JP2018168262A - Resin composition - Google Patents

Abstract

To provide a resin composition that yields an insulation member of a low dielectric constant showing a black color, which has excellent thin film insulation reliability and can suppress discoloration associated with a high-temperature heat history.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, (C) titanium black and (D) organic solvent. The content of (C) component is 0.5-10 mass% when nonvolatile components in the resin composition are 100 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, it is related with the sheet-like laminated material using this resin composition.

  In recent years, electronic circuit components have been miniaturized and thinned, and high insulation is required for insulating members contained therein. Electronic circuit components are required to be colored black with a colorant such as a dye or pigment depending on the application, but carbon black, which is a black colorant, is electrically conductive, so there is concern about the insulation reliability of the thin film insulating layer. Examples of the black colorant that brings about non-conductivity include titanium black composed of titanium nitride and titanium oxide such as titanium monoxide and titanium dioxide, and a technique for forming an insulating member using the titanium black. It has been proposed (for example, Patent Documents 1 and 2).

JP-A-63-81117 JP-A-63-215774

  However, the present inventors have a problem that titanium black is discolored as titanium nitride and titanium monoxide are oxidized to titanium dioxide due to a high-temperature thermal history during semiconductor mounting and the component composition ratio changes. Found. Further, when titanium black is used, it tends to result in an insulating member having a high dielectric constant.

  Another object of the present invention is to provide a resin composition that provides an insulating member having a low dielectric constant that exhibits a black color, which is excellent in thin-film insulation reliability and can suppress discoloration associated with high-temperature thermal history.

  As a result of intensive studies on the above problems, the present inventors have found a resin composition containing (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, (C) titanium black, and (D) an organic solvent. Then, when the content of the component (C) is 100% by mass of the nonvolatile component in the resin composition, it is found that the resin composition of 0.5 to 10% by mass can realize the above problem, The invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, (C) titanium black and (D) an organic solvent, wherein the content of the component (C) is a resin. The resin composition which is 0.5-10 mass% when the non-volatile component in a composition is 100 mass%.
[2] The resin composition according to [1], wherein the content of the component (B) is 0.1 to 40% by mass when the nonvolatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the content of the component (D) is 5% by mass or more.
[4] The content of titanium nitride in the component (C) is 20% by mass or more when the total mass of the component (C) is 100% by mass, according to any one of [1] to [3]. Resin composition.
[5] The resin composition according to any one of [1] to [4], which is used for an insulating layer of a printed wiring board or for semiconductor encapsulation.
[6] A sheet-shaped laminated material including a resin composition layer formed from the resin composition according to any one of [1] to [5].
[7] The sheet-shaped laminated material according to [6], wherein the resin composition layer has a thickness of 100 μm or less.
[8] The sheet-shaped laminated material according to [6] or [7], wherein the resin composition layer has a thickness of 20 μm or less.
[9] A printed wiring board including an insulating layer obtained by thermosetting the resin composition layer of the sheet-like laminated material according to any one of [6] to [8].
[10] A sheet form according to any one of [6] to [8], including a circuit board, a semiconductor mounted on the circuit board, and a sealing material for sealing the semiconductor. A semiconductor package formed from a cured product of a resin composition layer of a laminated material.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which is excellent in thin film insulation reliability and can provide the insulating member of the low dielectric constant which exhibits black which can suppress the fading accompanying a high temperature heat history can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, (C) titanium black and (D) an organic solvent, and the content of the (C) component is a resin composition. When the non-volatile component in a thing is 100 mass%, it is 0.5-10 mass%, It is characterized by the above-mentioned.

  Titanium black is a non-conductive colorant, and an insulating member formed using it is expected to be excellent in thin film insulation reliability. However, when an insulating member is formed using titanium black, titanium nitride and titanium monoxide are oxidized to titanium dioxide due to a high-temperature thermal history during semiconductor mounting, etc. The present inventors have found that

  In recent years, when manufacturing electronic circuit components such as printed wiring boards and semiconductor packages, a technique for forming an insulating member using a sheet-like laminated material has been proposed (for example, JP 2011-132507 A). In particular, the inventors of the present invention have confirmed that the problem of fading of the above-described titanium black tends to become serious when such a technique is applied. When producing a sheet-like laminated material, a resin composition containing titanium black is prepared in the state of a resin varnish (resin ink), and the resin varnish is dried and solidified to form a resin layer. Due to the ease of contact between titanium black and atmospheric oxygen, heat input during drying / solidification, etc., the composition ratio of titanium black is likely to change due to high-temperature thermal history during subsequent semiconductor mounting. One of the reasons is considered to be the state.

  On the other hand, the resin composition of the present invention containing a compound having a phenolic hydroxyl group in combination with a predetermined amount of titanium black and containing an organic solvent is a thin film insulation reliability inherently expected for titanium black. Can be achieved at a high level and an insulating member exhibiting a low dielectric constant can be provided.In addition, when preparing in the state of a resin varnish suitable for the production of a sheet-like laminated material, The accompanying discoloration can be remarkably suppressed.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin (also referred to as “component (A)”). Examples of the epoxy resin include 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, trisphenol type epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition is a combination of a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and a solid epoxy resin (also referred to as “solid epoxy resin”) at a temperature of 20 ° C. It is preferable to include. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are alicyclic epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having butadiene structure, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type An epoxy resin is more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL”, “825” manufactured by Mitsubishi Chemical Corporation. ”,“ Epicoat 828EL ”(bisphenol A type epoxy resin),“ jER807 ”,“ 1750 ”(bisphenol F type epoxy resin),“ jER152 ”(phenol novolac type epoxy resin),“ 630 ”,“ 630LSD ”(glycidylamine) Type epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type manufactured by Nagase ChemteX Corporation) Epoxy resin), manufactured by Daicel Corporation “Celoxide 2021P” (an alicyclic epoxy resin having an ester skeleton), “PB-3600” (an epoxy resin having a butadiene structure), “ZX1658”, “ZX1658GS” (liquid 1, 4) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -Glycidylcyclohexane), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferred. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200" (Dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA -7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN "manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC7000L "(naphthol novolak type) Poxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak) Type epoxy resin), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin), Mitsubishi “JER1010” manufactured by Chemical Co., Ltd. (Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  (A) As a component, when using together a liquid epoxy resin and a solid epoxy resin, those quantity ratios (liquid epoxy resin: solid epoxy resin) are 1: 0.1-1: 15 by mass ratio. A range is preferred. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a sheet-like laminated material, ii) the form of the sheet-like laminated material When used in the above, sufficient flexibility is obtained, handling properties are improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.5 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.7 to 1: 8 is more preferable.

  The content of the component (A) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3 from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is at least mass%. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 60 mass% or less, More preferably, it is 55 mass% or less, 50 mass% or less, or 40 mass% or less. is there.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of (A) component becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  (A) The weight average molecular weight of a component becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  In one embodiment, the content of the naphthalene type epoxy resin in the component (A) is 12% by mass or less (preferably 10% by mass or less, preferably 9% by mass) when the nonvolatile component of the component (A) is 100% by mass. Hereinafter, it is 8 mass% or less, 7 mass% or less, 6 mass% or less, or 5 mass% or less. In another embodiment, the component (A) does not substantially contain a naphthalene type epoxy resin. Here, “substantially free of naphthalene type epoxy resin” means that the content of naphthalene type epoxy resin is less than 1% by mass.

<(B) Compound having phenolic hydroxyl group>
The resin composition of the present invention contains (B) a compound having a phenolic hydroxyl group (also referred to as “component (B)”). The phenolic hydroxyl group means a hydroxyl group that exists in a form in which a hydrogen atom of an aromatic ring structure is substituted with a hydroxyl group (hydroxy group).

  The component (B) is not particularly limited as long as it has a phenolic hydroxyl group in the molecule, but in combination with the component (C) described later, phenolic per molecule from the viewpoint of suppressing discoloration associated with high-temperature heat history. A compound containing two or more hydroxyl groups is preferred. The hydroxyl equivalent of the component (B) is preferably 30000 or less, more preferably 20000 or less, 10,000 or less, 5000 or less, 2000 or less, or 1000 or less. The lower limit of the hydroxyl group equivalent is preferably 50 or more, more preferably 80 or more, 100 or more, or 120 or more. The hydroxyl equivalent is the number of grams of resin containing 1 gram equivalent of hydroxyl group.

  Examples of the component (B) include one or more monomers, oligomers, and polymers having two or more phenolic hydroxyl groups per molecule. Among them, the resin is in a resin varnish suitable for producing a sheet-like laminated material. From the viewpoint of further suppressing the fading associated with high-temperature heat history when preparing the composition, phenol novolak resin, naphthol novolak resin, cresol novolak resin, dicyclopentadiene type phenol resin, terpene type phenol resin, triphenol methane One or more selected from mold resins, phenol aralkyl resins, naphthol aralkyl resins, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Novolac resin, naphtho Novolak resin, phenol aralkyl resin, naphthol aralkyl resin, one or more selected from 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphatonin phenanthrene-10-oxide is more preferable. In the resin composition of the present invention, the component (B) may be used alone or in combination of two or more. Examples of the component (B) include a compound having a phenolic hydroxyl group and a function of curing an epoxy resin (hereinafter simply referred to as “curing agent having a phenolic hydroxyl group”), a phenolic hydroxyl group and a resin. A compound having a function of imparting flame retardancy to the cured product of the composition (hereinafter simply referred to as “a flame retardant having a phenolic hydroxyl group”) may be used. As the curing agent having a phenolic hydroxyl group, a phenolic curing agent having a novolak structure or a naphthol curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion (peel strength) to the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. . From the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer, a triazine skeleton-containing phenol novolac-based curing agent and a triazine skeleton-containing naphthol novolak-based curing agent are preferable. Examples of the flame retardant having a phenolic hydroxyl group include an organic phosphorus flame retardant having a phenolic hydroxyl group and an organic nitrogen-containing phosphorus compound having a phenolic hydroxyl group. Among these, an organic phosphorus flame retardant having a phenolic hydroxyl group (For example, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is preferable.

  Specific examples of the component (B) include “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN” manufactured by Nippon Kayaku Co., Ltd. , “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.” “SN-375”, “SN-395”, “LA-7052”, “LA-7054”, “LA-3018”, “LA-1356”, “TD2090” manufactured by DIC Corporation, manufactured by Sanko Co., Ltd. “HCA-HQ” and the like.

  The content of the component (B) in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% from the viewpoint of suppressing discoloration associated with high-temperature heat history in combination with the component (C). It is 0.5 mass% or more, More preferably, it is 0.5 mass% or more, 1 mass% or more, 3 mass% or more, 5 mass% or more, or 7 mass% or more. Although the upper limit of content of (B) component is not specifically limited as long as the effect of this invention is show | played, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, 30 mass% or less, 25 mass% or less. Or 20% by mass or less.

<(C) Titanium black>
The resin composition of the present invention contains (C) titanium black (also referred to as “(C) component”). Titanium black is a black colorant that brings about non-conductivity in a mixed system with a resin, and an insulating member containing the titanium black exhibits high thin film insulation reliability. In the resin composition of the present invention, titanium black may be used alone or in combination of two or more.

  As described above, the present inventors have found that when an insulating member is formed using titanium black, there is a problem of fading due to a high-temperature heat history during semiconductor mounting or the like. In particular, when manufacturing an electronic circuit component such as a printed wiring board or a semiconductor package, the present inventors have found that such problems become serious when applying a technique for forming an insulating member using a sheet-like laminated material. I have confirmed. In contrast, according to the resin composition of the present invention containing a compound having a phenolic hydroxyl group in combination with a predetermined amount of titanium black and containing an organic solvent, the thin film insulation originally expected for titanium black It is possible to provide an insulating member exhibiting a high level of reliability and exhibiting a low dielectric constant. Furthermore, when preparing in the state of a resin varnish suitable for producing a sheet-like laminated material, high temperature heat The fading associated with the history can be remarkably suppressed.

  It is possible to achieve thin film insulation reliability at a high level, and to provide an insulating member exhibiting a low dielectric constant. Furthermore, when prepared in the state of a resin varnish, the discoloration associated with high-temperature thermal history is remarkably suppressed. In view of the possibility, the content of titanium nitride in the component (C) is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably, when the total mass of the component (C) is 100% by mass. Is 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more, particularly preferably 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. The upper limit of the content is usually 80% by mass or less and 75% by mass or less.

  In one embodiment, the mass ratio [titanium nitride / titanium oxide] of titanium nitride and titanium oxide (titanium monoxide, titanium dioxide, etc.) in component (C) is preferably 0.1 or more, more preferably 0.00. 2 or more, more preferably 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, particularly preferably 0.45 or more, 0.5 or more, 0.55 or more, or 0.6 or more. is there. The upper limit of the mass ratio is usually 0.8 or less and 0.75 or less.

  The average particle diameter of the component (C) is not particularly limited, but is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, 40 nm or more, or from the viewpoint of easily obtaining a resin composition having an appropriate viscosity. It is 50 nm or more. The upper limit of the average particle diameter is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1.5 μm or less, 1 μm or less, 0.8 μm or less, or 0.5 μm or less from the viewpoint of realizing a good packing density. It is. The average particle size of the component (C) can be measured in the same manner as described for the average particle size of the component (F) described later.

  As the component (C), titanium black may be used as it is. Alternatively, titanium black whose surface is treated with a dispersant may be used from the viewpoint of obtaining a resin composition (and consequently an insulating member) that exhibits a desired black color by improving dispersibility.

  Specific examples of the component (C) include “13MC”, “13M”, “12S”, and “13MT” manufactured by Mitsubishi Materials Corporation.

  The content of the component (C) in the resin composition is in the range of 0.5 to 10% by mass from the viewpoint of realizing the desired black color and realizing an insulating member having a low dielectric constant. (C) Preferably the minimum of content of a component is 0.7 mass% or more, 0.9 mass% or more, or 1 mass% or more. (C) Preferably the upper limit of content of a component is 9.5 mass% or less, 9 mass% or less, or 8.5 mass% or less. In addition, from the viewpoint of suppressing discoloration associated with high-temperature heat history, the mass ratio of the (C) component to the (B) component ((C) component / (B) component) is preferably 100 or less, more preferably 80 or less. 60 or less, 50 or less, 40 or less, 30 or less, or 20 or less. The lower limit of the mass ratio is not particularly limited, but is preferably 0.0125 or more, more preferably 0.02 or more, 0.03 or more, 0.04 or more, or 0.05 or more.

<(D) Organic solvent>
The resin composition of the present invention contains (D) an organic solvent (also referred to as “(D) component”). By including (D) component, the resin composition of this invention can be prepared in the state of a resin varnish (resin ink), and can be used conveniently for preparation of a sheet-like laminated material.

  As the organic solvent, an organic solvent having a boiling point at 1 atm of preferably 160 ° C. or lower, more preferably 150 ° C. or lower, further preferably 140 ° C. or lower, 130 ° C. or lower, or 120 ° C. or lower is preferable. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the component (D) in the resin composition is not particularly limited as long as the resin composition can be prepared in a resin varnish together with other components. The content of the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, or 20% by mass when the mass of the entire resin composition is 100% by mass. That's it. (D) Preferably the upper limit of content of a component is 60 mass% or less, More preferably, it is 55 mass% or less, 50 mass% or less, 45 mass% or less, or 40 mass% or less.

<Other ingredients>
The resin composition of the present invention further contains one or more additives selected from the group consisting of a thermoplastic resin, an inorganic filler, a curing agent, a curing accelerator, a flame retardant, and an organic filler, if necessary. You may do it.

-(E) Thermoplastic resin-
The resin composition of the present invention may further contain (E) a thermoplastic resin (also referred to as “(E) component”). When the resin composition of the present invention contains the component (E), it is expected to provide a low dielectric constant insulating member exhibiting black color, which has excellent thin film insulation reliability and can suppress discoloration associated with high-temperature heat history. It is possible to realize an insulating member exhibiting the above effect and exhibiting better flexibility (and thus excellent crack resistance).

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” manufactured by Mitsubishi Chemical Corporation. "YL6954" (bisphenol acetophenone skeleton-containing phenoxy resin), "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX7553", "YL6794" manufactured by Mitsubishi Chemical Corporation, "YL7213", "YL7290", "YL7482", etc. are mentioned.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd.'s S-REC BH series, BX series, KS series, BL series, BM series and the like.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  When the component (E) is used, the content of the component (E) in the resin composition is preferably 0.5 from the viewpoint of obtaining an insulating member that exhibits the desired effect of the present invention and is also excellent in crack resistance. It is at least 1% by mass, more preferably at least 1% by mass, even more preferably at least 1.5% by mass, at least 2% by mass, at least 2.5% by mass, or at least 3% by mass. Although the upper limit of content of (E) component is not specifically limited, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less or 10 mass% or less.

-(F) Inorganic filler-
The resin composition of the present invention may further contain (F) an inorganic filler (also referred to as “(F) component”). When the resin composition of the present invention contains the component (F), it is possible to realize an insulating member having a lower linear thermal expansion coefficient.

  The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, and silica is particularly suitable. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical silica include “SO-C2” and “SO-C1” manufactured by Admatechs Co., Ltd., “IMSIL A-8” and “IMSIL A-10” manufactured by Unimin.

  The average particle size of the inorganic filler is preferably 4 μm or less, more preferably 3 μm or less, even more preferably 2.5 μm or less, even more preferably 2 μm or less, particularly preferably 1 μm or less, 0.7 μm or less, or 0.5 μm. It is as follows. The lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, “LA-500”, “LA-750”, “LA-950”, etc. manufactured by Horiba, Ltd. can be used.

  Inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents and the like from the viewpoint of improving moisture resistance and dispersibility. It is preferable to treat with one or more surface treatment agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further included. preferable.

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

  When using the component (F), from the viewpoint of obtaining an insulating member having a low coefficient of linear thermal expansion, the content of the component (F) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more. , 20% by mass or more, or 30% by mass or more. The upper limit of the content of the component (F) is preferably 90% by mass or less, more preferably 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass from the viewpoint of mechanical strength of the obtained insulating member. It is as follows.

-(G) Curing agent-
The resin composition of the present invention may further contain (G) a curing agent (also referred to as “(G) component”). Here, the component (G) is a component different from the component (B), that is, a curing agent other than the curing agent having a phenolic hydroxyl group.

  The component (G) is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include an active ester curing agent, a cyanate ester curing agent, a benzoxazine curing agent, and a carbodiimide curing agent. (G) A component may be used individually by 1 type and may be used in combination of 2 or more type.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like. Specifically, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolak, and an active ester compound containing a benzoylated product of a phenol novolak are preferred. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferred.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (made by DIC Corporation) as active ester compounds containing a dicyclopentadienyl diphenol structure. ), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and benzoyl of phenol novolac Examples of the active ester compound containing a compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And the like, and the like, and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

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

  The amount ratio between the epoxy resin and the curing agent [curing agent having phenolic hydroxyl group and component (G)] is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent], The range of 1: 0.2 to 1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

-(H) Curing accelerator-
The resin composition of the present invention may further contain (H) a curing accelerator (also referred to as “(H) component”). Examples of the component (H) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, and imidazoles. Type curing accelerators are preferred, and amine type curing accelerators and imidazole type curing accelerators are more preferred. (H) A component may be used individually by 1 type and may be used in combination of 2 or more type. When the component (H) is used, the content of the component (H) in the resin composition is not particularly limited, but it is preferably used in the range of 0.05% by mass to 3% by mass.

-(I) Organic filler-
The resin composition of the present invention may further contain (I) an organic filler (also referred to as “component (I)”). As the component (I), any organic filler that can be used for forming an insulating member of an electronic circuit component may be used. Examples thereof include rubber particles, polyamide fine particles, silicone particles, and the like, and rubber particles are preferable. . A commercially available product may be used as the rubber particles, and examples thereof include “AC3816N” manufactured by Aika Industry Co., Ltd. When using (I) component, content of (I) component in a resin composition is although it does not specifically limit, It is preferable to use in the range of 1 mass%-20 mass%.

  The resin composition of the present invention may further contain other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. Examples include metal compounds and resin additives such as thickeners, antifoaming agents, leveling agents, and adhesion-imparting agents.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing and dispersing the compounding components using a rotary mixer or the like.

  The viscosity (23 ° C.) of the resin composition of the present invention is preferably 50 mPa · s to 5 Pa · s, more preferably 100 mPa · s to 1 Pa · s.

  The insulating member formed using the resin composition of the present invention exhibits a black color. For example, the lightness index (dL) of the insulating member formed using the resin composition of the present invention is preferably less than −62, more preferably less than −63, even more preferably less than −64, and less than −66 at a thickness of 200 μm. , Less than −68, or less than −70. The brightness index (dL) can be measured according to the method described in <Measurement of brightness index dL> described later.

The insulating member formed using the resin composition of the present invention can remarkably suppress discoloration associated with high temperature heat history. For example, an insulating member formed using the resin composition of the present invention maintains a high lightness index (dL) even after being subjected to three reflow treatments (maximum temperature 260 ° C.). When the lightness index (dL) before being subjected to three reflow treatments is dL ₀ , and the lightness index (dL) after being subjected to three reflow treatments is dL ₃ , the resin composition of the present invention is used. In the insulating member (thickness: 200 μm), the difference | dL ₀ −dL ₃ | between dL ₀ and dL ₃ is preferably 3 or less, more preferably 2 or less, 1 or less, or 0.

  The resin composition of the present invention can realize a low dielectric constant insulating member exhibiting black color, which has excellent thin film insulation reliability and can suppress discoloration associated with high-temperature heat history. Therefore, the resin composition of the present invention can be suitably used for forming an insulating member of an electronic circuit component that is required to be colored black. For example, the resin composition of the present invention is a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board) or a resin composition for sealing a semiconductor ( It can be suitably used as a semiconductor sealing resin composition).

  When the resin composition of the present invention is prepared in the state of a resin varnish suitable for the production of a sheet-like laminated material, it is possible to remarkably suppress the fading accompanying the high temperature heat history. Therefore, the resin composition of the present invention can be suitably used for forming sheet-like laminated materials such as adhesive films and prepregs. The resin composition of the present invention can also be used in a wide range of applications where a resin composition is required, such as a solder resist, an underfill material, a die bonding material, a hole-filling resin, and a component-filling resin.

[Sheet laminated material]
The resin composition of the present invention can be used by being applied in a varnish state, but is preferably used in the form of a sheet-like laminated material including a resin composition layer from the resin composition.

  As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

  In one embodiment, the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is the resin composition of the present invention. Formed from.

  The sheet-like laminated material of the present invention provides an insulating member having excellent insulating properties. For example, even when the wiring line / space (L / S) ratio is as small as 5 μm / 5 μm, it is possible to realize an insulating member having excellent wiring line insulation. In one embodiment, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, 50 μm or less, or 40 μm or less. The sheet-like laminated material of the present invention can realize an insulating member that is particularly excellent in thin-film insulation. Therefore, in one embodiment, the thickness of the resin composition layer may be 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less, 11 μm or less, or 10 μm or less. May be. The sheet-like laminated material of the present invention significantly contributes to the miniaturization and thinning of electronic circuit components. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 0.5 micrometer or more, 1 micrometer or more, 2 micrometers or more.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.

  Although the thickness of a support body is not specifically limited, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The adhesive film can be produced, for example, by applying a resin composition (resin varnish) on a support using a die coater or the like and further drying to form a resin composition layer.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the component (D) in the resin composition layer is preferably 5% by mass or less, 4% by mass or less, or 3% by mass or less. Depending on the boiling point of the component (D) in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the component (D), it is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. Thus, the resin composition layer can be formed.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

  In one embodiment, the prepreg is formed by impregnating the sheet-like fiber base material with the resin composition of the present invention and drying. In such an embodiment, the whole dried sheet-like fiber base impregnated with the resin composition is referred to as a “resin composition layer”.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. The thickness of the sheet-like fiber base material is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, 50 μm or less, or 40 μm or less. From the viewpoint of miniaturization / thinning of electronic circuit components, the thickness of the sheet-like fiber base material is preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less. , 11 μm or less, or 10 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it is 5 micrometers or more.

  The thickness of the resin composition layer in the prepreg can be in the same range as the thickness of the resin composition layer in the adhesive film described above.

  A sheet-like laminated material formed using the resin composition of the present invention containing a compound having a phenolic hydroxyl group in combination with a predetermined amount of titanium black and containing an organic solvent is inherently expected for titanium black. In addition, it is possible to provide an insulating member exhibiting a low dielectric constant and a fading associated with high-temperature thermal history. Therefore, the sheet-like laminated material of the present invention can be suitably used for forming an insulating member of an electronic circuit component that is required to be colored black. For example, the sheet-like laminated material of the present invention is suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board) or for sealing a semiconductor (for semiconductor sealing). be able to.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of this invention contains the insulating layer obtained by thermosetting the resin composition layer of the sheet-like laminated material of this invention.

  The printed wiring board of this invention can be manufactured by laminating | stacking the sheet-like laminated material of this invention on an inner layer board | substrate, and thermosetting a resin composition layer and forming an insulating layer. Here, the “inner layer substrate” is mainly patterned on a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both sides of the substrate. A circuit board on which a conductive layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with built-in components may be used.

In one Embodiment, the printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned adhesive film.
(I) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer

  In step (I), the inner layer substrate and the adhesive film can be laminated by, for example, thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member that heat-presses the adhesive film to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the adhesive film but to press it through an elastic material such as heat resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the adhesive film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and the like.

  After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

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

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  When manufacturing a printed wiring board, (III) a step of drilling an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer on the surface of the insulating layer may be further performed. Good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V).

  In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when an adhesive film is used.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  Step (V) is a step of forming a conductor layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern.

  In other embodiments, the conductor layer may be formed using a metal foil. When forming a conductor layer using metal foil, it is suitable to implement process (V) between process (I) and process (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum laminating method. The conditions for stacking may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method.

  The metal foil can be produced by a known method such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foils manufactured by JX Metals, JXUT-III foils, 3EC-III foils and TP-III foils manufactured by Mitsui Metal Mining Co., Ltd.

  By using the sheet-like laminated material of the present invention, a printed wiring board having a low dielectric constant insulating layer exhibiting black color, which has excellent thin film insulation reliability and can suppress discoloration associated with high-temperature thermal history. It is possible to manufacture.

[Semiconductor package and manufacturing method thereof]
The semiconductor package of the present invention includes a circuit board, a semiconductor mounted on the circuit board, and a sealing material for sealing the semiconductor, and the sealing material is a resin composition of the sheet-like laminated material of the present invention. It is characterized by being formed from a cured product of the layer. Here, the structure and type of the circuit board and semiconductor constituting the semiconductor package of the present invention are not particularly limited, and any circuit board or semiconductor that is normally used when forming the semiconductor package may be used.

  The semiconductor package of this invention can be manufactured by sealing a semiconductor with the resin composition layer of the sheet-like laminated material of this invention. Conditions for sealing the semiconductor are not particularly limited, and any sealing conditions that are normally used when manufacturing a semiconductor package may be adopted.

  By using the sheet-like laminated material of the present invention, a semiconductor package provided with a black low-permittivity sealing material that has excellent thin-film insulation reliability and can suppress discoloration associated with high-temperature thermal history Can be manufactured.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board or the semiconductor package of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited at all by the following Examples. In the following description, “part” means “part by mass” unless otherwise specified.

<Measurement of brightness index dL>
(1) Sample preparation Resin after drying the resin composition (resin varnish) obtained in Examples and Comparative Examples on the release layer of a PET film with a release layer ("PET501010" manufactured by Lintec Corporation) It apply | coated uniformly with the die-coater so that the thickness of a composition layer might be set to 40 micrometers. Then, it was made to dry at 80-110 degreeC (average 95 degreeC) for 6 minutes, and the resin composition layer was formed on PET film (n = 5). Five sheets of this resin composition layer were bonded together to form a film having a thickness of 200 μm and heated in an oven at 190 ° C. for 2 hours to obtain a cured product sample. Moreover, a part of obtained hardened | cured material sample was cut out, and it heat-processed 3 times with the reflow apparatus ("HAS6116" by Antom Co., Ltd., the highest achieved temperature 260 degreeC). A cured product sample that has been heat-treated three times by a reflow apparatus is referred to as a “sample after three reflows”, and a cured sample that has not been subjected to the heat treatment by the reflow apparatus is referred to as a “sample after resin curing”.

(2) Measurement of lightness index dL About the sample after resin hardening and the sample after 3 reflows, using a color difference meter ("CR-10" manufactured by Minolta Co., Ltd.), a white calibration plate (manufactured by Minolta Co., Ltd.) The lightness index dL was measured based on C0-03). The value of the lightness index dL was defined as “◯” when less than −64, “Δ” when −64 or more but less than −62, and “×” when −62 or more.

<Measurement of dielectric constant>
The resin varnishes obtained in the examples and comparative examples were placed on a release-treated PET film ("PET501010" manufactured by Lintec Corporation) so that the thickness of the resin composition layer after drying was 40 µm. The film was uniformly coated with a tar and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed for 90 minutes at 200 degreeC in nitrogen atmosphere, and obtained the hardened | cured material film by peeling from a PET film.

  The cured product film was cut into a length of 80 mm and a width of 2 mm and used as an evaluation sample. With respect to this evaluation sample, dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Measurement was performed on five evaluation samples, and an average value was calculated. When the average value of the dielectric constant is less than 3.5, “◯” is given, and when the average value is 3.5 or more, “x” is given.

<Evaluation of interlayer insulation>
(1) Production of Adhesive Film A PET film with a release layer (“AL5” manufactured by Lintec Corporation) was prepared as a support. On the release layer of this support, the resin varnishes obtained in Examples and Comparative Examples were uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 12 μm. Then, it was made to dry at 80-110 degreeC (average 95 degreeC) for 6 minutes, and the adhesive film was obtained.

(2) Substrate treatment of inner layer circuit board Etching on both sides of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.8mm, Matsushita Electric Works "R5715ES") After forming a circuit pattern by the above, a roughening process was performed with a micro-etching agent (“CZ8100” manufactured by Mec Co., Ltd.) to produce an inner layer circuit board.

(3) Lamination of adhesive film The adhesive film produced in (1) above is prepared by using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) and the resin composition layer is an inner layer circuit board. Was laminated on both sides of the inner circuit board so as to be bonded to each other. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(4) Curing of resin composition layer After laminating the adhesive film, the support was peeled off to expose the resin composition layer. Subsequently, the resin composition layer was thermoset under the conditions of 100 ° C. for 30 minutes and 180 ° C. for 30 minutes to form an insulating layer.

(5) Roughening treatment The laminate obtained in (4) above is applied to a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether). 10 minutes at 80 ° C., then to a roughening solution (Atotech Japan Co., Ltd. “Concentrate Compact P”, KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally neutralized It was immersed for 5 minutes at 40 ° C. in a liquid (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd., sulfuric acid aqueous solution). Then, it was dried at 80 ° C. for 30 minutes. The obtained substrate is referred to as “evaluation substrate A”.

(6) Plating by semi-additive method A conductor layer was formed on the evaluation substrate A by a semi-additive method. Specifically, the evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. An annealing treatment was performed by heating at 150 ° C. for 30 minutes, and then an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 190 ° C. for 60 minutes. The obtained substrate is referred to as “evaluation substrate B”.

(7) Production of test piece for insulation test The evaluation substrate B was cut into a size of 10 cm × 10 cm, and 10 pieces of tape having a diameter of 1 cm were stuck on one side. The plating on the portion where the tape was not applied was etched with an etching solution at 40 ° C. containing iron (III) chloride as a main component. After washing with city water, the tape was peeled off and washed with pure water subjected to Millipore filtration. Then, after drying for 15 minutes in 100 degreeC oven, it hardened | cured for 60 minutes in 190 degreeC oven. The resin at the edge of the substrate was shaved to expose the underlying copper foil, and a copper wire was soldered as an electrode to the center of the 10 plated copper foils and the underlying copper foil. Subsequently, it wash | cleaned in order with a dichloromethane and methanol, and it was made to dry for 30 minutes in 130 degreeC oven, and the test piece was obtained.

(8) Measurement of resistance value The insulation resistance value of the test piece obtained in the above (7) was measured with a resistance measuring instrument ("ECM-100" manufactured by J-RAS). Thereafter, the test piece was subjected to an environment having a temperature of 130 ° C. and a relative humidity of 85% using a HAST testing machine (“PM422” manufactured by Enomoto Kasei Co., Ltd.), and a voltage of 3.3 V was applied to both ends of the electrode. . After 200 hours, the test piece was taken out and the insulation resistance value was measured. The test piece after 200 hours had an insulation resistance value of less than 1 × 10 ⁷ Ω, “◯” when there were less than 3 wires, and “×” when 3 or more wires were generated.

(9) Confirmation of interlayer insulation film thickness After the test of (8) above, the cross section of the test piece was confirmed with an optical microscope, and it was confirmed that the interlayer insulation film thickness was 9 to 11 µm.

<Evaluation of insulation between lines>
(1) Production of Adhesive Film A PET film with a release layer (“AL5” manufactured by Lintec Corporation) was prepared as a support. On the release layer of this support, the resin varnishes obtained in Examples and Comparative Examples were uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 20 μm. Then, it was made to dry at 80-110 degreeC (average 95 degreeC) for 6 minutes, and the adhesive film was obtained.

(2) Substrate treatment of inner substrate Substrate on both sides of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R5715ES” manufactured by Matsushita Electric Works Co., Ltd.) A roughening treatment was performed with an etching agent (“CZ8100” manufactured by MEC Co., Ltd.).

(3) Lamination of adhesive film Using the batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) It laminated | stacked on both surfaces of the inner-layer board | substrate so that it might join. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(4) Curing of resin composition layer After laminating the adhesive film, the support was peeled off to expose the resin composition layer. Subsequently, the resin composition layer was thermoset under the conditions of 100 ° C. for 30 minutes and 180 ° C. for 30 minutes to form an insulating layer.

(5) Roughening treatment The laminate obtained in (4) above is applied to a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether). 10 minutes at 80 ° C., then to a roughening solution (Atotech Japan Co., Ltd. “Concentrate Compact P”, KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally neutralized It was immersed for 5 minutes at 40 ° C. in a liquid (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd., sulfuric acid aqueous solution). Then, it was dried at 80 ° C. for 30 minutes. The obtained substrate is referred to as “evaluation substrate A”.

(6) Formation of electroless plating layer A conductor layer was formed on the evaluation substrate A by a semi-additive method. Specifically, the evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Annealing was performed by heating at 150 ° C. for 30 minutes.

(7) Lamination of dry film Using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) as a dry film ("RY-5107" manufactured by Hitachi Chemical Co., Ltd.), (6) It was laminated on one side of the substrate produced in (1). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(8) Exposure Using an exposure machine (projection exposure machine UX-2240SM manufactured by USHIO INC.), A dry film so as to have a comb-blade pattern wiring (line / space (L / S) ratio = 5 μm / 5 μm) (200 mJ), and then developed using a 1% by weight aqueous sodium carbonate solution.

(9) Formation of electroplating layer Copper sulfate electrolytic plating was performed on the substrate prepared in (8) to form a conductor layer with a thickness of 5 μm. Next, annealing was performed at 190 ° C. for 60 minutes.

(10) Formation of wiring of comb blade pattern The surface of the substrate obtained in (9) was washed, and the dry film was removed. Etching was then performed to form a comb-blade pattern wiring. The obtained substrate is referred to as “evaluation substrate B”.

(11) Lamination of Adhesive Film Using the batch-type vacuum pressure laminator (Mechanical Manufacturing Co., Ltd. “MVLP-500”), the resin composition layer of the evaluation substrate B is laminated on the adhesive film produced in (1) above. Lamination was performed so as to be bonded to the wiring of the comb blade pattern. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(12) Curing of resin composition layer After laminating the adhesive film, the support was peeled off to expose the resin composition layer. The resin composition layer was thermally cured at 190 ° C. for 90 minutes to form an insulating layer. The obtained substrate is referred to as “evaluation substrate C”.

(13) Production of Test Piece for Insulation Test Resin at both ends of the comb-blade pattern of the evaluation substrate C was scraped to expose copper, and copper wires were soldered using 10 locations as electrodes. Subsequently, it wash | cleaned in order with a dichloromethane and methanol, and it was made to dry for 30 minutes in 130 degreeC oven, and the test piece was obtained.

(14) Measurement of resistance value The insulation resistance value of the test piece obtained in the above (13) was measured with a resistance measuring instrument ("ECM-100" manufactured by J-RAS). Thereafter, the test piece was subjected to an environment having a temperature of 130 ° C. and a relative humidity of 85% using a HAST testing machine (“PM422” manufactured by Enomoto Kasei Co., Ltd.), and a voltage of 3.3 V was applied to both ends of the electrode. . After 200 hours, the test piece was taken out and the insulation resistance value was measured. The test piece after 200 hours had an insulation resistance value of less than 1 × 10 ⁷ Ω, “◯” when there were less than 3 wires, and “×” when 3 or more wires were generated.

(15) Confirmation of insulation film thickness between lines After the test of (14) above, the cross section of the test piece was confirmed with an optical microscope, and it was confirmed that the insulation film thickness between lines was 4 to 6 μm.

<Evaluation of crack resistance>
(1) Production of Adhesive Film A PET film with a release layer (“AL5” manufactured by Lintec Corporation) was prepared as a support. The resin varnishes obtained in Examples and Comparative Examples were uniformly coated on the release layer of the support with a die coater so that the thickness of the resin composition layer after drying was 100 μm. Then, it was made to dry for 7 minutes at 70-120 degreeC (average 95 degreeC), and the adhesive film was produced.

(2) Creation of inner layer circuit board Etching on both sides of glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18μm, board thickness 0.2mm, "E679FGR" manufactured by Hitachi, Ltd.) A circuit pattern was formed, and further a roughening treatment was performed with a microetching agent (“CZ8100” manufactured by MEC Co., Ltd.) to produce an inner layer circuit board. A 12 mm × 12 mm through hole was formed in the inner layer circuit board with a mechanical drill.

(3) Lamination of temporary adhesive film A polyimide-based temporary adhesive film ("PFDKE 1525PT" manufactured by Arisawa Manufacturing Co., Ltd.) was prepared, and the protective film was peeled off. Thereafter, the temporary adhesive film is laminated on one side of the inner circuit board using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) so that the adhesive layer is bonded to the inner circuit board. did. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(4) Temporary Fixing of Dummy Wafer and Lamination of Adhesive Film A 10 mm × 10 mm dummy wafer was inserted into the hole of the inner layer circuit board with temporary adhesive film produced in (3) above. Next, the adhesive film produced in the above (1) is bonded to the inner circuit board by using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). The inner layer circuit board was laminated on one side. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(5) Curing of resin composition layer After lamination of the adhesive film, the resin composition layer was thermally cured at 100 ° C for 30 minutes and at 170 ° C for 30 minutes to form an insulating layer. Thereafter, the PET film which is a support for the adhesive film was peeled off.

(6) Peeling of temporary adhesive film and complete curing of insulating layer After peeling the polyimide-based temporary adhesive film, the insulating layer was completely cured at 200 ° C for 60 minutes.

(7) Evaluation of crack resistance A part of the cured product sample obtained in the above (6) was cut out and subjected to heat treatment 20 times with a reflow apparatus (“HAS6116” manufactured by Antom Co., Ltd., maximum temperature reached 260 ° C.). It was. Thereafter, the circuit board with a built-in dummy wafer was observed with an optical microscope. When the number of cracks was 0, “◯” was obtained, when “1” or more and less than 3 places “△”, and when 3 or more, “x”.

<Example 1>
20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), 20 parts biphenyldimethylene type resin (epoxy equivalent 269, “NC3000” manufactured by Nippon Kayaku Co., Ltd.), naphthalene 3 parts of type 4 functional epoxy resin (epoxy equivalent 171; “HP4710” manufactured by DIC Corporation), 15 parts of phenoxy resin (“YL6954BH30” manufactured by Japan Epoxy Resin Corporation, MEK solution having a solid content of 30% by mass) (Hereinafter also referred to as “MEK1”.) 20 parts were stirred and dissolved with stirring. Thereto, 15 parts of a MEK solution having a solid content of 60% by mass of a triazine-containing phenol novolac resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, nitrogen content of approximately 12% by mass), naphthol-based curing agent (hydroxyl equivalent 215). 15 parts of MEK solution having a solid content of 60% by mass of “SN-485” manufactured by Tohto Kasei Co., Ltd., reactive flame retardant (hydroxyl equivalent 162, “HCA-HQ” manufactured by Sanko Co., Ltd.), phosphorus content 9. 2 parts, spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., with aminosilane treatment) 40 parts, titanium black black pigment (“13MC” manufactured by Mitsubishi Materials Corporation), dispersion 7 parts of propylene glycol-1-monomethyl ether-2-acetate dispersion having a solid content of 33% by mass of a curing agent), and a curing accelerator (dimethylaminopyridide manufactured by TCI Co., Ltd.) (DMAP), 5 parts by mass of MEK solution) was uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

<Example 2>
Instead of 15 parts of MEK solution having a solid content of 60% by mass of naphthol-based curing agent (hydroxyl equivalent 215, “SN-485” manufactured by Tohto Kasei Co., Ltd.), active ester curing agent (active group equivalent approximately 223, DIC Corporation) A resin varnish was prepared in the same manner as in Example 1 except that 15 parts of “HPC8000-65T” (a toluene solution having a nonvolatile content of 65% by mass) were used.

<Example 3>
A resin varnish was prepared in the same manner as in Example 1 except that the amount of the titanium black black pigment dispersion was changed from 7 parts to 2.5 parts.

<Example 4>
(1) In the same manner as in Example 1, except that the amount of titanium black black pigment dispersion was changed from 7 parts to 30 parts, and (2) the amount of MEK1 was changed from 20 parts to 5 parts, A resin varnish was prepared.

<Example 5>
(1) A blending amount of both a MEK solution having a solid content of 60% by mass of a triazine-containing phenol novolac resin (“LA7054”) and a MEK solution having a solid content of 60% by mass of a naphthol-based curing agent (“SN-485”). Except for the point changed from 15 parts to 0.15 parts, and (2) the amount of the reactive flame retardant (“HCA-HQ”) changed from 2 parts to 0.02 parts, the same as in Example 1. A resin varnish was prepared.

<Example 6>
(1) A blending amount of both a MEK solution having a solid content of 60% by mass of a triazine-containing phenol novolac resin (“LA7054”) and a MEK solution having a solid content of 60% by mass of a naphthol-based curing agent (“SN-485”). Resin in the same manner as in Example 1 except that it was changed from 15 parts to 37.5 parts, and (2) the amount of the reactive flame retardant (“HCA-HQ”) was changed from 2 parts to 5 parts. A varnish was prepared.

<Example 7>
Instead of 3 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 171; "HP4710" manufactured by DIC Corporation), 3 parts of tetraphenylethane type epoxy resin (epoxy equivalent 196, "1031S" manufactured by Mitsubishi Chemical Corporation)) A resin varnish was prepared in the same manner as in Example 1 except that it was used.

<Comparative Example 1>
Instead of 7 parts of titanium black black pigment dispersion, 10 parts of carbon black black pigment (“MHI Black # RK-173M” manufactured by Mikuni Dye Co., Ltd., dispersion-treated product having a carbon black content of 26 mass%, MEK dispersion) A resin varnish was prepared in the same manner as in Example 1 except that was used.

<Comparative example 2>
A resin varnish was prepared in the same manner as in Example 1, except that the amount of the titanium black black pigment dispersion was changed from 7 parts to 1 part.

<Comparative Example 3>
(1) A resin varnish was prepared in the same manner as in Example 1, except that the blending amount of the titanium black black pigment dispersion was changed from 7 parts to 45 parts, and (2) MEK1 was not used.

<Comparative example 4>
Instead of triazine-containing phenol novolac resin, naphthol-based curing agent and reactive flame retardant, active ester curing agent (active group equivalent of about 223, "HPC8000-65T" manufactured by DIC Corporation, toluene solution with a nonvolatile content of 65% by mass) A resin varnish was prepared in the same manner as in Example 1 except that 30 parts were used.

  The evaluation results of the above-described examples and comparative examples are shown in the following table.

  When the spherical silica “SOC2” is not blended, and when the curing accelerator (dimethylaminopyridine (DMAP)) is not blended, it is confirmed that the result is the same as the above-mentioned example although there is a difference in the degree. Yes.

Claims (10)

A resin composition comprising (A) an epoxy resin, (B) a compound having a phenolic hydroxyl group, (C) titanium black and (D) an organic solvent,
(C) The resin composition whose content of a component is 0.5-10 mass% when the non-volatile component in a resin composition is 100 mass%.   (B) The resin composition of Claim 1 whose content of a component is 0.1-40 mass% when the non-volatile component in a resin composition is 100 mass%.   (D) The resin composition of Claim 1 or 2 whose content of a component is 5 mass% or more.   The resin composition according to any one of claims 1 to 3, wherein the content of titanium nitride in the component (C) is 20% by mass or more when the total mass of the component (C) is 100% by mass. object.   The resin composition according to any one of claims 1 to 4, which is used for an insulating layer of a printed wiring board or for sealing a semiconductor.   The sheet-like laminated material containing the resin composition layer formed from the resin composition of any one of Claims 1-5.   The sheet-like laminated material according to claim 6, wherein the resin composition layer has a thickness of 100 μm or less.   The sheet-like laminated material according to claim 6 or 7, wherein the resin composition layer has a thickness of 20 µm or less.   The printed wiring board containing the insulating layer obtained by thermosetting the resin composition layer of the sheet-like laminated material of any one of Claims 6-8.   The sheet-shaped laminated material according to any one of claims 6 to 8, comprising a circuit board, a semiconductor mounted on the circuit board, and a sealing material that seals the semiconductor. A semiconductor package formed from a cured product of a resin composition layer.