TW202110633A - Resin sheet capable of suppressing appearance defect of resin composition layer even if thickness of resin composition layer is thick - Google Patents

Abstract

The present invention provides a resin sheet for suppressing the appearance defect of the resin composition layer even if the thickness of the resin composition layer is thick, a circuit board using the same, and a semiconductor chip package. The solution of the present invention is a resin sheet, which includes: a support body and a resin composition layer disposed on the support body, wherein the thickness of the resin composition layer is above 60 um. When the length of the support body while bonding with the resin composition layer is set as LA and the length of the support body while peeling from the resin composition layer is set as LB, LA/LB should be above 1.005 and below 1.2.

Description

Resin sheet

The present invention relates to resin sheets. Furthermore, the present invention relates to a circuit board using a resin sheet and a semiconductor chip package.

In recent years, the demand for high-performance electronic devices called smart phones and tablet devices has gradually increased. With this, insulating materials that can be used as sealing layers or insulating layers of these electronic devices are also required to be more highly functional.

The insulating material is generally a resin sheet provided with a resin composition layer on a support. For example, Patent Document 1 discloses a sealing sheet, which is used to seal parts contained in a circuit board. An insulating material is provided on the support. The resin composition layer. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2018-162418 A

[The problem to be solved by the invention]

When the resin composition layer in the resin sheet is used as the sealing layer, the thickness of the resin composition layer may be insufficient to sufficiently seal the internal parts of the electronic device, so the thickness of the resin composition layer may be increased.

However, when the thickness of the resin composition layer is thick, the appearance of the resin composition layer may be poor.

The present invention is an innovative proposal made in view of the foregoing problems, and its purpose is to provide a resin sheet in which appearance defects of the resin composition layer are suppressed even if the thickness of the resin composition layer is thick; a circuit board using the resin sheet, And semiconductor chip packaging. [Means to solve the problem]

In order to solve the aforementioned problems, the inventor of the present invention has conducted careful examination and found that the poor appearance of the resin composition is caused by the wrinkles generated by the support being transferred to the resin composition layer. In addition, the present inventors found that the length of the support when joined with the resin composition layer and the length of the support after peeling the support from the resin composition layer meet the specified relationship of the resin sheet, because it can suppress the wrinkles on the support. Therefore, even if the thickness of the resin composition layer is thick, the appearance defects of the resin composition layer are still suppressed, and the present invention is successfully completed.

That is, the present invention includes the following contents. [1] A resin sheet comprising: a first support, and a resin composition layer joined to the first support, the thickness of the resin composition layer is 60 μm or more, and one or more in-plane directions of the support The ratio L _A /L _B satisfies the relationship of 1.005 or more and 1.2 or less, L _A represents the length of the first support in the aforementioned in-plane direction when it is joined to the resin composition layer, and L _B represents the aforementioned after peeling from the resin composition layer The length of the first support in the in-plane direction. [2] The resin sheet as in [1], wherein the resin sheet includes a first support, a resin composition layer, and a second support in this order. [3] The resin sheet as in [1] or [2], wherein the minimum melt viscosity of the resin composition layer at 60°C to 200°C is 1,000 poise or more and 20,000 poise. [4] The resin sheet as in any one of [1] to [3], wherein the lowest melt viscosity of the resin composition layer at 60°C to 200°C is set to M (poise), and the resin composition layer When the thickness is set to T (μm), M/T satisfies the relationship between 5 and 200. [5] A circuit board comprising: an insulating layer formed by a cured product of the resin composition layer in the resin sheet of any one of [1] to [4]. [6] A semiconductor chip package comprising: the circuit substrate as in [5], and a semiconductor chip mounted on the aforementioned circuit substrate. [7] A semiconductor chip package comprising: a semiconductor chip and a cured product of a resin composition layer in the resin sheet of any one of [1] to [4] that seals the aforementioned semiconductor chip. [Effects of Invention]

According to the present invention, it is possible to provide a resin sheet in which appearance defects of the resin composition layer are suppressed even if the thickness of the resin composition layer is thick; a circuit board using the resin sheet, and a semiconductor chip package can be provided.

Hereinafter, embodiments and examples are shown to explain the present invention in detail. However, the present invention is not limited to the embodiments and exemplified materials exemplified below, and can be implemented with arbitrary changes without departing from the scope of the patent application of the present invention and the equivalent scope.

[Resin composition] Before explaining the resin sheet of the present invention in detail, the resin composition used when forming the resin composition layer will be explained.

For the resin composition used when forming the resin composition layer, the cured product system may be one with sufficient insulation. In one embodiment, the resin composition contains (A) curable resin. The resin composition may further contain (B) inorganic filler, (C) hardening accelerator, (D) thermoplastic resin, (E) amphiphilic polyether block copolymer, (F) elastomer and (G) Other additives. Hereinafter, each component contained in the resin composition will be explained in detail.

＜(A) Curing resin＞ The resin composition contains (A) curable resin as the (A) component. As the (A) curable resin, a curable resin that can be used when forming an insulating layer of a printed wiring board can be used, and a thermosetting resin is preferred.

Examples of curable resins include epoxy resins, phenolic resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, and amine resins. Resins, acid anhydride resins, etc. (A) A component system may be used individually by 1 type, and may combine 2 or more types at arbitrary ratios. Below, there are phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins. The resin that the oxygen resin reacts to harden the resin composition is collectively referred to as the "hardener". As the resin composition, it is preferable to include an epoxy resin and a curing agent as the (A) component.

As the epoxy resin used as the component (A), for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, Bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, phenol type epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol type ring Oxygen resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, epoxy propyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, Biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane Type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A). From the standpoint of remarkably achieving the desired effect of the present invention, relative to 100% by mass of the non-volatile components of component (A), the ratio of epoxy resin having 2 or more epoxy groups per molecule is preferably 50% by mass or more , Preferably 60% by mass or more, particularly preferably 70% by mass or more.

For the epoxy resin, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as In the case of "solid epoxy resin"). In the resin composition, as the component (A), only a liquid epoxy resin may be included, a solid epoxy resin may be included alone, or a liquid epoxy resin and a solid epoxy resin may be included in combination.

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

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 type epoxy resin, epoxy resin Propylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, epoxypropyl amine type Epoxy resins and epoxy resins with butadiene structure are preferred, and bisphenol A epoxy resins and bisphenol F epoxy resins are preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. "825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol Phenolic epoxy resin); "630" and "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. Mixture with bisphenol F epoxy resin); "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX; "Ceroxide 2021P" (resin with ester skeleton) manufactured by Daicel Cyclic epoxy resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel; "ZX1658", "ZX1658GS" (liquid 1,4 -Glyoxypropyl cyclohexane type epoxy resin) and so on. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in a molecule is preferred, and an aromatic solid epoxy resin having 3 or more epoxy groups in a molecule is preferred. good.

As solid epoxy resins, dixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, ginseng Phenolic epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF epoxy resin , Tetraphenylethane type epoxy resin is preferred, and naphthalene type epoxy resin is preferred.

As a solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthalene type tetrafunctional epoxy resin, naphthalene type epoxy resin Phenolic epoxy resins and biphenyl epoxy resins are preferred. 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" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (bicyclic Pentadiene epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether epoxy Resin); "EPPN-502H" (ginseng phenolic epoxy resin), "NC7000L" (naphthol phenolic epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd. "(Biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H" manufactured by Mitsubishi Chemical Corporation , "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin); "PG-100" manufactured by Osaka Gas Chemical Corporation, "CG-500", "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (茀 type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "JER1031S" (tetraphenylethane type epoxy resin), etc. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), the amount ratio (liquid epoxy resin: solid epoxy resin) is based on a mass ratio of 1:0.1 ~1:20 is better, preferably 1:0.3~1:15, particularly preferably 1:0.5~1:10. If the ratio of the liquid epoxy resin to the solid epoxy resin is within this range, the desired effect of the present invention can be significantly achieved. And, usually when used in the form of an adhesive film, it will give proper adhesiveness. In addition, when used in the form of an adhesive film, sufficient flexibility can be obtained and the operability can be improved. In addition, hardened products with sufficient breaking strength can usually be obtained.

The epoxy equivalent of the epoxy resin as component (A) is preferably 50g/eq.~5000g/eq., preferably 50g/eq.~3000g/eq., more preferably 80g/eq.~2000g/ eq., more preferably 110g/eq.~1000g/eq. By being in this range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin as the component (A) is preferably 100 to 5000, preferably 250 to 3000, and more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the epoxy resin as the component (A), from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, when the non-volatile content in the resin composition is 100% by mass, 1% by mass or more More preferably, it is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit of the epoxy resin content is preferably 45% by mass or less, preferably 40% by mass or less, particularly preferably 35% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

As the active ester resin used as the component (A), a resin having one or more active ester groups per molecule can be used. Among them, as active ester resins, phenol esters, thiophenol esters, N-hydroxy amine esters, heterocyclic hydroxyl compound esters, etc., resins having two or more highly reactive ester groups per molecule Better. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is preferred.

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

As the phenol compound or naphthol compound, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Alkylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compounds , Phenolic phenolic and so on. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol on one molecule of dicyclopentadiene.

Preferred specific examples of active ester resins include active ester resins containing dicyclopentadiene-type diphenol structure, active ester resins containing naphthalene structure, and phenolic phenolic acetoxy compounds. Ester resins, active ester resins containing benzyl phenolic aldehydes. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene type diphenol structure are preferred. "Dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit containing phenylene-dicyclopentene-phenylene.

As a commercially available product of active ester resins, among them, active ester resins containing a dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T ", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); examples of the active ester resin containing naphthalene structure include EXB-8100L-65T", "EXB-8150L-65T ", "EXB9416-70BK", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T" (manufactured by DIC Corporation); Examples of the active ester resins of acetyl compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of the active ester resins of benzyl compounds containing phenolic phenol include "YLH1026" (Mitsubishi Chemical Corporation). Manufacture); as the active ester resin of the phenol phenolic acetyl compound, such as "DC808" (manufactured by Mitsubishi Chemical Corporation); as the active ester resin of the phenol phenolic benzyl compound, such as " "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

As the phenol resin and naphthol resin used as the component (A), those having a phenolic structure are preferred from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol curing agent is preferred, and a phenol resin containing a triazine skeleton is preferred.

Specific examples of phenol resins and naphthol resins 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 Chemical & Materials Co., Ltd. "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. manufactured by DIC.

As specific examples of the benzoxazine-based resin as the component (A), "JBZ-OD100" (benzoxazine ring equivalent 218), "JBZ-OP100D" (benzoxazine ring equivalent) manufactured by JFE Chemical Co., Ltd. Oxazine ring equivalent 218), "ODA-BOZ" (benzoxazine ring equivalent 218); "Pd" (benzoxazine ring equivalent 217) manufactured by Shikoku Chemical Industry Co., Ltd., "Fa" (benzoxazine Ring equivalent 217); "HFB2006M" (benzoxazine ring equivalent 432) manufactured by Showa Polymer Corporation, etc.

Examples of the cyanate resin used as the component (A) include bisphenol A dicyanate, polyphenol cyanate, and oligo(3-methylene-1,5-phenylene cyanate). Ester), 4,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanide Ester, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl Phenyl) methane, 1,3-bis (4-cyanate phenyl-1-(methylethylene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyano Bifunctional cyanate ester resins such as acid ester phenyl) ether; polyfunctional cyanate ester resins derived from phenol phenolic and cresol phenolic; prepolymers in which part of these cyanate ester resins are triazineized, etc. Specific examples of cyanate ester resins include "PT30", "PT30S" and "PT60" (phenol novolac type polyfunctional cyanate resin) manufactured by Lonza Japan, and "ULL-950S" (multifunctional Cyanate resin), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazineized and becomes a trimer), etc.

As a specific example of the carbodiimide resin as the component (A), for example, Carbodilite (registered trademark) V-03 (carbodiimide equivalent: 216, V-05 (carbon) manufactured by Nisshinbo Chemical Co., Ltd. Diimide equivalent: 216), V-07 (carbodiimide equivalent: 200); V-09 (carbodiimide equivalent: 200); Stabaxol (registered trademark) P ( Carbodiimide equivalent: 302).

Examples of the amine-based resin used as the component (A) include resins having one or more amine groups in one molecule, for example, aliphatic amines, polyether amines, alicyclic amines, Among the aromatic amines, among them, from the viewpoint of achieving the desired effect of the invention, aromatic amines are preferred. The amine resin is preferably a first-stage amine or a second-stage amine, and more preferably a first-stage amine. As specific examples of amine hardeners, for example, 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiamino sulfide, 4,4'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, m-phenylenediamine, m-diaminodiamine, diethyltoluene Diamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl -4,4-Diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1 ,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4 '-Bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfonate, bis(4-(3-aminophenoxy)phenyl)sulfonate Wait. Commercially available amine resins can also be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd. , "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc.

Examples of acid anhydride resins used as the component (A) include resins having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride resins include anhydrous phthalic acid, tetrahydro anhydrous phthalic acid, hexahydro anhydrous phthalic acid, methyl tetrahydro anhydrous phthalic acid, methyl hexahydro anhydrous phthalic acid, methyl nadic anhydride, Hydrogenated methyl nadic anhydride, trialkyltetrahydro anhydrous phthalic acid, dodecenyl anhydrous succinic acid, 5-(2,5-di-side oxytetrahydro-3-furyl)-3-methyl-3 -Cyclohexene-1,2-dicarboxylic anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, Oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2, 5-Dilateral oxy-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrous trimellitate), styrene and maleic acid Polymeric acid anhydrides such as styrene and maleic acid resins which are copolymerized.

When epoxy resin and hardener are contained as component (A), the ratio of the amount of epoxy resin to all hardeners is based on [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener] In terms of ratio, the range of 1:0.01~1:5 is preferred, 1:0.3~1:3 is preferred, and 1:0.5~1:2 is more preferred. Here, the "epoxy group number of the epoxy resin" refers to the value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent, and totaling all of them. In addition, the "number of active groups of the hardening agent" is a value obtained by dividing the mass of the non-volatile components of the hardening agent present in the resin composition by the equivalent of the active group for the ester, and adding up all the values. As the component (B), an insulating layer with excellent flexibility can be obtained by setting the ratio of the amount of the epoxy resin to the hardening agent within this range.

The content of the hardener as the component (A), from the viewpoint of obtaining an insulating layer with excellent flexibility, relative to 100% by mass of the non-volatile components in the resin composition, preferably 0.1% by mass or more, preferably 0.5% by mass Above, it is more preferably 1% by mass or more, more preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less.

＜(B) Inorganic fillers＞ In the resin composition, as an optional component, an inorganic filler may be contained as the (B) component. (B) As the material of the inorganic filler, an inorganic compound can be used. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and aluminum Stone, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth oxide, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among them, silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, as the silica, spherical silica is preferred. (B) The inorganic filler system may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) Commercial products of inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YC100C", "YA050C" and "SP507-05" manufactured by Admatex. "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "Sylfil NSS-3N", "Sylfil NSS-4N", "Sylfil NSS-5N" manufactured by Tokuyama Corporation; "Sylfil NSS-5N" manufactured by Admatex SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc.

(B) The average particle size of the inorganic filler is preferably 0.01 μm or more, preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and more preferably 5 μm or less from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 2 μm or less, more preferably 1 μm or less.

(B) The average particle size of inorganic fillers can be measured by the laser diffraction/scattering method based on Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device can be used to create the particle size distribution of the inorganic filler by using a volume basis, and measure the median diameter average particle size. As a measurement sample system, 100 mg of inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial, and ultrasonic waves are applied for 10 minutes to disperse it. Use a laser diffraction particle size distribution measuring device for the measurement sample, make the wavelength of the light source blue and red, and use the flow cell method to measure (B) the volume-based particle size distribution of the inorganic filler Calculate the average particle size from the obtained particle size distribution as the median diameter. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

(B) ratio of the surface area of the inorganic filler of the present invention to obtain a desired effect from the viewpoint of significantly to 1m ² / g or more preferably, preferably 2m ² / g or more, particularly preferably 3m ² / g or more. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is based on the BET method. It can be obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the surface of the sample and calculating the surface area using the BET multipoint method.

(B) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, fluorine-containing silane coupling agent, aminosilane coupling agent, epoxy silane coupling agent, mercaptosilane coupling agent, silane coupling agent, alkoxysilane, organosilicon nitrogen Alkyl compounds, titanate-based coupling agents, etc. Moreover, the surface treatment agent system may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

Commercial products of surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercapto Propyl trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl-3-aminopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Trimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and KBM manufactured by Shin-Etsu Chemical Co., Ltd. -4803" (long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment using the surface treatment agent should preferably fall within the specified range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated by 0.2 parts by mass to 5 parts by mass of the surface treatment agent, preferably by 0.2 parts by mass to 3 parts by mass, and is preferably surface-treated by 0.3 parts by mass. ~2 parts by mass is better for surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of inorganic fillers, the amount of carbon per unit surface area of the inorganic filler is ^{preferably 0.02 mg/m 2} or more, preferably 0.1 mg/m ² or more, and 0.2 mg/m ² or more For better. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the resin sheet layer, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less For better.

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

(B) The content of the inorganic filler is 10% by mass or more, preferably 15% by mass, when the non-volatile content in the resin composition is made 100% by mass from the viewpoint of obtaining an insulating layer with low dielectric tangent. Above, it is more preferably 20% by mass or more, more preferably 90% by mass or less, more preferably 88% by mass or less, and more preferably 85% by mass or less.

＜(C) Hardening accelerator＞ The resin composition may contain (C) a hardening accelerator as an optional component. Examples of hardening accelerators include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, etc., such as amine hardening accelerators, imidazole hardening accelerators, etc. Hardening accelerators are preferred, and imidazole-based hardening accelerators are preferred. The hardening accelerator system may be used individually by 1 type, and may be used in combination of 2 or more types.

As the phosphorus-based hardening accelerator, for example, triphenylphosphine, boric acid phosphonium compound, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium caprate, (4 -Methyl phenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., with triphenyl phosphine, tetrabutyl phosphonium thiocyanate, etc. Salt is better.

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

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl- (1')]-Ethyl-s-triazine, 2,4-Diamino-6-[2'-Methylimidazolyl-(1')]-Ethyl-s-Triazine Heterocyanuric Acid Acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , 2,3-Dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2 -Imidazole compounds such as phenylimidazoline and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can also be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation and the like can be mentioned.

As the guanidine-based hardening accelerator, for example, dicyandiamide, 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 biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecane Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. , Preferably dicyanodiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. As specific examples of organometallic complexes, organic cobalt complexes such as cobalt acetopyruvate (II), cobalt acetopyruvate (III), etc., and organic cobalt complexes such as copper acetopyruvate (II) can be cited. Copper complexes, organic zinc complexes such as zinc acetopyruvate (II), organic iron complexes such as iron (III) acetopyruvate, and organic nickel complexes such as nickel (II) acetopyruvate Manganese (II) acetylpyruvate and other organic manganese complexes. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(C) When the content of the hardening accelerator is 100% by mass of the non-volatile components in the resin composition, it is preferably 0.01% by mass or more, preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, and 3 The mass% or less is preferable, 1 mass% or less is more preferable, and 0.5 mass% or less is especially preferable.

＜(D) Thermoplastic resin＞ The resin composition may contain (D) thermoplastic resin as an optional component. (D) The thermoplastic resin includes, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyimide resin, polyetherimide resin, and polyimide resin. Resin, polyether turpentine resin, polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc., preferably phenoxy resin. The thermoplastic resin system may be used individually by 1 type, or may be used in combination of 2 or more types.

(D) The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably 38,000 or more, preferably 40,000 or more, and more preferably 42,000 or more. The upper limit is preferably 100,000 or less, preferably 70,000 or less, and more preferably 60,000 or less. (D) The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by the gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of (D) thermoplastic resin in terms of polystyrene can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation and Shodex K-800P/K-804L/ manufactured by Showa Denko Corporation. K-804L is used as the column, chloroform etc. are used as the mobile phase, and the column temperature is 40°C. The measurement is performed 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, stilbene skeleton, and dicyclopentadiene skeleton. A phenoxy resin with one or more skeletons consisting of an alkene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, adamantane skeleton, a terpene skeleton, and a 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 system 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" (both phenoxy resins containing bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation, and "YX8100" (containing bisphenol S skeleton). Phenoxy resin), and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton). Other examples include "FX280" and "FX293" manufactured by Nippon Steel Chemical & Materials Co., Ltd., and Mitsubishi Chemical Corporation. "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" etc.

Examples of polyvinyl acetal resins include polyvinyl formaldehyde resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include, for example, "Electrochemical butyral 4000-2", "Electrochemical butyral 5000-A" and "Electrochemical butyral 6000-C" manufactured by Denki Kagaku Kogyo Co., Ltd. , "Electrochemical Butyral 6000-EP", S-REC 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, "Rikacote SN20" and "Rikacote PN20" manufactured by Nu Skin Nippon Chemical Co., Ltd. can be cited.

Specific examples of polyimide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. As specific examples of polyimide resins, modified polyimide resins such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyimide imide) manufactured by Hitachi Chemical Co., Ltd. can also be cited. Amide imine.

As a specific example of the polyether sulfide resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited. As a specific example of the polyphenylene ether resin, oligophenylene ether and styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Corporation, etc. can be cited. As a specific example of the polyether ether ketone resin, "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd. can be cited. As a specific example of the polyetherimide resin, "Ultem" manufactured by GE Corporation and the like can be cited.

As a specific example of the polymer resin, for example, the polymer "P1700" and "P3500" manufactured by Solvay Advanced Polymers can be cited.

Examples of polyolefin resins include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, etc. Ethylene copolymer resins; Polyolefin elastomers such as polypropylene, ethylene-propylene block copolymers, etc.

Examples of polyester resins include polyethylene terephthalate resins, polyethylene naphthalate resins, polybutylene terephthalate resins, polybutylene naphthalate resins, and polyethylene terephthalate resins. Trimethylene ester resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, etc.

Among them, (D) thermoplastic resins are preferably phenoxy resins and polyvinyl acetal resins. Therefore, in a suitable embodiment, the thermoplastic resin includes one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, as the thermoplastic resin, a phenoxy resin is preferred, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferred.

(D) When the content of the thermoplastic resin is 100% by mass of the non-volatile components in the resin composition, it is preferably 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 5% by mass or less, preferably 4% by mass or less, and more preferably 3% by mass or less.

＜(E) Amphiphilic polyether block copolymer＞ The resin composition may also contain (E) an amphiphilic polyether block copolymer. In the specification of this case, the amphiphilic polyether block copolymer refers to a block copolymer containing at least one epoxy resin-miscible polyether block segment and at least one epoxy resin non-miscible polyether block segment. Things. By including the component (E) in the resin composition, the toughness of the resin composition can be improved, and the stress relaxation performance can be improved, thereby reducing the amount of warpage of the hardened resin composition.

As the epoxy resin miscible polyether block segment, for example, an epoxy resin miscible polyether block segment derived from an alkylene oxide (alkylene oxide) can be cited. As the epoxy resin miscible polyether block segment derived from alkylene oxide, for example, it contains a block selected from polyethylene oxide block, polypropylene oxide block, poly(ethylene oxide-co- Propylene oxide) block, poly(ethylene oxide-ran-propylene oxide) block, and one or more polyalkylene oxide blocks of these mixtures are preferred, and the polyethylene oxide block is Better.

As the epoxy resin immiscible block segment, for example, at least one epoxy resin immiscible polyether block segment derived from alkylene oxide and the like can be cited. As at least one epoxy resin immiscible polyether block segment derived from alkylene oxide, for example, it can be selected from polybutylene oxide blocks and polyether block segments derived from 1,2-epoxyhexane. Oxyxane block, polyoxydodecane block derived from 1,2-epoxydodecane, and one or more polyalkylene oxides of these mixtures are preferred, and polyepoxy The butane block is preferred.

The amphiphilic polyether block copolymer preferably has one or more types of epoxy resin miscible block segments, and preferably has two or more types of epoxy resin miscible block segments. Similarly, it is preferable to have one or more types of epoxy resin immiscible block segments, and it is preferable to have two or more types of epoxy resin immiscible block segments. Therefore, the (E) component is selected from the group consisting of diblock, linear triblock, linear tetrablock, high-order multi-block structure, branched block structure, star-shaped block structure, and combinations thereof, for example. Groups of epoxy resin mixed block segments, or epoxy resin non-mixed block segments are preferred.

The amphiphilic polyether block copolymer can also contain other segments in the molecule without impairing its scope of effect. As other segments, for example, polyethylene propylene (PEP), polybutadiene, polyisoprene, polydimethylsiloxane, polybutylene oxide, poly(ethylene oxide), polyethylene oxide Polyalkyl methacrylates such as hexyl methacrylate, and mixtures of these, etc.

The number average molecular weight of the amphiphilic polyether block copolymer is preferably 3,000~20,000. The number average molecular weight is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

Examples of amphiphilic polyether block copolymers include poly(ethylene oxide)-b-poly(butylene oxide) (PEO-PBO); poly(ethylene oxide)-b-poly (Butylene oxide)-b-poly(ethylene oxide) (PEO-PBO-PEO) and other amphiphilic polyether triblock copolymers, etc. Commercially available products can be used for the amphiphilic block copolymer system. Examples of commercially available products include "Fortegra 100" (PEO-PBO-PEO) manufactured by The Dow Chemical Company.

(E) When the content of the component is 100% by mass of the non-volatile components in the resin composition, from the viewpoint of improving the fracture properties, it is preferably 0.3% by mass or more, preferably 0.4% by mass or more, and more preferably 0.5 Above mass%. The upper limit is not particularly limited as long as the effect of the invention is achieved. It is preferably 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less.

＜(F) Elastomer＞ The resin composition may contain (F) elastomer as an optional component. (F) A component system may be used individually by 1 type, and may use 2 or more types together.

The component (F) is selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, and polyisoprene structure in the molecule. Resins with one or more structures of olefin structure, polyisobutylene structure, and polycarbonate structure are preferred, and have a resin structure selected from the group consisting of polybutadiene structure, poly(meth)acrylate structure, polyalkylene oxide structure, and polyisobutylene structure. A resin having one or more structures of pentadiene structure, polyisobutylene structure, or polycarbonate structure is preferable, and it has one or more structures selected from polybutadiene structure and polyoxyalkylene structure The resin is more preferable, and the resin with a polybutadiene structure is particularly preferable. Furthermore, "(meth)acrylate" refers to a term including methacrylate, acrylate, and combinations thereof. These structures can be included in the main chain or in the side chain.

In order to reduce the warpage of the resin composition after curing, the component (F) preferably has a high molecular weight. (F) The number average molecular weight (Mn) of the component is preferably 1,000 or more, preferably 1,500 or more, and more preferably 3,000 or more and 5,000 or more. The upper limit is preferably 1,000,000 or less, and more preferably 900,000 or less. The number average molecular weight (Mn) is the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

From the viewpoint of reacting with the epoxy resin as the (A) component to harden the resin composition to increase the peel strength, the (F) component preferably has a functional group capable of reacting with the epoxy resin as the (A) component. Furthermore, as a functional group that can react with the epoxy resin as the component (A), a functional group that appears due to heating is also included.

In a suitable embodiment, the functional group capable of reacting with the epoxy resin as the component (A) is selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. One or more functional groups in a group. Among them, as the functional group, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group are preferable, and a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, and an epoxy group are preferable. Phenolic hydroxyl is particularly preferred. However, when an epoxy group is included as a functional group, the number average molecular weight (Mn) is preferably 5,000 or more.

A suitable embodiment of the component (F) is a resin containing a polybutadiene structure. The polybutadiene structure may be included in the main chain or in the side chain. Furthermore, part or all of the polybutadiene structure can be hydrogenated. The resin containing polybutadiene structure is called polybutadiene resin.

Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", and "Ricon 130MA8" manufactured by Clay Valley. "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "GQ-1000" (polybutadiene with hydroxyl and carboxyl group introduced) manufactured by Soda Corporation, "G-1000", "G-2000 ”, “G-3000” (Polybutadiene with two-terminal hydroxyl), “GI-1000”, “GI-2000”, “GI-3000” (Hydrogenated polybutadiene with two-terminal hydroxyl), manufactured by Nagase ChemteX "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), etc. As an embodiment, for example, a linear polyimide using hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as a raw material (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208 Recorded polyimide), butadiene containing phenolic hydroxyl group, etc. The content of the butadiene structure of the polyimide resin is preferably 60% to 95% by mass, preferably 75% to 85% by mass. For the details of the polyimide resin, refer to the description in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208, and the content can be incorporated into this specification.

A suitable embodiment of the component (F) is a resin containing a poly(meth)acrylate structure. A resin containing a poly(meth)acrylate structure is called a poly(meth)acrylic resin. Examples of poly(meth)acrylic resins include Teisan Resin manufactured by Nagase ChemteX, and "ME-2000", "W-116.3", "W-197C", and "KG-25" manufactured by Negami Kogyo Co., Ltd. , "KG-3000", etc.

A suitable embodiment of the component (F) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin. Examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., "C-1090", "C-2090", and "C- 3090" (polycarbonate diol) and the like. In addition, linear polyimines using hydroxyl-terminated polycarbonate, diisocyanate compounds, and tetrabasic acid anhydrides as raw materials can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% to 95% by mass, preferably 75% to 85% by mass. For the detailed content of the polyimide resin, please refer to the record in International Publication No. 2016/129541, and import the content into this specification.

In addition, as another embodiment of the component (F), there is a resin containing a silicone structure. The resin containing the silicone structure is called silicone resin. Examples of silicone resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Polysiloxane, which use amine-terminated polysiloxane and tetrabasic acid anhydride as raw materials The linear polyimide (International Publication No. 2010/053185, Japanese Patent Application Publication No. 2002-12667, Japanese Patent Application Publication No. 2000-319386, etc.).

As another embodiment of the component (F), for example, a resin containing an alkylene structure and an alkylene structure. A resin containing an alkylene structure is called an alkylene resin, and a resin containing an alkoxy structure is called an alkoxy resin. The polyalkylene oxide structure is preferably a polyalkylene oxide structure with 2 to 15 carbon atoms, and a polyalkylene oxide structure with 3 to 10 carbon atoms is preferred, and a polyalkylene oxide structure with 5 to 6 carbon atoms is preferred. The polyalkyleneoxy structure is more preferable. Specific examples of alkylene resins and alkoxylated resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fiber Corporation.

As another embodiment of the component (F), for example, a resin containing an isoprene structure. The resin containing the isoprene structure is called isoprene resin. As specific examples of the isoprene resin, "KL-610" and "KL613" manufactured by Kuraray Co., Ltd. can be cited.

As another embodiment of the component (F), for example, a resin containing an isobutylene structure. The resin containing isobutylene structure is called isobutylene resin. Specific examples of isobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka. )Wait.

When the non-volatile component in the resin composition is 100% by mass, the content of (F) elastomer is preferably 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less.

＜(G) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include flame retardants; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners; defoamers; leveling agents; Adhesion imparting agent; coloring agent; pigment and other resin additives. These additives can be used individually by 1 type, and can also be used in combination of 2 or more types by arbitrary ratios. Individual content can be set appropriately by industry professionals.

The method of preparing the resin composition is not particularly limited. For example, a method of mixing and dispersing the compounding components with a solvent or the like as necessary, using a rotary mixer, etc., can be mentioned.

[Resin Sheet] The resin sheet of the present invention includes a first support and a resin composition layer bonded to the first support in a peelable manner. Usually, the first support and the resin composition layer are directly bonded. The "direct" joining of two members means that there is no other layer between the two members to be joined. The thickness of the resin composition layer is 60 μm or more, and the ratio L _A /L _B of one of the first supports in the upper surface inward direction satisfies the relationship of 1.005 or more and 1.2 or less. The in-plane direction of the first support means the direction perpendicular to the thickness direction of the first support. And, L _A represents the length of the first support within the time of the engagement with the resin composition of the layer surface direction. And, L _B represents the length of the first post of the support within the resin composition layer is peeled from the direction of the plane. By using such a resin sheet, even if the thickness of the resin composition layer is thick, the appearance defect of the resin composition layer can be suppressed. In addition, by using the resin sheet of the present invention, it is usually also possible to suppress the occurrence of curling.

As shown in an example shown in FIG. 1, the resin sheet 1 of the present invention includes a first support 3 and a resin composition layer 2. As shown in an example shown in FIG. 2, the resin sheet of the present invention may also include the first support 3, the resin composition layer 2, and the second support 4 in this order. The first support 3 and the second support 4 may be formed of the same material, or may be formed of different materials. Generally, the first support system functions as a protective film.

The inventors speculate that the mechanism for achieving the effects of the present invention is as follows. However, the technical scope of the present invention is not affected by the following mechanism. As described above, when the thickness of the resin composition layer is thick, wrinkles generated on the support may be easily transferred to the resin composition layer, which may cause poor appearance of the resin composition layer. For example, when bonding the support body and the resin composition layer together, it is generally bonded by applying an appropriate bonding tension to the support body. Therefore, the stress corresponding to the aforementioned tension will remain on the support. During storage of the resin sheet, if wrinkles are generated on the support due to the aforementioned stress, the wrinkles may be transferred to the resin composition layer, resulting in poor appearance. Many resin sheets are stored in a state wound on a roll. When stored in this roll shape, the formation of wrinkles and appearance defects is particularly noticeable. In addition, it is considered that when the thickness of the resin composition layer is thick, stress is generated, and wrinkles generated on the support body are easily transferred to the resin composition layer due to the stress.

The resin sheet of the present invention is in one or more in-plane directions, the length L _A of the first support when joined with the resin composition layer, and the first support after the first support is peeled from the resin composition layer The length L _B will satisfy a specific relationship. That is, the resin of the present invention, a first sheet support system having at least a ratio of L _A / L _B will satisfy the specific relationship of the plane direction. Since the length L _{A represents the length of the first support in the state of applying tension, the length L B} represents the length of the first support in the state after the tension is released, so the aforementioned ratio L _A /L _B represents the tension caused The degree of stretching of the first support. Therefore, the aforementioned ratio L _A /L _B indirectly represents the amount of tension applied to the first support in the state of being bonded to the resin composition layer. When the ratio L _A /L _B satisfies the specific relationship, it means that the first support is given a specific range of tension that can suppress wrinkles during storage. Thereby, even if the thickness of the resin composition layer is thick, the wrinkles are prevented from being transferred to the resin composition layer. In addition, by using the resin sheet of the present invention, it is usually also possible to suppress the occurrence of curling.

＜Resin composition layer＞ The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of a resin composition. The resin composition system is as described above.

From the viewpoint of sealing electronic parts, the thickness of the resin composition layer is 60 μm or more, preferably 80 μm or more, preferably 100 μm or more, and more preferably 150 μm or more. Moreover, generally speaking, the appearance defect tends to occur more easily as the thickness of the resin composition layer is thicker. Therefore, the thickness in the aforementioned range refers to the thickness of the resin composition layer that causes the problem of poor appearance. However, from the viewpoint of suppressing the poor appearance even with the resin composition layer of such a thickness, the resin sheet of the present invention Those of technical significance. The upper limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1000 μm or less, 500 μm or less, 300 μm or less.

The minimum melt viscosity of the resin composition layer at 60°C to 200°C is preferably 10,000 poise or more, preferably 2,000 poise or more, more preferably 3,000 poise or more, 4,000 poise or more, or 4500 poise or more. In such a case where the minimum melt viscosity is high, since the rigidity of the resin composition layer becomes hard, it is difficult to receive the wrinkle transfer from the first support. On the other hand, the upper limit of the melt viscosity is arbitrary. However, in the past, the lower the minimum melt viscosity, the more likely it is to produce poor appearance due to wrinkle transfer. However, the present invention can suppress the appearance even when a resin composition layer that is prone to such poor appearance is used. bad. Therefore, from the viewpoint that such effective utilization can suppress the appearance defects that have easily occurred in the past, the lowest melt viscosity is preferably low. Specifically, the aforementioned minimum melt viscosity is preferably 20,000 poise or less, preferably 15,000 poise or less, more preferably 10,000 poise or less, or 7500 poise or less. The lowest melt viscosity can be measured with a dynamic viscoelastic measuring device. The measurement of the aforementioned minimum melt viscosity can be measured according to the method described in the following embodiments.

As mentioned above, the appearance defects are more likely to occur when the resin composition layer is thicker, and the lowest melt viscosity of the resin composition layer is more likely to occur. Therefore, from the viewpoint of effectively utilizing the effect of suppressing appearance defects, it is desirable that the thickness and minimum melt viscosity of the resin composition layer satisfy the specific relationship that is particularly likely to cause appearance defects in the past. Specifically, when the minimum melt viscosity of the resin composition layer at 60°C to 200°C is set to M (poise), and the thickness of the resin composition layer is set to T (μm), M/T is preferably 5 or more , Preferably 10 or more, more preferably 15 or more, more preferably 200 or less, preferably 190 or less, more preferably 180 or less.

＜The first support body＞ Examples of the first support include a film containing a plastic material and release paper, and a film containing a plastic material is preferred.

When a film containing a plastic material is used as the first support, as the plastic material, for example, polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate (Hereinafter abbreviated as "PEN") and other polyesters; low-density polyethylene, non-stretched polypropylene and other polyolefins; polycarbonate (hereinafter abbreviated as "PC"); polymethyl Acrylic polymers such as methacrylate (hereinafter abbreviated as "PMMA"); cyclic polyolefin; triacetyl cellulose (hereinafter abbreviated as "TAC"); polyether vulcanization Polyether sulfide (hereinafter abbreviated as "PES"); polyether ketone; polyimide; polyvinyl chloride, etc. Among them, polyethylene terephthalate, polyethylene naphthalate, polyolefin, and vinyl chloride are also preferred, and polyolefin and vinyl chloride are particularly preferred.

Commercially available products can be used for the first support system. Examples of commercially available products include "GF-1" manufactured by Tamapoly; "Torayfan NO9405S" manufactured by Toray Film Processing Co., Ltd.; "Type C+" manufactured by Achilles Co., Ltd., and the like.

The surface of the first support body that is bonded to the resin composition layer may be treated with matting treatment, corona treatment, anti-static treatment, or the like.

In addition, as the first support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer can also be used. As the release agent used in the release layer of the support with the release layer, for example, a group selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins More than one release agent. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based release agents. Also, as a support with a release layer, for example, "Lumirror T60" manufactured by Toray Corporation; "Purex" manufactured by Teijin Corporation; "Unipeel" manufactured by Unitika Corporation.

One of the first supports has L _A /L _B in the upper inner direction of 1.005 or more, preferably 1.01 or more, preferably 1.05 or more, and more preferably 1.08 or more. By making the lower limit of L _A /L _B within this range, the generation of wrinkles can be suppressed. In addition, _{the upper limit of L A} /L _B is 1.2 or less, preferably 1.18 or less, preferably 1.17 or less, and more preferably 1.15 or less. By making the _{upper limit of L A} /L _B within this range, it becomes possible to further improve the operability when forming a resin sheet.

The first length of the support lines L _A and L _B can be measured using the method of the following. The first length L _A of the support system can be at a temperature of 23 ℃, the conditions of humidity of 70% was measured. Further, the first length L _B of the support system can be at a temperature of 23 ℃, under humidity of 70% using Tensilon universal testing machine, the first support member toward the thickness direction at a stretch release 0.008kgf / cm of force After that, the measurement was performed at the aforementioned temperature and humidity.

The number of in-plane directions of the first support whose ratio L _A /L _B satisfies the aforementioned specific relationship may be one or two or more. When the resin sheet has a long shape to the extent that it can be wound into a roll, the first support system has a ratio L _A /L that satisfies the aforementioned specific relationship in an in-plane direction parallel to the longitudinal direction of the resin sheet _B is better. The first support having an elongated shape is usually subjected to the bonding of the resin composition layer in a state where tension is applied to the longitudinal direction of the first support. _{Therefore, when the first support has a ratio L A} /L _B that satisfies the aforementioned specific relationship in the in-plane direction parallel to the longitudinal direction, the tension that may cause wrinkles can be appropriately adjusted, and the appearance defect can be effectively suppressed.

The modulus of elasticity of the first support at 23°C is preferably 2 GPa or less, preferably 1.8 GPa or less, more preferably 1.6 GPa or less, and more preferably 0.05 GPa or more, preferably 0.06 GPa or more, more preferably Above 0.07GPa. By making the elastic modulus of the first support within this range, it becomes possible to further suppress the curling of the resin composition layer. The modulus of elasticity can be measured by the method according to ASTM D882.

The thickness of the first support is preferably in the range of 5 μm to 75 μm, preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, the thickness of the entire support with a release layer is preferably within the above-mentioned range.

＜Second support body＞ As shown in an example shown in FIG. 2, the resin sheet system may have the second support 4 in combination with the first support 3 and the resin composition layer 2. The first support 3 and the second support 4 may be formed of the same material as described above, or may be formed of a different material. From the viewpoint of suppressing wrinkles of the resin composition layer, they are preferably formed of a different material.

In the case of the resin sheet having the support 2, L _a second support member within a second or more of the in-plane direction of the support / L _b preferably based at least 0.95, preferably 0.98 or more, more preferably 1 Above, it is preferably 1.5 or less, preferably 1.3 or less, and more preferably 1.1 or less. L _a represents a line length of the second support member within the time of the engagement with the resin composition of the layer surface direction. In addition, L _b represents the length of the second support in the aforementioned in-plane direction after peeling from the resin composition layer. When the second support member having an inner surface having a L _a / L _b of a direction within the aforementioned range, in particular, to effectively suppress appearance defects based resin composition layers. The length of the second support lines L _a and L _b may be measured by a first length L _A of the support 1 and the same procedures as L _B.

The elastic modulus of the second support at 23°C is preferably in the same range as the elastic modulus of the first support at 23°C. Thereby, it becomes possible to more suppress the curling of the resin composition layer.

When the resin sheet has a first support and a second support, the difference between the elastic modulus of the first support at 23°C and that of the second support at 23°C (the elastic modulus of the second support Number-elastic modulus of the first support), preferably 2 GPa or more, preferably 2.2 GPa or more, more preferably 2.4 GPa or more, and more preferably 4 GPa or less, preferably 3.95 GPa or less, more preferably 3.9 Below GPa. By making the difference between the elastic modulus of the first and second supports within this range, it becomes possible to further suppress the curling of the resin composition layer.

＜Manufacturing method of resin sheet＞ The resin sheet can be manufactured by a method including, for example, a step of coating a resin composition on an appropriate support member such as a second support to form a resin composition layer; and, for the resin composition layer The step of attaching the first support in a state where tension has been applied to the surface that is not joined to the second support (that is, the surface opposite to the second support).

The coating of the resin composition can be performed using a coating device such as a die coater. In the step of forming the resin composition layer, if necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to form the resin composition layer. By using a solvent, the viscosity can be adjusted to improve the coatability. When a resin varnish is used, the resin varnish is usually dried after coating to form a resin composition layer.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbohydrate. Acetate solvents such as alcohol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethyl ethyl Amide solvents such as amide (DMAc) and N-methylpyrrolidone. An organic solvent system may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

The drying system can be performed by a known method such as heating and blowing hot air. Drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass organic solvent, dry it at 50°C to 150°C for 3 minutes to 10 minutes. A resin composition layer is formed.

After the resin composition layer is formed, the resin composition layer and the first support are bonded together to obtain a resin sheet. The bonding is usually performed in a state where appropriate tension is applied to the first support. The tension added to the first support is the same level as the tension added when attaching the protective film when manufacturing the conventional resin sheet.

In addition, the resin sheet can be wound into a roll for storage. In this case, the resin sheet is preferably wound on the inside of the roll with the first support.

＜Use of resin sheet＞ The resin sheet can be suitably used for forming an insulating layer in the manufacture of semiconductor chip packages (insulating resin sheets for semiconductor chip packages). For example, the resin sheet can be used for forming the insulating layer of the circuit board (resin sheet for the insulating layer of the circuit board). As examples of packages using such substrates, there are FC-CSP, MIS-BGA packages, and ETS-BGA packages.

Moreover, the resin sheet system can be suitably used for sealing a semiconductor wafer (resin sheet for semiconductor wafer sealing). Suitable conductor chip packages include, for example, fan-out wafer-level packaging (WLP), fan-in wafer-level packaging (WLP), and fan-out wafer-level packaging (WLP). out) type panel level package (PLP), fan-in type panel level package (PLP), etc.

In addition, the resin sheet can also be used as the material of MUF used after the semiconductor chip is connected to the substrate.

In addition, the resin sheet can be used in other wide-ranging applications that require high insulation reliability. For example, the resin sheet can be suitably used for forming an insulating layer of a circuit board such as a printed wiring board.

＜Characteristics of resin sheet＞ The above-mentioned resin sheet can obtain a resin composition layer in which the generation of wrinkles is suppressed. Therefore, the appearance defects of the resin composition layer can be suppressed. The evaluation of wrinkles is, for example, by peeling the first support cut into a resin sheet of 50 cm×50 cm, and visually observing whether the resin composition layer has wrinkles. At this time, usually, there are no wrinkles on the resin composition layer. The details of the evaluation of wrinkles can be performed by the method described in the examples described later.

The above-mentioned resin sheet can usually be obtained with a resin composition layer in which curl generation is suppressed. Therefore, it becomes possible to provide a resin sheet in which the occurrence of warpage is suppressed. The evaluation of curling is, for example, by placing the first support body cut into a 50cm×50cm resin sheet facing up and placing it on a flat place, and calculating and measuring the curling amount of the resin sheet. At this time, the amount of curl is preferably less than 50 mm. The lower limit of the amount of curl is not particularly limited, and may be 0.01 mm or more. The details of the evaluation of the curl can be performed by the method described in the following Examples.

[Circuit Board] The circuit board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. The circuit board can be manufactured by, for example, a manufacturing method including the following steps (1) and (2). (1) The step of forming a resin composition layer on a substrate. (2) The step of thermally curing the resin composition layer to form an insulating layer.

Step (1) is to prepare the substrate. Examples of substrates include glass epoxy substrates, metal substrates (stainless steel or cold rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Substrate. In addition, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces can be used. When such a base material is used, the conductor layer, which is a wiring layer that can function as a circuit wiring, is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of the material of the metal layer include copper foil, copper foil with a carrier, and the material of the conductor layer described later, and copper foil is preferred. Moreover, a commercially available product can be used as such a base material with a metal layer, and for example, "Micro Thin", an ultra-thin copper foil with a carrier made by Mitsui Metals Co., Ltd., can be used.

In addition, a conductive layer can be formed on one or both surfaces of the substrate. In the following description, a member including a substrate and a conductor layer formed on the surface of the substrate may be appropriately referred to as "a substrate with a wiring layer". Examples of the conductive material contained in the conductive layer include those selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. One or more metal materials. As the conductor material, a single metal can be used, and an alloy can also be used. As the alloy, for example, an alloy of two or more metals selected from the above group (for example, nickel･chromium alloy, copper･nickel alloy, and copper･titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal; and, as an alloy Nickel･chromium alloy, copper･nickel alloy, copper･titanium alloy alloy is preferred. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys are preferred, and single metals of copper are particularly preferred.

The conductor layer may be patterned in order to function as a wiring layer, for example. At this time, the ratio of line width (circuit width)/pitch (width between circuits) of the conductor layer is not particularly limited. It is preferably 20/20μm or less (that is, the pitch is 40μm or less), preferably 10/10μm or less, It is more preferably 5/5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch does not need to be all the same in the entire conductor layer. The minimum pitch of the conductor layer can be set to 40 μm or less, 36 μm or less, or 30 μm or less, for example.

The thickness of the conductor layer varies according to the design of the circuit substrate, preferably 3μm~35μm, preferably 5μm~30μm, more preferably 10μm~20μm, particularly preferably 15μm~20μm.

The conductor layer can be formed, for example, by a method including the following steps: a step of laminating a dry film (photoresist film) on a substrate; using a photomask and exposing and developing the dry film under specified conditions to form The step of obtaining the pattern dry film from the pattern; the step of using the developed pattern film as an electroplating mask and forming a conductor layer by electroplating such as electrolytic plating; and the step of peeling off the pattern dry film . As the dry film system, a photosensitive dry film containing a photoresist composition can be used. For example, a dry film formed of a resin such as a novolak resin or an acrylic resin can be used. The lamination conditions of the substrate and the dry film can be the same as the lamination conditions of the substrate and the resin sheet described later. The peeling of the dry film can be performed using an alkaline peeling liquid such as sodium hydroxide solution.

After preparing the substrate, a resin composition layer is formed on the substrate. When the conductor layer is formed on the surface of the substrate, the formation of the resin composition layer is preferably carried out in such a way that the conductor layer is embedded in the resin composition layer.

The formation of the resin composition layer is performed, for example, by laminating a resin sheet and a substrate. This lamination is performed by, for example, heating and pressing a resin sheet onto the base material, and bonding the resin composition layer onto the base material. As a member for heating and pressing the resin sheet to the substrate (hereinafter referred to as "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller, etc.) Wait. However, instead of directly pressing the heating and pressing member on the resin sheet, it is better to press the resin sheet in such a way that the resin sheet can fully follow the surface irregularities of the substrate through an elastic material such as heat-resistant rubber.

The lamination system of the base material and the resin sheet can be implemented, for example, by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa. The heating and pressing 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 13 hPa or less.

After the lamination, the member is pressed under normal pressure (under atmospheric pressure), for example, by pressing and heating the member to smooth the laminated resin sheet. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. Furthermore, the lamination and smoothing treatment system can be continuously performed using a vacuum laminator.

In addition, the formation of the resin composition layer can be performed by, for example, a compression molding method. The specific operation of the compression molding method is to prepare an upper mold and a lower mold as molds, for example. The resin composition is coated on the substrate. The base material coated with the resin composition is mounted on the lower mold. After that, the upper film tool and the lower mold are clamped, and heat and pressure are applied to the resin composition to perform compression molding.

In addition, the specific operation system of the compression molding method can be performed as follows, for example. Prepare upper mold and lower mold as molds for compression molding. Put the resin composition on the lower mold. In addition, a substrate is mounted on the upper mold. Thereafter, the upper mold and the lower mold are clamped by bringing the resin composition placed on the lower mold into contact with the substrate mounted on the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions in the compression molding method vary according to the composition of the resin composition. The mold temperature during molding is preferably a temperature that can exert the excellent compression moldability of the resin composition. For example, 80°C or higher is preferred, 100°C or higher is preferred, 120°C or higher, and 200°C or lower is more preferred. More preferably, it is preferably 170°C or lower, more preferably 150°C or lower. In addition, the pressure applied during forming is preferably 1 MPa or more, preferably 3 MPa or more, more preferably 5 MPa or more, and more preferably 50 MPa or less, preferably 30 MPa or less, and more preferably 20 MPa or less. The curing time is preferably 1 minute or more, preferably 2 minutes or more, particularly preferably 5 minutes or more, and more preferably 60 minutes or less, preferably 30 minutes or less, particularly preferably 20 minutes or less. Usually after the formation of the resin composition layer, the mold is removed. The removal of the mold can be performed before the thermal curing of the resin composition layer, or can be performed after the thermal curing.

After the resin composition layer is formed on the substrate, the resin composition layer is thermally cured to form an insulating layer. Although the thermal curing conditions of the resin composition layer vary according to the type of resin composition, the curing temperature is usually in the range of 120°C to 240°C (150°C to 220°C is preferred, preferably 170°C to 200°C). ℃ range), the curing time is in the range of 5 minutes to 120 minutes (10 minutes to 100 minutes is preferred, preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be heated at a temperature lower than the curing temperature to perform preliminary heating treatment. For example, before the resin composition layer is thermally cured, the resin composition layer can be preheated at a temperature above 50°C and less than 120°C (more preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less). Usually more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

Through the above operations, a circuit substrate with an insulating layer can be manufactured. In addition, the manufacturing method of the circuit board may further include arbitrary steps. For example, when a resin sheet is used to manufacture a circuit board, the method of manufacturing the circuit board may include a step of peeling the first support and the second support of the resin sheet. The first support and the second support system can be peeled off before the thermal curing of the resin composition layer, or can be peeled off after the thermal curing of the resin composition layer.

The manufacturing method of the circuit board may include, for example, the step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, a flat grinding disc can be used to grind the surface of the insulating layer.

The manufacturing method of the circuit board, for example, may also include the step (3) of connecting the conductor layers between layers, that is, the step of making holes in the insulating layer. Thereby, holes such as via holes and through holes can be formed in the insulating layer. As a method of forming the through hole, for example, laser irradiation, etching, mechanical drilling, etc. can be cited. The size or shape of the through hole can be appropriately determined according to the design of the circuit substrate. Furthermore, in step (3), the interlayer connection can also be performed by grinding or grinding the insulating layer.

After the through hole is formed, it is better to perform the step of removing the residue in the through hole. This step is called the desmear step. For example, when the conductive layer is formed on the insulating layer by an electroplating step, the through hole can also be subjected to a wet de-residue treatment. In addition, when the conductor layer is formed on the insulating layer by the sputtering step, a dry de-slagging step such as a plasma treatment step may also be performed. In addition, the insulating layer may be roughened by the step of removing the residue.

Furthermore, before forming the conductor layer on the insulating layer, the insulating layer may be roughened. Through the roughening treatment, the surface of the insulating layer including the through hole is usually roughened. As the roughening treatment, either dry or wet roughening treatment can be performed. As an example of dry roughening treatment, plasma treatment etc. are mentioned. In addition, as an example of the wet roughening treatment, a method of sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid can be cited.

After forming the through holes, a conductor layer is formed on the insulating layer. By forming a conductor layer at the position where the through hole is formed, the newly formed conductor layer and the conductor layer on the surface of the substrate are electrically connected to perform interlayer connection. The method of forming the conductor layer includes, for example, electroplating, sputtering, vapor deposition, etc. Among them, electroplating is also preferred. In a suitable embodiment, the surface of the insulating layer is electroplated by a suitable method such as a semi-additive method or a full-additive method to form a conductor layer with a desired wiring pattern. In addition, when the first support or the second support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by subtraction. The material of the formed conductor layer can be a single metal or an alloy. In addition, the conductor layer may have a single-layer structure, or may have a multi-layer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which a conductor layer is formed on the insulating layer will be described in detail. On the surface of the insulating layer, a plating seed layer is formed by electroless plating. Secondly, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern is formed that exposes a part of the plating seed layer. After forming an electrolytic plating layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating layer can be removed by processing such as etching to form a conductor layer with a desired wiring pattern. Furthermore, when forming the conductor layer, the dry film used to form the mask pattern is the same as the above dry film.

The manufacturing method of the circuit board may also include the step (4) of removing the base material. By removing the base material, a circuit substrate with an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be carried out, for example, when a substrate having a peelable metal layer is used.

[Semiconductor Chip Packaging] The semiconductor chip package of the first embodiment of the present invention includes the above-mentioned circuit board and a semiconductor chip mounted on the circuit board. The semiconductor chip package can be manufactured by bonding a semiconductor chip on a circuit substrate.

The bonding conditions between the circuit board and the semiconductor wafer can be any conditions under which the terminal electrodes of the semiconductor wafer and the circuit wiring of the circuit board can be connected by conductors. For example, the conditions used in flip chip mounting of semiconductor chips can be adopted. In addition, for example, it is also possible to bond between the semiconductor wafer and the circuit board via an insulating adhesive.

As an example of the bonding method, a method such as pressing a semiconductor wafer to a circuit board can be mentioned. As the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is usually 1 second~ The range of 60 seconds (preferably 5 seconds to 30 seconds).

In addition, as another example of the bonding method, a method of bonding by reflow soldering a semiconductor wafer to a circuit board can be cited. The reflow conditions can be made in the range of 120℃~300℃.

After the semiconductor wafer is bonded to the circuit board, the underfill material of the mold can also be used to fill the semiconductor wafer. As the mold underfill material, the above-mentioned resin composition can be used, and the above-mentioned resin sheet can also be used.

The semiconductor chip package of the second embodiment of the present invention includes a semiconductor chip and a cured product of the aforementioned resin composition for sealing the semiconductor chip. In this type of semiconductor chip package, usually the cured product of the resin composition functions as a sealing layer. As the semiconductor chip package of the second embodiment, for example, a fan-out (fan-out) wafer level package (WLP) can be cited.

The manufacturing method of this fan-out wafer-level packaging (WLP) semiconductor chip package includes: (A) The step of temporarily fixing the film by laminating the substrate, (B) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (C) The step of laminating the resin composition of the resin sheet of the present invention on a semiconductor wafer, or coating the resin composition of the present invention on the semiconductor wafer, and thermally curing it to form a sealing layer, (D) The step of peeling the substrate from the semiconductor wafer and temporarily fixing the film, (E) The step of forming a rewiring forming layer (insulating layer) on the surface of the peeled substrate and the temporarily fixed film of the semiconductor wafer, (F) The step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and (G) The step of forming a solder resist layer on the conductor layer. In addition, the manufacturing method of the semiconductor chip package can further include: (H) a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages and singulating them.

The detailed content of the manufacturing method of this semiconductor chip package can refer to the description of paragraphs 0066~0081 of International Publication No. 2016/035577, and the content can be imported into this specification.

The semiconductor chip package of the third embodiment of the present invention is, for example, in the semiconductor chip package of the second embodiment, a rewiring forming layer or a solder resist layer is formed with a cured product of the resin composition of the present invention.

[Semiconductor Device] As the above-mentioned semiconductor device with a semiconductor chip package mounted thereon, for example, it is provided in electrical products (for example, computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) And various semiconductor devices of transportation tools (for example, locomotives, automobiles, trams, ships and aircrafts, etc.). [Example]

Hereinafter, examples are shown to specifically explain the present invention. However, the present invention is not limited by the following examples. In the following description, the "parts" and "%" indicating the quantity refer to "parts by mass" and "% by mass" respectively when they are not clearly defined otherwise. In addition, the operations described below are carried out in an environment of normal temperature and pressure unless otherwise clearly defined.

(Synthesis of synthetic resin A) In a flask equipped with a stirring device, a thermometer, and a condenser, 368.41 g of ethyl diethylene glycol acetate as a solvent, SOLVESSO 150 (aromatic solvent, manufactured by Exxon Mobil), 368.41 g, add 100.1g (0.4 mol) of diphenylmethane diisocyanate and polycarbonate diol (number average molecular weight: about 2000, hydroxyl equivalent: 1000, non-volatile matter: 100%, Kuraray Co. "C -2015N") 400g (0.2 mol), reacted at 70°C for 4 hours. Next, put in 195.9g (0.2 mol) of nonylphenol phenolic resin (hydroxy equivalent 229.4g/eq, average 4.27 functions, average calculated molecular weight 979.5g/mole) and 41.0g ethylene glycol bis-anhydrous trimellitate (0.1 mol), the temperature was raised to 150°C over 2 hours, and the reaction was carried out for 12 hours. By FT-IR, it was confirmed that the NCO peak at ^{2250 cm -1 disappeared.} After confirming the disappearance of the NCO peak, it was regarded as the end of the reaction. After the reactant was cooled to room temperature, it was filtered using a 100-mesh filter cloth to obtain a resin with a polycarbonate structure (50% by mass of non-volatile content). The number average molecular weight of the obtained resin (synthetic resin A) was 6,100.

(Preparation of Silica A) By using KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.), ^{spherical silica with an average particle diameter of 3 μm and a specific surface area of 4.4 m 2} /g is surface-treated to obtain spherical silicon dioxide. Silica A.

(Preparation of resin varnish 1) The epoxy resin ("ZX1059" made by Nippon Steel & Sumikin Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq. ) 10 parts, biphenyl type epoxy resin (Nippon Kayaku Corporation "NC3000L", epoxy equivalent 269g/eq.) 41 parts, amphiphilic polyether block copolymer (Dow Chemical Co. "Fortegra 100 ``) 3 parts, 380 parts of spherical silica (average particle size 0.5μm, Admatex "SO-C2") surface-treated with a phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) , Phenol phenolic resin (Phenolic hydroxyl equivalent 105, DIC company "TD2090-60M" solid content 60% MEK solution) 8.3 parts, phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30% by mass Cyclohexanone: a 1:1 solution of methyl ethyl ketone (MEK)) 16.6 parts, 30 parts methyl ethyl ketone, and 0.3 parts of an imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.) The resin varnish 1 was prepared by uniformly dispersing it using a high-speed rotating mixer.

(Preparation of resin varnish 2) 2 parts of synthetic resin A, 2 parts of rubber particles ("PARALOID EXL-2655" manufactured by The Dow Chemical Company), and 2 parts of naphthalene type epoxy resin ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). The epoxy equivalent is about 332g /eq.) 3 parts, liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), Epoxy equivalent 169g/eq.) 6 parts, phenolic phenolic hardener containing triazine skeleton ("LA-7054" made by DIC Corporation, hydroxyl equivalent 125g/eq., non-volatile content 60% MEK solution) 8.3 parts, Silicon dioxide A 125 parts, hardening accelerator (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.) 0.1 part, methyl ethyl ketone (MEK) 10 parts, cyclohexanone 8 The parts are mixed and uniformly dispersed using a high-speed rotary mixer to prepare resin varnish 2.

＜Measurement of elastic modulus of support＞ The support was cut out into a dumbbell-shaped No. 1 shape to obtain a test piece. The tensile strength of this test piece was measured using a tensile testing machine "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23°C was determined. The measurement is implemented in accordance with JIS K7127. This operation was performed 3 times and the average value is shown in the following table.

<Example 1> On the release surface of a 38μm-thick PET film (the second support, made by Lintec Co., Ltd., "AL5", with a modulus of elasticity of 4GPa at 23°C) that has been subjected to a release treatment, the thickness after drying becomes For the 200μm method, use a die coater to coat the resin varnish 1. After coating, the resin composition layer was formed by drying at 75 to 120°C for 12 minutes.

Secondly, a first support (low density polyethylene, manufactured by Tamapoly, "GF-1", thickness 30μm, modulus of elasticity at 23°C: 0.24GPa) was attached to the surface of the resin composition layer to support The body was wound into a roll shape of 50 m so that the body became the inner side to produce a resin sheet.

<Example 2> In Example 1, resin varnish 1 was replaced with resin varnish 2, and the first support (low density polyethylene, manufactured by Tamapoly, "GF-1", modulus of elasticity at 23°C: 0.24 GPa) was replaced with the first Support (non-stretched polypropylene, manufactured by Toray Film Processing Co., "Torayfan NO9405S", modulus of elasticity at 23°C is 0.72GPa). Except for the above matters, other systems were performed in the same manner as in Example 1 to produce a resin sheet.

<Example 3> In Example 1, the first support (low-density polyethylene, manufactured by Tamapoly, "GF-1", with an elastic modulus of 0.24 GPa at 23°C) was replaced with the first support (polyvinyl chloride, Achilles Made by the company, "Type C+", the modulus of elasticity at 23°C is 0.25GPa), and it is dried at 75~120°C for 14 minutes. Except for the above matters, other systems were performed in the same manner as in Example 1 to produce a resin sheet.

<Example 4> In Example 1, the resin varnish 1 was replaced with the resin varnish 2, and the resin varnish 2 was applied, and then dried at 75 to 120° C. for 10 minutes. Except for the above matters, other systems were performed in the same manner as in Example 1 to produce a resin sheet.

＜Comparative example 1＞ In Example 1, the first support (low density polyethylene, manufactured by Tamapoly, "GF-1", with a modulus of elasticity of 0.24 GPa at 23°C) was replaced with the first support (polyethylene terephthalate) , "AL-5" manufactured by Lindeco, with a modulus of elasticity of 4GPa at 23°C, and dry for 8 minutes at 75~120. Except for the above matters, other systems were performed in the same manner as in Example 1 to produce a resin sheet.

＜Comparative example 2＞ In Example 1, the first support (low-density polyethylene, manufactured by Tamapoly, "GF-1", with an elastic modulus of 0.24 GPa at 23°C) was replaced with the first support (biaxially stretched polypropylene, Prince "Alphan MA-411" manufactured by AFT Company, the modulus of elasticity at 23°C is 2GPa). Dry at 75~120℃ for 7 minutes. Except for the above matters, other systems were performed in the same manner as in Example 1 to produce a resin sheet.

＜Measuring the lowest melt viscosity of resin composition layer＞ For the resin composition layer of the resin sheet, a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Corporation) was used to measure the lowest melt viscosity. For 1g of the sample resin composition taken from the resin composition layer, using a parallel plate with a diameter of 18mm, the temperature is increased at a temperature rise rate of 5°C/min from a starting temperature of 60°C to 200°C, the measurement temperature interval is 2.5°C, and the number of vibrations is 1Hz. Measure the dynamic viscoelastic modulus and the lowest melt viscosity (poise) under the measuring condition of 1deg deformation.

<Measurement support member of a length L _A and L _B of> resin sheet drawn 50cm, and cut into 50cm × 50cm. The winding direction of the cut resin sheet is regarded as the length of the first support, and the measurement is performed under the conditions of a temperature of 23°C and a humidity of 70%, and this is regarded as the length of the first support L _A. Next, under the conditions of a temperature of 23°C and a humidity of 70%, the Tensilon universal material testing machine was used to stretch the first support with a force of 0.008kgf/cm in the thickness direction of the first support to peel off the first support, and measure the peeling The length of the first support in the winding direction is taken as the length L _{B of the} first support, and the value of _{L A} /L _{B is calculated.}

＜Evaluation of wrinkles＞ Pull out the resin sheet by 50cm and cut it into 50cm×50cm. The first support of the cut resin sheet was peeled off, and the resin composition layer was visually confirmed for wrinkles. Those with wrinkles and poor appearance were rated as "×", and those without wrinkles and good appearance were rated as "〇".

＜Evaluation of curling＞ Pull out the resin sheet by 50cm and cut it into 50cm×50cm. Place the PET film with a thickness of 38μm that has been subjected to a release treatment downwards and place it on a flat place, and confirm the curling of the resin sheet. Those with a curl amount of 50 mm or more were rated as "×", and those with less than 50 mm were rated as "〇".

1: Resin sheet 2: Resin composition layer 3: The first support 4: The second support

[Fig. 1] Fig. 1 is a schematic cross-sectional view of the resin sheet of the present invention. [Fig. 2] Fig. 2 is a schematic cross-sectional view of the resin sheet of the present invention.

Claims (7)

A resin sheet comprising: a first support, and a resin composition layer joined to the first support, the thickness of the resin composition layer is 60 μm or more, and the ratio of one or more in-plane directions of the support L _A / L _B to satisfy the relationship 1.005 to 1.2 of; L _A represents the length of the first support member within the plane when the layer engaging direction of the resin composition, L _B represents the resin composition within the surface after the layer peeling The length of the first support in the direction. The resin sheet of claim 1, wherein the resin sheet is provided with a first support, a resin composition layer, and a second support in this order. Such as the resin sheet of claim 1, wherein the minimum melt viscosity of the resin composition layer at 60°C to 200°C is 1,000 poise or more and 20,000 poise or less. Such as the resin sheet of claim 1, wherein the minimum melt viscosity of the resin composition layer at 60°C to 200°C is set to M (poise), and the thickness of the resin composition layer is set to T (μm), M/ T satisfies the relationship between 5 and 200. A circuit board comprising an insulating layer formed by a cured product of a resin composition layer in a resin sheet according to any one of claims 1 to 4. A semiconductor chip package comprising: a circuit substrate as claimed in claim 5, and a semiconductor chip mounted on the aforementioned circuit substrate. A semiconductor chip package comprising: a semiconductor chip, and a cured product of a resin composition layer in the resin sheet of any one of claims 1 to 4 that seals the aforementioned semiconductor chip.

Images