the resin composition of the present invention is thermally cured at 100°C for 30 minutes and then at 180°C for 30 minutes to obtain a cured product, the contact angle of the cured product surface to water before the surface of the cured product is roughened X (°), when the contact angle of the hardened surface to water after roughening the hardened surface is Y (°), it is XY≦0°, preferably XY≦-3°, more preferably It is XY≦-5°. The lower limit of X-Y is not particularly limited, but is preferably -50° or more, more preferably -40° or more, and even more preferably -30° or more. With X-Y≦0°, the film insulation becomes good. X-Y can be measured in accordance with the method described in the below-mentioned <Measurement of Contact Angle>.

When the resin composition of the present invention is cured at 100°C for 30 minutes, and then heat-cured at 180°C for 30 minutes to obtain a cured product, the surface of the cured product is roughened and the surface of the cured product has a contact angle to water Y , Y≧80°, preferably Y≧83°, more preferably Y≧85°. The upper limit of the contact angle Y is not particularly limited, but is preferably 180° or less, more preferably 150° or less, and even more preferably 120° or less. With Y≧80°, the film insulation becomes good. The contact angle Y can be measured in accordance with the method described in the below-mentioned <Measurement of Contact Angle>.

When the resin composition of the present invention is thermally cured at 100°C for 30 minutes, and then at 180°C for 30 minutes to obtain a cured product, the contact angle X of the cured product surface to water before the surface of the cured product is roughened , Preferably X<80°, more preferably X≦79°. The lower limit of the contact angle X is not particularly limited, but is preferably 30° or more, more preferably 40° or more, and even more preferably 50° or more. With X<80°, the film insulation becomes good. The contact angle X can be measured in accordance with the method described in the below-mentioned <Measurement of Contact Angle>.

The procedure of the roughening treatment at the time of measuring the contact angle can be carried out in accordance with the method described in the below-mentioned <Measurement of Contact Angle>. For details, it is in a specific swelling solution at 60°C for 5 minutes, followed by a specific oxidizing agent solution at 80°C for 10 minutes, and finally immersed in a neutralizing solution at 40°C for 5 minutes and then dried at 80°C for 15 minutes.

[Resin Sheet]

The resin sheet of the present invention includes a support and a resin composition layer provided on the support, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, and still more preferably 8 μm or less from the viewpoint of thinning of the printed wiring board. Although the lower limit of the thickness of the resin composition is not particularly limited, it is usually 1 μm or more, 1.5 μm or more, 2 μm or more.

Examples of the support include a film made of a plastic material, metal foil, and release paper, and a film made of a plastic material or metal foil is preferred.

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter also abbreviated as "PET"), polyethylene naphthalate ( Hereinafter also referred to as “PEN”), such as polyester, polycarbonate (hereinafter also referred to as “PC”), polymethylmethacrylate (hereinafter also referred to as “PMMA”), such as acrylic, cyclic polyolefin, triethyl Acetyl cellulose (TAC), polyether ether (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as the support, as the metal foil, for example, copper foil, aluminum foil, etc. can be cited, and copper foil is preferred. As the copper foil, a foil composed of a single metal of copper may also be used, and a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may also be used.

The support may also be subjected to matte treatment, corona treatment, and anti-static treatment to the surface joined with the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined with a resin composition layer can also be used. As the mold release agent used for the mold release layer of the support with the mold release layer, for example, one may be selected from the group consisting of alkyd resin resin, polyolefin resin, urethane resin, and silicone resin. One or more release agents. The support with a release layer can also use commercially available products, for example, "SK-1", "AL -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by UNITIKA, etc.

The thickness of the support is not particularly limited, but it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support with a release layer, the thickness of the entire support with a release layer is preferably within the aforementioned range.

The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, coating the resin varnish on a support using a die coater or the like, and drying to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, and diethylene glycol monoethyl. Acetate esters such as ether acetate, diethylene glycol ethyl ethers such as ethylene glycol ethyl ether and diethylene glycol butyl ether, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide Amine-based solvents such as amine (DMAc) and N-methylrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can also be performed by well-known methods, such as heating and blowing hot air. The drying condition is not particularly limited, but it is dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies with the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% to 60% by mass of organic solvent is used, dry it at a temperature of 50°C to 150°C for 3 minutes ~10 minutes, the resin composition layer can be formed.

In the resin sheet, a protective film corresponding to the support may be laminated on the surface that is not bonded to the support of the resin composition layer (that is, the surface on the opposite side to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 µm to 40 µm. By layering the protective film, it is possible to prevent dust and mustard from adhering to or damaging the surface of the resin composition layer. The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet of the present invention achieves an insulating layer (cured product of the resin composition layer) with excellent film insulation. That is, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed wiring board (for forming an insulating layer of a printed wiring board), and can be more suitably used as a resin sheet for forming a printed wiring board. Resin sheet for interlayer insulating layer (resin sheet for interlayer insulating layer of printed wiring board). In addition, for example, in a printed wiring board provided with a first conductor layer, a second conductor layer, and an insulating layer provided between the first conductor layer and the second conductor layer, the insulating layer can be formed by the resin sheet of the present invention. The thickness of the insulating layer between the first conductor layer and the second conductor layer is 6 μm or less (preferably 5.5 μm or less, more preferably 5 μm or less) and is excellent in insulation performance.

The insulating layer formed using the resin sheet (or resin composition) of the present invention exhibits good plating adhesion. That is, an insulating layer showing good peeling strength of the plating layer can be achieved. The peel strength of the plating layer is preferably 1.5 kgf/cm or less, more preferably 1 kgf/cm or less, and still more preferably 0.8 kgf/cm or less. The upper limit must be 0.1kgf/cm or more. The evaluation of the plating peel strength can be measured in accordance with the method described in (Measurement of plating adhesion (plating peel strength)) described later.

The insulating layer formed using the resin sheet (or resin composition) of the present invention showed good results in the insulation resistance value after 200 hours under an environment of 130°C, 85RH%, and 3.3V applied. That is, an insulating layer showing a good insulation resistance value can be achieved. The upper limit of the insulation resistance value is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, and even more preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁷ Ω or more, and more preferably 10 ⁸ Ω or more. The insulation resistance value can be measured in accordance with the method described in <Evaluation of Insulation Reliability of Insulation Layer> described later.

[Printed Wiring Board, Manufacturing Method of Printed Wiring Board]

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention, a first conductor layer, and a second conductor layer. The insulating layer is provided between the first conductor layer and the second conductor layer to insulate the first conductor layer from the second conductor layer (the conductor layer is also referred to as a wiring layer). Since the insulating layer formed by the cured product of the resin composition of the present invention has excellent film insulating properties, it has excellent insulating properties even if the thickness of the insulating layer between the first and second conductor layers is 6 μm or less.

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and still more preferably 5 μm or less. The lower limit is not particularly limited, and 0.1 μm or more can be adopted. The thickness of the insulating layer between the first and second conductor layers, as an example shown in FIG. 1, refers to the thickness t1 of the insulating layer 7 between the main surface 51 of the first conductor layer 5 and the main surface 61 of the second conductor layer 6 . The first and second conductor layers are conductor layers adjacent to each other with an insulating layer interposed therebetween, and the main surface 51 and the main surface 61 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured in accordance with the method described in the below-mentioned "Measurement of the thickness of the insulating layer between the conductor layers".

In addition, the thickness t2 of the entire insulating layer is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 12 μm or less. The lower limit is not particularly limited, and 1 μm or more can be adopted.

The printed wiring board of the present invention, using the aforementioned resin sheet, can be manufactured by a method including the following steps (I) and (II).

(I) A step of laminating the resin composition layer of the resin sheet and the inner substrate on the inner substrate

(II) A step of thermally curing the resin composition layer to form an insulating layer.

The "inner substrate" used in step (I) mainly refers to substrates such as glass polyester substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, or It is a circuit board in which a patterned conductor layer (circuit) is formed on one or both sides of the board. In addition, when the printed wiring board is manufactured, the inner layer circuit board to which the insulating layer and/or the conductor layer should be formed is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner-layer substrate with built-in parts must be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner layer substrate from the support side. As a member for heat-compressing the resin sheet to the inner substrate (hereinafter also referred to as "heat-compression bonding member"), for example, a heated metal plate (SUS mirror plate, etc.) or metal roll (SUS roll) can be cited. In addition, instead of directly pressing the heat-compression bonding member on the resin sheet, it is preferable to press the resin sheet with an elastic material such as heat-resistant rubber interposing an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner substrate.

The lamination of the inner substrate and the resin sheet is preferably implemented by a vacuum lamination method. In the vacuum lamination method, the heating and compression bonding temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and compression bonding pressure is preferably 0.098MPa~1.77MPa, more preferably 0.29MPa~ In the range of 1.47MPa, the heating and crimping time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Mingji Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials, and the like.

After the lamination, the layered resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing and heating the compression member from the support side. The pressing conditions for the smoothing treatment may be the same as the heating and pressing conditions for the lamination described above. The smoothing treatment can be performed with a commercially available vacuum laminator. In addition, the lamination and smoothing treatment can also be continuously performed using the aforementioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermally cured to form an insulating layer.

The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally used when forming the insulating layer of a printed wiring board can be used.

For example, the thermosetting conditions of the resin composition layer will vary depending on the type of 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 170°C~200°C), the curing time can be in the range of 5~120 minutes (preferably 10~100 minutes, more preferably 15~90 minutes).

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

When manufacturing a printed wiring board, it is also possible to further implement (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer. These steps (III) to (V) can also be implemented in accordance with various methods known to those skilled in the art for the manufacture of printed wiring boards. In addition, when the support is removed after step (II), the removal of the support can also be performed between step (II) and step (III), step (III) and step (IV), or step (IV). ) And step (V). In addition, as required, the formation of the insulating layer and the conductor layer of steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the aforementioned range.

Step (III) is a step of making holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. Step (III), depending on the composition of the resin composition formed on the insulating layer, for example, it can be implemented using drills, lasers, plasma, etc. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and conventional procedures and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the swelling treatment according to the swelling liquid, the roughening treatment according to the oxidizing agent, and the roughening treatment according to the neutralization treatment of the neutralization liquid may be sequentially performed. The swelling liquid is not particularly limited, and an alkali solution, a surfactant solution, etc. can be mentioned, and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferred. As a commercially available swelling liquid, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU manufactured by Atotech Japan, etc. can be mentioned, for example. The swelling treatment of the swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to a moderate level, it is better to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited. For example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. According to the roughening treatment of the oxidant such as alkaline permanganic acid solution, it is better to immerse the insulating layer in the oxidant solution heated to 60℃~80℃ for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securiganth P manufactured by Atotech Japan. In addition, as the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercially available product, for example, Reduction Solution Securiganth P manufactured by Atotech Japan can be cited. The treatment according to the neutralization solution can be performed by immersing the treated surface that has been subjected to the roughening treatment according to the oxidizing agent in the neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability, etc., the method of immersing the object subjected to the roughening treatment by the oxidizing agent in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. In addition, the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less, and the lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured with a non-contact surface roughness meter. The details can be described later (arithmetic average roughness (Ra), Measurement of root mean square roughness (Rq)).

Step (V) is a step of forming a conductor layer. When a conductor layer is not formed on the inner substrate, step (V) is a step of forming a first conductor layer. When a conductor layer is formed on the inner substrate, the conductor layer is the first conductor layer, and step (V) This is the step of forming the second conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a suitable implementation mode, the conductor layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium . The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the aforementioned group (for example, nickel/chromium alloy, copper/copper/nickel alloy and Copper/titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning formed by the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel/chromium Alloy, copper/nickel alloy, copper/titanium alloy alloy layer is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layer Better.

The conductor layer may have a single-layer structure, a single metal layer composed 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 has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel/chromium alloy.

The thickness of the conductor layer varies with the design of the desired printed wiring board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductive layer can also be formed by plating. For example, the surface of the insulating layer can be plated by a previously known technique such as a semi-active method or a right-active method to form a conductor layer with a desired wiring pattern. The following shows an example of forming the conductor layer by the semi-active method.

First, on the surface of the insulating layer, a plating seed layer is formed by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed corresponding to the desired wiring pattern so that a part of the plating seed layer is exposed. After the metal layer is formed by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

The resin sheet of the present invention can achieve a good insulating layer with respect to the embedding of parts, so even when the printed wiring board is a circuit board with built-in parts, it can be suitably used. The built-in circuit board of the part can be manufactured by a conventional manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may also be an insulating layer provided with a cured product of the resin composition layer of the resin sheet of the present invention, or an embedded wiring layer in which the insulating layer is embedded.

[Semiconductor device]

The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) on the conductive parts of the printed wiring board. The so-called "conducting place" refers to the "place where the printed wiring board transmits electrical signals." The place can be the surface or the place where it is buried. In addition, the semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting a semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively perform its functions. Specifically, a wire bonding method, a flip-chip mounting method, and an Mounting method of bump embedded layer (BBUL), mounting method based on anisotropic conductive film (ACF), mounting method based on non-conductive film (NCF), etc. Here, the "mounting method based on bumpless embedded layer (BBUL)" refers to "the mounting method of directly embedding the semiconductor chip in the recess of the printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board" .

[Example]

Hereinafter, the present invention will be described in detail with examples. The present invention is not limited by these examples. In addition, in the following, "parts" and "%" mean "parts by mass" and "% by mass (% by mass)" unless otherwise specified.

<Measurement of the average particle size of inorganic fillers>

In a vial, 100 mg of inorganic filler, 0.1 g of dispersant ("SN9228" manufactured by Sannopco), and 10 g of methyl ethyl ketone were weighed out, and dispersed by ultrasound for 20 minutes. Using a laser diffraction type particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation), the particle size distribution was measured by the graded cell method, and the average particle size based on the median diameter was calculated.

<Measurement of the specific surface area of inorganic fillers>

Using a BET automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), the specific surface area of the inorganic filler was measured.

<Inorganic filler used>

Inorganic filler 1: For 100 parts of spherical silica ("SPH516-05" manufactured by Nippon Steel & Sumikin Materials, with an average particle size of 0.29μm and a specific surface area of 16.3m ² /g), 3,3,3- Trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103) has been surface-treated on one part.

Inorganic filler 2: For 100 parts of spherical silica ("SPH516-05" manufactured by Nippon Steel & Sumikin Materials, with an average particle size of 0.29μm and a specific surface area of 16.3m ² /g), N-phenyl-3 -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) with one part surface-treated.

Inorganic filler 3: For 100 parts of spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078μm, specific surface area 30.7m ² /g), 3,3,3-trifluoro Propyl trimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-7103) has been surface-treated in 2 parts.

Inorganic filler 4: For 100 parts of spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078μm, specific surface area 30.7m ² /g), N-phenyl-3-amine Surface-treated two parts of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573).

Inorganic filler 5: For spherical silica ("SC1500SQ" made by Admatechs ("SO-C1" treated with hexamethyldisilazane), the average particle size is 0.63μm, and the specific surface area is 11.2m ² /g ) 100 parts, surface treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573).

[Preparation of resin composition]

<Preparation of Resin Composition 1>

Combine 6 parts of bisxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 185), and naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of approximately 332) 10 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 238) 10 parts, bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epoxy equivalent is about 169, bisphenol A type and bisphenol F type 1:1 mixture) 4 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) is a 1:1 solution) 2 parts, stirred in a mixed solvent of 20 parts of solvent naphtha (solvent naphtha) and 10 parts of cyclohexanone, and heated to dissolve at the same time. After cooling to room temperature, mix 3 parts of a novolac hardener containing a triazine skeleton ("LA7054" made by DIC, with a hydroxyl equivalent of about 125 and a solid content of 60% in MEK solution). Naphthol hardens ("SN-495V" manufactured by DIC Company, hydroxyl equivalent is about 231) 6 parts, 90 parts of inorganic filler 1, and amine hardening accelerator (4-dimethylaminopyridine (DMAP)) 0.05 parts, with After being uniformly dispersed in a high-speed rotary mixer, it was filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Preparation of resin composition 2>

Combine 6 parts of bisxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 185), and naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of approximately 332) 10 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 238) 10 parts, bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epoxy equivalent is about 169, bisphenol A type and bisphenol F type 1:1 mixture) 4 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) is a 1:1 solution) 2 parts, stirred in a mixed solvent of 20 parts of solvent naphtha (solvent naphtha) and 10 parts of cyclohexanone, and heated to dissolve at the same time. After cooling to room temperature, an o-cresol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, with a hydroxyl equivalent of about 151 and a solid content of 50% 2-methoxypropane Alcohol solution) 4 parts, active ester hardener ("EXB-8000L-65M" manufactured by DIC company, active base equivalent of about 220, non-volatile content 65% by mass MEK solution) 7 parts, 90 parts of inorganic filler 2 , And 0.05 parts of amine hardening accelerator (4-dimethylaminopyridine (DMAP)), after uniformly dispersing with a high-speed rotating mixer, filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare Resin composition 2.

<Preparation of resin composition 3>

Combine 6 parts of bisxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 185), and naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of approximately 332) 20 parts, 2 parts of anisole type epoxy resin ("EXA-7311-G4" manufactured by DIC Company, epoxy equivalent of about 213), stirred in 20 parts of solvent naphtha and cyclohexanone 10 parts of mixed solvents are heated and dissolved at the same time. After cooling to room temperature, an o-cresol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, with a hydroxyl equivalent of about 151 and a solid content of 50% 2-methoxypropane Alcohol solution) 4 parts, active ester hardener ("EXB-8000L-65M" manufactured by DIC company, active base equivalent of about 220, non-volatile content 65% by mass MEK solution) 7 parts, 50 parts of inorganic filler 3 , And 0.05 parts of imidazole-based hardening accelerator (1B2PZ, 1-benzyl-2-phenylimidazole), uniformly dispersed in a high-speed rotary mixer, and filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO), Resin composition 3 was prepared.

<Preparation of Resin Composition 4>

Combine 6 parts of bisxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 185), and naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of approximately 332) 10 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) 10 parts, naphthyl ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, Epoxy equivalent is about 213) 2 parts, stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and heated to dissolve at the same time. After cooling to room temperature, an o-cresol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, with a hydroxyl equivalent of about 151 and a solid content of 50% 2-methoxypropane Alcohol solution) 4 parts, active ester hardener ("EXB-8000L-65M" manufactured by DIC company, active base equivalent of about 220, non-volatile content 65% by mass MEK solution) 7 parts, 50 parts of inorganic filler 4 , And 0.05 parts of amine hardening accelerator (4-dimethylaminopyridine (DMAP)), after uniformly dispersing with a high-speed rotating mixer, filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare Resin composition 4.

<Preparation of resin composition 5>

Combine 6 parts of bisxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 185), and naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of approximately 332) 20 parts, 4 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135), stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, at the same time Heat it to dissolve. After cooling to room temperature, mix 3 parts of a novolac hardener containing a triazine skeleton ("LA7054" made by DIC, with a hydroxyl equivalent of about 125 and a solid content of 60% in MEK solution). Naphthol hardens ("SN-495V" manufactured by DIC Corporation, hydroxyl equivalent is about 231) 6 parts, 80 parts of inorganic filler 5, and amine hardening accelerator (4-dimethylaminopyridine (DMAP)) 0.05 parts, with After being uniformly dispersed in a high-speed rotating mixer, it was filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 5.

<Preparation of resin composition 6>

Combine 6 parts of bisxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 185), and naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of approximately 332) 20 parts, anisole type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent of about 213) 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass of cyclohexanone: 2 parts of methyl ethyl ketone (MEK) 1:1 solution), stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and heated and dissolved at the same time. After cooling to room temperature, an o-cresol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, with a hydroxyl equivalent of about 151 and a solid content of 50% 2-methoxypropane Alcohol solution) 4 parts, active ester hardener ("EXB-8000L-65M" manufactured by DIC company, active base equivalent of about 220, non-volatile content 65% by mass MEK solution) 7 parts, 80 parts of inorganic filler 5 , And 0.05 parts of imidazole-based hardening accelerator (1B2PZ, 1-benzyl-2-phenylimidazole), uniformly dispersed in a high-speed rotary mixer, and filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO), Resin composition 6 was prepared.

The components used in the preparation of resin compositions 1 to 6 and their blending amounts (mass parts of non-volatile components) are shown in the table below. In addition, the abbreviations in the table below are as follows.

YX4000HK: Bisxylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 185

ESN475V: Naphthalene epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Made, epoxy equivalent is about 332

YL7760: Bisphenol AF type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 238

EXA-7311-G4: Naphthyl ether type epoxy resin, manufactured by DIC Company, epoxy equivalent of about 213

ZX1059: Bisphenol type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent is about 169, a 1:1 mixture of bisphenol A type and bisphenol F type

ZX1658GS: Cyclohexane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 135

LA3018-50P: Ortho-methyl phenolic hardener containing triazine skeleton, manufactured by DIC company, hydroxyl equivalent is about 151, solid content 50% 2-methoxypropanol solution

LA7054: Novolac hardener containing triazabenzene skeleton, manufactured by DIC, a MEK solution with a hydroxyl equivalent of about 125 and a solid content of 60%

SN-495V: Naphthol-based hardener, manufactured by DIC, with a hydroxyl equivalent of about 231

EXB-8000L-65M: Active ester hardener, manufactured by DIC Company, with an active base equivalent of about 220 and a non-volatile content of 65% by mass in MEK solution

YX7553BH30: Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, 30 mass% solid content cyclohexanone: methyl ethyl ketone (MEK) 1:1 solution

DMAP: Amine-based hardening accelerator, 4-dimethylaminopyridine

1B2PZ: Imidazole-based hardening accelerator, 1-benzyl-2-phenylimidazole

[Production of resin sheet]

As a support, a PET film ("Lumirror R80" made by Toray Company" made with an alkyd resin-based mold release agent ("AL-5" made by LINTEC) was prepared, with a thickness of 38μm and a softening point of 130°C. "Release PET").

Put each resin composition on the demoulded PET, uniformly coat it with a die coater so that the thickness of the resin composition layer after drying becomes 13μm, and dry it at 70°C to 95°C for 2 minutes, and get it on the demoulded PET Resin composition layer. Next, on the surface of the resin sheet that is not bonded to the support, the rough surface of the polypropylene film ("ALPHAN MA-411" manufactured by Oji F-TEX Co., Ltd., thickness 15μm) as a protective film is layered with the resin composition The bonding method is layered. Thereby, a resin sheet consisting of a mold-releasing PET (support), a resin composition layer, and a protective film in this order is obtained.

[Evaluation Test]

<Measurement of Thickness and Peeling Strength of Coating>

(Modulation of evaluation substrate)

(1) Bottom treatment of the inner circuit board

As the inner circuit board, a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 3μm, with a circuit conductor (copper) formed with a wiring pattern of L/S=2μm/2μm on both sides was prepared The thickness of the substrate is 0.15mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Corporation, size 255×340mm). The both sides of the inner layer circuit board were treated with organic coating on the copper surface with "FlatBOND-FT" manufactured by MEC Corporation.

(2) Laminating of resin sheets

The protective film was peeled off from each resin sheet produced in the Examples and Comparative Examples, and a batch-type vacuum pressure laminator (manufactured by Nikko-Materials, 2-station build-up laminator, CVP700) was used to layer the resin composition with the inner layer. Layer circuit boards are connected to each other, and both sides of the inner layer circuit boards are laminated. The lamination was carried out by reducing the pressure for 30 seconds to 13 hPa or less, and crimping at 130°C and 0.74 MPa for 45 seconds. Next, hot extrusion was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of the resin composition layer

The inner layer circuit board with laminated resin sheets is put into a furnace at 100°C for 30 minutes, and then moved to a furnace at 180°C for 30 minutes, thermally cured to form an insulating layer with a thickness of 5 μm, and the release PET is peeled off. Think of this as "evaluation base A".

(4) Steps for roughening treatment

The evaluation substrate A on which the insulating layer was formed was subjected to a desmear treatment as a roughening treatment. In addition, as the desmear treatment, the following wet desmear treatment was performed.

Wet slag removal treatment:

Dip it in a swelling solution ("Swelling-dip sequricant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then in an oxidant solution (manufactured by Atotech Japan) "Concentrate compact CP", an aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) was immersed at 80°C for 10 minutes, and finally in a neutralization solution ("Reduction solution sequricant" manufactured by Atotech Japan). P (transliteration)", sulfuric acid aqueous solution) was immersed at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Steps to form conductor layer

(5-1) Electroless plating steps

In order to form a conductor layer on the surface of the aforementioned circuit board, a plating step including the following steps 1 to 6 (a copper plating step using a chemical solution manufactured by Atotech Japan) was performed to form the conductor layer.

1. Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer provided with via holes)

Use the trade name: Cleaning Cleaner Securiganth 902 (trade name) to wash at 60°C for 5 minutes.

2. Soft etching (cleaning inside the through hole)

A sulfuric acid acid sodium peroxodisulfate aqueous solution was used for treatment at 30°C for 1 minute.

3. Pre-impregnation (to adjust the charge on the surface of the insulating layer given to Pd)

Using Pre.Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.

4. Activator (impartment of Pd to the surface of the insulating layer)

Using Activator Neoganth 834 (trade name), it was treated at 35°C for 5 minutes.

5. Reduction (reduction of Pd imparted to the insulating layer)

A mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name) was used and treated at 30°C for 5 minutes.

6. Electroless copper plating step (precipitate copper from the surface of the insulating layer (Pd surface))

A mixture of Basic Solution Printganth MSK-DK (trade name) and Copper solution Printganth MSK (trade name) and Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) was used and treated at 35°C for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electrolytic plating steps

Next, using a chemical solution manufactured by Atotech Japan, an electrolytic copper plating step was performed under the conditions that copper was filled in the through holes. Thereafter, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm that is conducted to the through hole and a circular conductor pattern with a diameter of 10 mm that is not connected to the underlying conductor are used on the insulating layer. A conductor layer with lands and conductor patterns was formed on the surface with a thickness of 10 μm. Next, an annealing treatment was performed at 200°C for 90 minutes. This board is referred to as "evaluation board B".

(Determination of Arithmetic Average Roughness (Ra) and Root Mean Square Roughness (Rq))

Use a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments) on the surface of the insulating layer other than the circular conductor pattern of the evaluation substrate B. In the VSI contact mode, the measurement range is 121μm with a 50x lens. ×92μm to obtain the value of Ra and Rq. Calculate the average value of 6 points respectively, and round the next digit to the nearest whole number. The results are shown in the table below.

(Measurement of coating adhesion (coating peel strength))

To the conductor layer of the evaluation substrate B, cut into the part with a width of 10mm and a length of 100mm, peel off one end and clamp it with a grabbing tool (manufactured by TSE, Autocom type inspection machine AC-50C-SL), and use the Instron universal The tester measures the load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min at room temperature as the peel strength.

<Measurement of the thickness of the insulating layer between conductor layers>

Using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology), a cross-sectional observation of the evaluation substrate B was performed. In detail, a cross-section in the vertical direction is cut from the surface of the conductor layer by FIB (Clustered Ion Beam), and the thickness of the insulating layer between the conductor layers is measured from the cross-sectional SEM image. For each sample, observe the cross-sectional SEM images of 5 randomly selected locations, and use the average value as the thickness of the insulating layer between the conductor layers (μm), which is shown in the table below.

<Evaluation of the insulation reliability of the insulating layer>

The 10mm diameter circular conductor side of the evaluation substrate B obtained above was used as a positive (+) electrode, and the grid conductor (copper) side of the inner circuit board connected to the land with a diameter of 1mm was a negative (-) electrode , Using a highly accelerated life test device ("PM422" manufactured by ETAC), the insulation resistance value after 200 hours under the conditions of 130℃, 85% relative humidity and 3.3V DC voltage applied, with electrochemical migration tester ("ECM-100" manufactured by J-RAS) was measured. Perform this measurement 6 times. If all the resistance values of the test piece for 6 times are above 10 ⁷ Ω, it is "○", and if it is less than 10 ⁷ Ω once, it is "×". Compare the evaluation result with the insulation resistance value. Shown in the table below. The insulation resistance value listed in the table below is the lowest value of the insulation resistance value of the 6-point test piece.

<Measurement of contact angle>

The contact angle of the surface of the hardened material according to the drop method of water droplets was measured using an automatic contact angle meter (DropMaster DMs-401 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a syringe was filled with pure water, and 1.0 μL of water droplets were made to adhere to the surface of the insulating layer of the evaluation substrate A. The contact angle after 2000 ms after the attachment of water droplets was measured with the aforementioned automatic contact angle meter, and it was X (°).

Next, the roughening treatment of the insulating layer of the evaluation substrate A was carried out in the same manner as the step of carrying out the roughening treatment in (4) above. After that, the syringe was filled with pure water, and 1.0 μL of water droplets were produced and adhered to the roughened insulating layer surface of the evaluation substrate A. The contact angle after 2000 ms after the attachment of water droplets was measured with the aforementioned automatic contact angle meter, and it was Y (°). When X-Y is 0 or less, it is "○", and when X-Y is more than 0, it is "×". In addition, if Y is 80° or more, it is "○", and if it is less than 80°, it is "×".

Claims (14)

A resin composition characterized by containing (A) epoxy resin and (B) curing agent. When the resin composition is cured at 100°C for 30 minutes and then at 180°C for 30 minutes to obtain a cured product, The contact angle of the hardened surface to water before the surface roughening treatment is X(°), and the contact angle of the hardened surface to water after roughening the hardened surface is Y(°) When it meets the relationship of XY≦0° and Y≧80°, X<80°. Such as the resin composition of item 1 of the scope of patent application, which further contains (C) inorganic filler. For example, in the resin composition of item 2 of the scope of patent application, when the non-volatile content in the resin composition is 100% by mass, the content of component (C) is 50% by mass or more. For example, the resin composition of item 2 or 3 in the scope of patent application, wherein the average particle size of component (C) is 0.05μm~0.35μm. For example, the resin composition of item 1 in the scope of the patent application contains a fluorine compound. For example, the resin composition of item 5 of the scope of patent application, wherein the fluorine compound is a fluorine-containing epoxy resin. For example, the resin composition of item 5 in the scope of patent application, wherein the fluorine compound is (D) fluorine-containing silane coupling agent. Such as the resin composition of item 7 in the scope of patent application, in which (C) component is surface-treated by (D) component. For example, the resin composition of item 1 in the scope of patent application is used to form the insulating layer of the printed wiring board. A resin sheet is characterized by comprising a support body and a resin composition layer formed of the resin composition of any one of items 1 to 9 in the scope of patent application provided on the support body. For example, the resin sheet of item 10 in the scope of patent application, wherein the thickness of the resin composition layer is 15 μm or less. For example, the resin sheet of item 11 of the scope of patent application, which is a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer with a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer For the formation of the insulating layer. A printed wiring board characterized by a printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer with a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer, the insulating layer being The cured product of the resin composition of any one of items 1 to 9 in the scope of patent application. A semiconductor device characterized by the printed wiring board of item 13 of the scope of patent application.

Images