KR20140061245A - Insulating resin material - Google Patents

Abstract

The objective of the present invention is to provide an insulating resin material with high dimensional stability and low warpage during curing. The present invention relates to an insulating resin material which includes a thermosetting resin, an inorganic filler, and a polymer resin with a glass transition temperature of 30 deg. C or lower. The content of the inorganic filler is 50-95 mass% relative to 100 mass% of non-volatile components among the insulating resin material.

Description

[0001] INSULATING RESIN MATERIAL [0002]

The present invention relates to an insulating resin material. The present invention also relates to a printed circuit board using the insulating resin material, a circuit board such as a wafer level chip size package, and the like.

In an insulating resin material used for a circuit board such as a printed wiring board or a wafer level chip size package, a material having a low elastic modulus is required in order to suppress warping of the substrate. For example, Patent Document 1 discloses a thermosetting resin composition containing a specific linearly modified polyimide resin and a thermosetting resin as a thermosetting resin composition having a low elastic modulus of a cured product. However, such an insulating resin material having such a low modulus of elasticity generally has a problem that the coefficient of linear thermal expansion is high and dimensional stability is poor. Since the circuit board is exposed to various environments such as a low temperature such as room temperature and a high temperature such as a reflow, if the coefficient of linear thermal expansion is high and the dimensional stability is poor, the insulating resin material in the circuit board repeats expansion and contraction, Cracks are generated by the deformation of the resulting substrate. As a method of suppressing the coefficient of linear thermal expansion to a low level, a method of compounding a large amount of an inorganic filler into an insulating resin material is known. However, if a large amount of an inorganic filler is blended with an insulating resin material, the elasticity of the insulating resin material becomes high this time, and it becomes difficult to suppress warpage of the substrate. Therefore, a practical insulating resin material satisfying both the requirements of low modulus of elasticity and low coefficient of linear thermal expansion is not always satisfactory.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-37083

SUMMARY OF THE INVENTION In consideration of the above-described phenomenon, the technical problem to be solved by the present invention is to provide an insulating resin material having high dimensional stability and less warping at the time of curing.

In order to solve the above problems, the inventors of the present invention have conducted intensive investigations and, as a result, have surprisingly found that even when a large amount of inorganic filler is blended in an insulating resin material containing a thermosetting resin and a specific polymer resin, So that an insulating resin material excellent in both of low elastic modulus and low linear thermal expansion coefficient can be obtained.

That is, the present invention includes the following contents.

[1] An insulating resin material comprising a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30 ° C or lower, wherein the content of the inorganic filler is 50 to 95% by mass relative to 100% by mass of the nonvolatile component in the insulating resin material , Insulating resin material.

[2] the cured product of the insulating resin material has a coefficient of linear thermal expansion of 3 to 30 ppm / ° C at 25 ° C to 150 ° C and a coefficient of linear thermal expansion of 5 to 32 ppm / ° C at 150 ° C to 220 ° C, The insulating resin material according to [1], wherein the cured product of the material has a modulus of elasticity at 25 캜 of 0.5 to 14 GPa.

[3] The cured product of the insulating resin material has a coefficient of linear thermal expansion of 3 to 10 ppm / DEG C at 25 DEG C to 150 DEG C and a coefficient of linear thermal expansion of 5 to 15 ppm / DEG C at 150 DEG C to 220 DEG C, The insulating resin material according to [1], wherein the cured product has a modulus of elasticity of 0.5 to 6 GPa at 25 캜.

(4) When the coefficient of linear expansion of the cured product of the insulating resin material at 25 ° C to 150 ° C is A (ppm / ° C) and the coefficient of linear thermal expansion at 150 ° C to 220 ° C is B (ppm / The insulating resin material according to [1], wherein 0? BA? 15.

(5) When the coefficient of linear expansion of the cured product of the insulating resin material at 25 ° C to 150 ° C is A (ppm / ° C) and the coefficient of linear thermal expansion at 150 ° C to 220 ° C is B (ppm / The insulating resin material according to [1], wherein 0?

[6] The insulating resin material according to [1], wherein the thermosetting resin is an epoxy resin.

[7] The insulating resin material according to [1], wherein the thermosetting resin is a liquid epoxy resin.

[8] The insulating resin material according to [1], wherein the content of the thermosetting resin is 1 to 15% by mass with respect to 100% by mass of the nonvolatile component in the insulating resin material.

[9] The insulating resin material according to [1], wherein the inorganic filler is silica.

[10] The insulating resin material according to [1], wherein the polymer resin has a number average molecular weight of 300 to 100,000.

[11] The insulating resin material according to [1], wherein the polymer resin has a number average molecular weight of 8,000 to 20,000.

[12] The insulating resin material according to [1], wherein the polymer resin has at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton.

[13] The insulating resin material according to [1], wherein the polymer resin has a butadiene skeleton, an imide skeleton and a urethane skeleton.

[14] The insulating resin material according to [1], wherein the content of the polymer resin is 1 to 30% by mass with respect to 100% by mass of the nonvolatile component in the insulating resin material.

[15] An adhesive film comprising an insulating resin material according to any one of [1] to [14] formed on a support.

[16] A sheet-shaped cured product obtained by thermally curing the insulating resin material according to any one of [1] to [14].

[17] An insulating resin material according to any one of [1] to [14], which is layered on a silicon wafer and thermally cured to form a sheet-like cured product on a silicon wafer, The sheet-like cured product according to [16], wherein the cured product is 5 mm.

[18] A printed wiring board comprising the insulating resin material according to any one of [1] to [14].

[19] A printed wiring board on which a conductive layer is formed on a sheet-like cured product as described in [16].

[20] A printed wiring board on which a conductive layer is formed on a sheet-like cured product according to [17].

[21] A wafer level chip size package comprising the insulating resin material according to any one of [1] to [14].

[22] A wafer level chip size package having a conductor layer formed on the sheet-like cured material as described in [16].

[23] A wafer level chip size package having a conductor layer formed on the sheet-like cured material as described in [17].

The present invention provides an insulating resin material having high dimensional stability and small warping at the time of curing.

[Insulating resin material]

The insulating resin material of the present invention is a resin composition containing a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30 캜 or lower, and may further contain a curing accelerator and other components as required. This will be described in detail below.

(a) Thermosetting resin

The thermosetting resin used in the present invention is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, a cyanate ester resin, and a benzoxazine resin. Among them, it is preferable to use an epoxy resin from the viewpoint of improving the plating adhesion.

The epoxy resin is not particularly limited, but it preferably contains an epoxy resin having two or more epoxy groups in one molecule. Specific examples thereof include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tertiary-butyl-catechol type epoxy resin, Naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, and halogenated epoxy resin. These may be used singly or in combination of two or more.

Among them, at least one selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, and an epoxy resin having a butadiene structure is preferably used as the epoxy resin. Further, the epoxy resin contains a liquid epoxy resin to further lower the modulus of elasticity of the cured product, thereby making it possible to reduce warpage at the time of curing. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 占 폚. The term "aromatic epoxy resin" in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When a liquid epoxy resin is used as the epoxy resin, the amount of the liquid epoxy resin is preferably 60 to 100 parts by mass, more preferably 75 to 100 parts by mass, more preferably 85 to 100 parts by mass based on 100 parts by mass of the entire epoxy resin More preferably by mass. Examples of commercially available epoxy resins include "jER828EL" (liquid bisphenol A type epoxy resin, epoxy equivalent 180) manufactured by Mitsubishi Chemical Corporation, "HP4032" (liquid naphthalene type epoxy resin, epoxy equivalent 151) manufactured by DIC Corporation, And the like.

Examples of the phenolic resin include, but are not limited to, phenol novolak resins, biphenyl skeleton-containing phenol resins, naphthalene skeleton-containing phenol resins, and triazine skeleton-containing phenol resins. As the phenol novolak resin, for example, " TD2090 " manufactured by DIC Corporation may, for example, be mentioned. Examples of the biphenyl skeleton-containing phenol resin include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Chemical Industries, Ltd. Examples of the naphthalene skeleton-containing phenol resin include "NHN", "CBN" and "GPH" manufactured by Nippon Kayaku Co., SN180, SN190, SN475, SN485, SN495, SN375 and SN395, manufactured by Shinnitetsu Chemical Co., EXB9500 " manufactured by DIC Corporation; And the like. Examples of the triazine skeleton-containing phenol-based curing agent include "LA3018", "LA7052", "LA7054", and "LA1356" manufactured by DIC Corporation.

Examples of the cyanate ester resin include, but are not limited to, novolac type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type A type, bisphenol F type, bisphenol S type, etc.) cyanate ester resins, and prepolymers obtained by partially trimerizing these. Specific examples of the cyanate ester resin include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenol novolak, cresol novolac, dicyclopentadiene structure-containing phenol resin, etc., and the like, such as bis (cyanate phenyl) thioether and bis , Prepolymers in which these cyanate resins are partially triarized, and the like. These may be used singly or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolac-type polyfunctional cyanate ester resins (PT30S, cyanate equivalent 124, manufactured by Longzoo Japan Co., Ltd.), and some or all of bisphenol A dicyanate are tri- (BA230S, cyanate equivalent 232) and dicyclopentadiene structure cyanate ester resin (DT-4000, DT-7000, manufactured by Longzoo Japan K.K.) have.

Examples of the benzooxazine-based resin include "B-a type benzoxazine photograph" and "B-m type benzoxazine photograph" manufactured by Shikoku Kasei Corporation.

The content of the thermosetting resin is preferably from 1 to 15 mass%, more preferably from 2 to 13 mass%, and even more preferably from 3 to 11 mass%, based on 100 mass% of the nonvolatile component in the insulating resin material.

(b) inorganic filler

The insulating resin material of the present invention can lower the coefficient of linear thermal expansion by containing an inorganic filler. The inorganic filler is not particularly limited and examples thereof include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica and spherical silica is preferable, and fumed silica and spherical silica are more preferable from the viewpoint of improving packing property, Silica is even more preferred. These may be used singly or in combination of two or more. Examples of commercially available spherical fused silica include "SO-C5", "SO-C2", and "SO-C1" manufactured by Adomax Japan.

The average particle diameter of the inorganic filler is not particularly limited. However, it is necessary to make low roughness in order to enable fine wiring formation after roughening treatment of the surface of the insulating layer, more preferably 3 mu m or less, more preferably 2 mu m or less, still more preferably 1 mu m or less, particularly preferably 0.8 mu m or less, from the viewpoint that the via shape , And particularly preferably not more than 0.6 mu m. On the other hand, when the resin composition is a resin varnish, the average particle diameter of the inorganic filler is preferably 0.01 占 퐉 or more, more preferably 0.03 占 퐉 or more from the viewpoint of increasing the viscosity of the varnish and preventing the handling property from being lowered More preferably 0.05 mu m or more, still more preferably 0.07 mu m or more, and particularly preferably 0.1 mu m or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba Seisakusho Co., Ltd. or the like can be used.

The content of the inorganic filler is preferably 50% by mass or more based on 100% by mass of the nonvolatile component in the insulating resin material in order to lower the coefficient of linear thermal expansion of the cured product. Since the insulating resin material of the present invention can maintain the modulus of elasticity low even when the coefficient of linear thermal expansion is increased, the content of the inorganic filler can be increased to 60 mass% or more, 70 mass% or more, or 80 mass% or more. On the other hand, the content of the inorganic filler is preferably 95% by mass or less based on 100% by mass of the nonvolatile component in the insulating resin material in that the cured product is prevented from being receded and the surface of the insulating layer after the roughening treatment is made low , More preferably 90 mass% or less.

The inorganic filler is preferably surface-treated with a surface treating agent, and specifically, examples thereof include an aminosilane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, an acrylate silane coupling agent Surface treatment with at least one surface treatment agent selected from coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds and titanate coupling agents . This makes it possible to improve the dispersibility and moisture resistance of the inorganic filler.

Examples of specific coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylamino Aminosilane coupling agents such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, -Glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidyloxypropyltrimethoxysilane, Epoxysilane-based coupling agents such as silylbutyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy Silane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane, and other mercapto Styryl silane coupling agents such as silane coupling agents and p-styryltrimethoxysilane, coupling agents such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethyl Methacryloxypropyltriethoxysilane, and 3-methacryloxypropyldiethoxysilane, isocyanate silane coupling agents such as 3-isocyanatepropyltrimethoxysilane, and bis ( (Triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, and other sulfide-based coupling agents such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryl Silane-based coupling agents such as trimethylolpropane trimethoxy silane, hydroxypropyl trimethoxy silane, imidazole silane, triazinilane and t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetra Methyldisilazane, hexaphenyldisilazane, Hexamethyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyl, 1,3-di-n-octyldimethylsilane, 1,3-dimethyltetramethyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl- Organosilazane compounds such as 1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane and tetramethyldisilazane, tetra-n -Butyl titanate dimer, titanium-i-propoxy octylen glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolamine), dihydroxy titanium bis lactate , Dihydroxybis (ammonium lactate) titanium, bis (dioctylpyrophosphate) ethylene titanate, Butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctylphosphate) oxyacetate titanate, tri- (Ditridecylphosphate) titanate, tetra (2,2-diaryloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, isopropyltri octanoyl titanate, isopropyl Isopropyltriisostearoyltitanate, isopropyltrimethoxysilane titanate, isopropyltrimethoxysilane titanate, isopropyltrimethoxysilane titanate, tricumyl phenyl titanate, isopropyltriisostearoyl titanate, isopropyl isostearoyldiacrylate titanate, isopropyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate , Isopropyltridodecylbenzenesulfonyltitanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethylaminoethyl) tita And titanate-based coupling agents such as nate. Of these, an aminosilane-based coupling agent, an epoxy silane-based coupling agent, a mercaptosilane-based coupling agent and an organosilazane compound are preferable, and an aminosilane-based coupling agent is more preferable. Examples of commercially available products include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., , KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., SZ-31 " (hexamethyldisilazane) manufactured by Kagaku Kogyo K.K. and the like.

It is preferable that the inorganic filler is surface-treated with a surface treatment agent and then added to the resin composition. In this case, the dispersibility of the inorganic filler can be further increased.

The surface treatment method is not particularly limited, and examples thereof include a dry method and a wet method. As a dry method, an inorganic filler is injected into a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is added dropwise or sprayed with stirring, and the mixture is further stirred and classified into a sieve. Thereafter, the surface treatment agent and the inorganic filler are dehydrated and condensed by heating to obtain an inorganic filler surface-treated with the surface treatment agent. As the wet method, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, followed by stirring, followed by filtration, drying and sieving. Thereafter, the surface treatment agent and the inorganic filler are dehydrated and condensed by heating to obtain an inorganic filler surface-treated with the surface treatment agent. It is also possible to use an integral brand method in which a surface treatment agent is added to the resin composition.

(c) a polymer resin having a glass transition temperature of 30 DEG C or lower

The insulating resin material of the present invention contains a polymer resin having a glass transition temperature of 30 占 폚 or lower, so that the modulus of elasticity of the cured product can be lowered and the peel strength of the conductor layer and the insulating layer can be improved. Further, the polymeric resin having a glass transition temperature of 30 캜 or lower is hardly changed in the linear thermal expansion coefficient in a wide temperature range of 25 캜 to 220 캜, and the difference in the coefficient of linear thermal expansion of the cured product can be suppressed low. For this reason, the glass transition temperature is more preferably 20 DEG C or lower, and further preferably 10 DEG C or lower. The lower limit value of the glass transition temperature is not particularly limited, but is generally -30 ° C or higher.

The polymer resin having a glass transition temperature of 30 占 폚 or less is not particularly limited and may include polymer resins having a butadiene skeleton, an amide skeleton, an imide skeleton, an acetal skeleton, a carbonate skeleton, an ester skeleton, a urethane skeleton, an acrylic skeleton or a siloxane skeleton have. Of these, it is preferable to use a polymer resin having at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton from the viewpoint of more flexibility and adhesion, , A polymer resin having at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton and having at least one skeleton selected from an amide skeleton, an imide skeleton and a urethane skeleton is more preferable. More preferably, it is a polymer resin having a butadiene skeleton, an imide skeleton and a urethane skeleton, a polymer resin having an acrylic skeleton, and a polymer resin having an imide skeleton and a siloxane skeleton. In the polymer resin having a butadiene skeleton, the content of the butadiene skeleton in the polymer resin is preferably 45 to 90 mass% (preferably 60 to 80 mass%). In the polymer resin having a siloxane skeleton, it is preferable that the content of the siloxane skeleton in the polymer is 40 to 80 mass% (preferably 50 to 75 mass%).

Here, the measurement of the glass transition temperature of the polymer resin can be carried out as follows. The polymer resin is coated on the PET film and heated at 180 캜 for 90 minutes to dry the solvent to give a film. The film was cut into test pieces each having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was carried out by the tensile weighting method using "EXSTAR TMA / SS6000" manufactured by Sanyo Chemical Industries, Ltd. under the trade name "EXSTAR TMA / SS6000". Specifically, after mounting the test piece on the above apparatus, the test piece is continuously measured twice under the measurement conditions of 1 g load and temperature raising rate of 5 deg. C / minute, and Tg is calculated in the second measurement.

The number average molecular weight of the polymer resin is preferably in the range of 300 to 100000, more preferably in the range of 800 to 80,000, more preferably in the range of 1500 to 60000, still more preferably in the range of 5000 to 40000 , And particularly preferably in the range of 8000 to 20,000. When the number average molecular weight is within this range, compatibility and flexibility in the insulating resin material can be achieved. The number average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the number average molecular weight by the GPC method was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K-804L / K-804L can be measured using a calibration curve of standard polystyrene at a column temperature of 40 DEG C by using chloroform or the like as the mobile phase.

Specific examples thereof include a polymer resin having a butadiene skeleton ("G-1000", "G-3000", "GI-1000", "GI-3000" manufactured by Nippon Soda Co., Ricon130 "," Ricon 142 "," Ricon 150 "," Ricon 657 ", and" Ricon 130 MA "manufactured by Dai-ichi Kogaku Kogyo K.K.)," Epophor AT501 " (Polymer resin described in JP-A No. 2006-37083) having a butadiene skeleton and a polyimide skeleton, a polymer resin having an acrylic skeleton ("SG-P3" manufactured by Nagase ChemteX Corporation, "SG-600LB SG-280, SG-790, SG-K2, SN-50, AS-3000E and ME-2000 manufactured by Negami Kogyo Co., Ltd.) .

The content of the polymer resin is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more based on 100% by mass of the nonvolatile component in the insulating resin material so as to lower the elastic modulus of the cured product desirable. On the other hand, the content of the polymer resin is preferably 30% by mass or less based on 100% by mass of the nonvolatile component in the insulating resin material, from the viewpoint of making uniform the cured product without compromising the compatibility of the resin varnish By mass, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

(d) Curing accelerator

The insulating resin material of the present invention can further effectively cure the thermosetting resin by further containing a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include an imidazole-based curing accelerator, an amine-based curing accelerator, a guanidine-based curing accelerator, and a phosphonium-based curing accelerator.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- Water, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 2-phenylimidazoline, And imidazole compounds and adducts of epoxy resins and the like.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) -Diazabicyclo [5.4.0] -7-undecene (hereinafter abbreviated as DBU), and the like.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like.

Examples of the phosphonium curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) Triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.

When the curing accelerator is used, the amount of the curing accelerator to be used is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass based on 100 parts by mass of the thermosetting resin.

(e) Other ingredients

In the insulating resin material of the present invention, other components may be blended as necessary within a range not hindering the effect of the present invention. Examples of the other components include organic fillers such as silicone powder, nylon powder, fluorine powder and rubber particles, thickeners such as orthobenzene and benzene, defoaming agents or leveling agents of silicone, fluorine, and high molecular weight, thiazole, Silane coupling agents, coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides And the like.

The insulating resin material of the present invention may be prepared by appropriately mixing the above components and further mixing them with a kneader such as a three roll, a ball mill, a bead mill, a sand mill, or a super mixer, a planetary mixer, For example, by kneading or mixing. Further, it can be prepared as a resin varnish by further adding an organic solvent.

Since the insulating resin material of the present invention can exhibit excellent performance in that the warp of the cured product can be reduced while enhancing the dimensional stability of the cured product, it is preferable to use the insulating resin material as a sheet-like cured product obtained by thermally curing the insulating resin material Do. The sheet-like cured product may be any thermally cured insulating resin material on the sheet, and the sheet-like cured product may be laminated on the circuit board.

The cured product of the insulating resin material of the present invention preferably has a coefficient of linear thermal expansion of 3 to 30 ppm / DEG C at 25 DEG C to 150 DEG C and a coefficient of linear thermal expansion at 150 DEG C to 220 DEG C of 5 To 32 ppm / ° C. The upper limit of the linear thermal expansion coefficient at 25 캜 to 150 캜 is more preferably 25 ppm / 캜 or less, still more preferably 20 ppm / 캜 or less, still more preferably 15 ppm / 캜 or less, and particularly preferably 10 ppm / 캜 or less. On the other hand, the lower limit of the coefficient of linear thermal expansion at 25 占 폚 to 150 占 폚 is not particularly limited, but is 3 ppm / 占 폚 or higher, 4 ppm / 占 폚 or higher, 5 ppm / The upper limit of the linear thermal expansion coefficient at 150 캜 to 220 캜 is more preferably 30 ppm / 캜 or less, still more preferably 25 ppm / 캜 or less, still more preferably 20 ppm / 캜 or less, and particularly preferably 15 ppm / Do. On the other hand, the lower limit of the coefficient of linear thermal expansion at 150 캜 to 220 캜 is not particularly limited, but is 5 ppm / 캜 or more, 6 ppm / 캜 or more, 7 ppm /

The cured product of the insulating resin material of the present invention preferably has a linear expansion coefficient at 25 캜 to 150 캜 at 150 캜 to 150 캜 and at 150 캜 to 220 캜 so as to reduce the fluctuation of the coefficient of linear thermal expansion and further improve the dimensional stability of the cured product. (Ppm / DEG C), and when the coefficient of linear thermal expansion at 150 DEG C to 220 DEG C is B (ppm / DEG C), 0? BA? 15 is preferable. More preferably, 0? B-A? 12, more preferably 0? B-A? 9, still more preferably 0 B-A? 6, and particularly preferably 0 B-A?

The cured product of the insulating resin material of the present invention preferably has a modulus of elasticity at 25 DEG C of from 0.5 to 14 GPa in order to reduce warpage of the cured product. The upper limit of the elastic modulus at 25 캜 is more preferably 12 GPa or less, further preferably 10 GPa or less, even more preferably 8 GPa or less, and particularly preferably 6 GPa or less. On the other hand, the lower limit value of the elastic modulus at 25 캜 is not particularly limited, but is 1 GPa or more, 2 GPa or more, and 3 GPa or more.

The warpage amount of the sheet-form cured product of the present invention is confirmed as follows. A circular silicon wafer having a thickness of 100 mu m and a diameter of 100 mm is prepared and an insulating resin material is layered on a silicon wafer and thermally cured to form a sheet cured product on a silicon wafer. Next, the laminate having the sheet-like cured product formed on the silicon wafer is pressed firmly with one finger from above the cured product at a room temperature (25 占 폚) with the silicon wafer being placed on a flat tabletop. Then, by measuring the distance between the edge of the silicon wafer on the diagonal line and a flat tabletop, the amount of warping of the laminate can be obtained. The amount of warping of the laminate at 25 DEG C is preferably 0 to 5 mm.

The form of the insulating resin material of the present invention is not particularly limited, but is suitably applied to a circuit board such as an adhesive film, a printed wiring board or a wafer level chip size package. The insulating resin material of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but it is generally preferable to use it in the form of an adhesive film industrially.

[Adhesive film]

The adhesive film of the present invention can be produced by a method known to a person skilled in the art, for example, by preparing a resin varnish obtained by dissolving an insulating resin material in an organic solvent, applying the resin varnish to a support using a die coater or the like, Or an organic solvent is dried by hot air blowing or the like to form a resin composition layer on a support, whereby an insulating resin material can be produced as an adhesive film having a layer formed thereon.

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

The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent (residual solvent amount) in the resin composition layer is, for example, 1 to 10% by mass or less, preferably 2 to 6% by mass or less. The amount of the organic solvent in the varnish, and the boiling point of the organic solvent. However, the resin composition layer can be formed by drying a varnish containing, for example, 30 to 60 mass% of organic solvent at 50 to 150 캜 for about 3 to 10 minutes have.

The thickness of the resin composition layer formed in the adhesive film is preferably not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 mu m, the resin composition layer preferably has a thickness of 10 to 200 mu m, more preferably 15 to 100 mu m, Mu m is more preferable.

Examples of the support include films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride, films of polyester such as polyethylene terephthalate (hereinafter, sometimes abbreviated as " PET "), polyethylene naphthalate, Film, polyimide film, and the like. In addition, a release paper or a metal foil such as copper foil and aluminum foil may be used. Above all, in view of versatility, a plastic film is preferable, and a PET film is more preferable. The support and the protective film to be described later may be subjected to a surface treatment such as a mud treatment or a corona treatment. In addition, the releasing treatment may be carried out with a release agent such as a silicone resin-based releasing agent, an alkyd resin-based releasing agent, or a fluororesin-based releasing agent. The thickness of the support is not particularly limited, but is preferably 10 to 150 mu m, more preferably 25 to 50 mu m.

On the surface of the resin composition layer on which the support is not closely adhered, a protective film corresponding to the support can be further laminated. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 占 퐉, preferably 5 to 20 占 퐉. By laminating a protective film, it is possible to prevent adhesion and scratches of dust on the surface of the resin composition layer. The adhesive film may be rolled and stored.

[Printed wiring board]

Examples of the printed wiring board of the present invention include a rigid circuit board, a flexible circuit board, a single-sided laminated board, a thin substrate and the like. An example of a method for producing a printed wiring board using the adhesive film produced as described above will be described.

First, the adhesive film is laminated (laminated) on one side or both sides of the inner layer circuit board by using a vacuum laminator. Examples of the substrate used for the inner layer circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the inner layer circuit board refers to a patterned conductor layer (circuit) formed on one or both surfaces of the substrate. Further, in the multilayered printed circuit board in which the conductor layer and the insulating layer are alternately laminated, the outermost layer of the multilayered printed circuit board has a conductor layer (circuit) patterned on one side or both sides thereof. . In addition, the surface of the conductor layer may be previously subjected to a roughening treatment by blackening treatment, copper etching, or the like.

In the case where the adhesive film has a protective film in the laminate, after removing the protective film, the adhesive film and the circuit board are preheated if necessary, and the adhesive film is laminated on the circuit board while being pressed and heated. In the adhesive film of the present invention, a method of laminating a circuit substrate under reduced pressure by a vacuum laminating method is suitably used. Condition of the laminate is not particularly limited, for example, contact bonding temperature (lamination temperature) of preferably 70 to 140 ℃, contact pressure (laminate pressure), for preferably 1 to ^{1lkgf / cm 2 (9.8 × 10} 4 To 107.9 × 10 ⁴ N / m ² ), and the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less with a compression time (laminating time) of preferably 5 to 180 seconds. The lamination method may be a batch method or a continuous method in a roll. Vacuum laminates can be carried out using commercially available vacuum laminators. As a commercially available vacuum laminator, there are, for example, a vacuum applicator manufactured by Nichigo Motton Co., Ltd., a vacuum-pressurized laminator manufactured by Mitsui Mining Co., Ltd., a vacuum-press type laminator manufactured by Hitachi, Ltd., a roll type dry coater made by Hitachi Industries, Ltd., Manufacturing vacuum laminator, and the like.

When the adhesive film is laminated on the inner layer circuit board and then cooled to about room temperature, when the support is peeled off, the adhesive film is peeled off, and the resin composition is thermally cured to form a cured product, whereby the insulating layer can be formed on the innerlayer circuit board. The conditions of the thermosetting may be appropriately selected depending on the kind and content of the resin component in the resin composition, but preferably 20 to 180 minutes at 150 to 220 캜, more preferably 30 to 120 Min. ≪ / RTI > After forming the insulating layer, if the support is not peeled off prior to curing, the support may be peeled off here if necessary. Like the thickness of the resin composition layer formed in the adhesive film, the thickness of the insulating layer preferably has a thickness of 10 to 200 mu m, more preferably 15 to 100 mu m, and more preferably 20 to 60 mu m Is more preferable.

Next, the insulating layer formed on the inner layer circuit board is perforated to form a via hole and a through hole. The drilling can be carried out by a known method such as drilling, laser, plasma, or the like, or by combining these methods as necessary. However, drilling with a laser such as a carbon dioxide gas laser or a YAG laser is most effective This is a common method. In the case where the support is not peeled off before the drilling, the support is peeled off here.

Next, the surface of the insulating layer is roughened. In the case of the harmonization treatment of the wet type, the swelling treatment by the swelling liquid, the harmonic treatment by the oxidizing agent, and the neutralization treatment by the neutralizing liquid are carried out in this order. . The wet roughening treatment is preferable in that the smear in the via hole can be removed while forming the anchors of the irregularities on the surface of the insulating layer. The swelling treatment with the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 캜 for 5 to 20 minutes (preferably at 55 to 70 캜 for 8 to 15 minutes). Examples of the swelling solution include an alkaline solution and a surfactant solution, and preferably an alkaline solution. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by Atotech Japan K.K., . The roughening treatment with an oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 to 80 占 폚 for 10 to 30 minutes (preferably at 70 to 80 占 폚 for 15 to 25 minutes). As the oxidizing agent, for example, an alkaline permanganic acid solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like can be given. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10 wt%. Examples of the commercially available oxidizing agent include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Limited, and Dosing Solution Securigans P manufactured by Atotech Japan K.K. The neutralization treatment with a neutralizing liquid is carried out by immersing in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably 35 to 45 ° C for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products include, for example, Reduction Solution · Securigans P manufactured by Atotech Japan Co., Ltd.

The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 220 to 1000 nm, more preferably 300 to 800 nm, from the viewpoint of formation of fine wiring and stabilization of the fill strength. Specifically, the Ra value can be obtained from the values obtained by setting the measurement range to 121 mu m x 92 mu m in the VSI contact mode and the 50x magnification lens using a non-contact surface roughness meter (WYKO NT3300 manufactured by Vico Instruments Inc.) have.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, ion plating and the like can be used. Examples of the wet plating include a method of forming a conductor layer by a combination of electroless plating and electrolytic plating, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and forming a conductor layer only by electroless plating .

The fill strength of the conductor layer and the insulating layer is preferably 0.5 kgf / cm or more, more preferably 0.6 kgf / cm or more, and further preferably 0.7 kgf / cm or more. The upper limit value of the peel strength is not particularly limited and is 1.5 kgf / cm or less, 1.0 kgf / cm or less, and the like.

As a method of forming the pattern thereafter, for example, a subtractive method, a semi-individual method and the like known to those skilled in the art can be used. By repeatedly repeating the series of the above steps a plurality of times, A printed wiring board may be formed. Thus, in the present invention, since the dimensional stability of the cured product is high and the warpage of the cured product is small, it can be suitably used for a printed circuit board such as a rigid circuit board, a flexible circuit board, a one-side laminated board, Since the dimensional stability of the cured product is high and the warpage of the cured product is small, it can be more suitably used as a build-up layer of the multilayer printed wiring board.

[Wafer level chip size package]

By using the insulating resin material of the present invention, it is possible to manufacture a wafer level chip size package excellent in dimensional stability and low warpage property. The insulating resin material may be laminated on both sides of the wafer level chip size package, or may be laminated on one side. The wafer-level chip-size package is designed with a variable structure, but can be largely classified into a fan-in structure and a fan-out structure. The thickness of the silicon wafer is preferably 50 to 150 占 퐉, more preferably 80 to 120 占 퐉, from the viewpoint of thinning.

As an example of a method for producing a wafer level chip size package having a fan-like structure using the adhesive film produced as described above, there is a method including the following steps.

(1) A step of forming a circuit and an electrode pad on a silicon wafer.

(2) A step of laminating the adhesive film of the present invention on a silicon wafer.

(3) A step of curing the adhesive film, peeling the support, performing perforation, and performing a desmear treatment to form a re-wiring layer by electroless plating and electrolytic plating.

(4) A step of repeating (2) and (3) above, if necessary, on the re-wiring layer.

(5) A step of forming a solder ball on the re-wiring layer.

(6) A step of performing dicing.

As an example of a manufacturing method of a wafer level chip size package having a different fan-like structure, there is a method described in, for example, Japanese Patent No. 3618330, and a method including the following steps can be mentioned.

(1) A step of producing a silicon wafer in which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed.

(2) A step of forming columnar electrodes on the upper surface of the electrode pad portion on the silicon wafer.

(3) A step of bonding and curing the adhesive film of the present invention on the columnar electrode surface side, and peeling the support to form an insulating layer.

(4) A step of exposing the upper surface of the columnar electrode by appropriately polishing and removing the insulating layer and the upper surface portion of the columnar electrode.

(5) A step of forming a solder ball on the upper surface of the exposed columnar electrode.

(6) A step of performing dicing.

As an example of a method for producing a wafer level chip size package of a fan-out structure using the adhesive film produced as described above, a method including the following steps can be mentioned.

(1) A step of dicing a silicon wafer and fabricating chip pieces.

(2) a step of fixing the chip reorganization on the support substrate through a film.

(3) A step of laminating the adhesive film of the present invention on the side of chip reorganization.

(4) A step of curing the film, peeling the support, performing perforation, and performing a desmear treatment to form a rewiring layer by electroless plating and electrolytic plating.

(5) If necessary, a step of further laminating the film.

(6) A step of forming a solder ball on the re-wiring layer.

As an example of a method of manufacturing a wafer level chip-size package having a different fan-out structure, there is a method described in, for example, Japanese Laid-Open Patent Publication No. 2005-167191, and a method including the following steps can be mentioned.

(1) A step of producing a silicon wafer in which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed.

(2) A step of producing a semiconductor chip piece by dicing.

(3) A step of widely arranging and fixing the semiconductor chips via the film on the support in a positional relationship with a distance between the semiconductor chips having a sufficient space for forming the fan-out ball array in the following step.

(4) A step of laminating the adhesive film of the present invention so as to fill the space between the semiconductor chips on the side where the semiconductor chip is fixed.

(5) The step of curing the adhesive film, peeling the support, etching the insulating layer on the pad of the semiconductor chip, forming the opening, and forming the conductive layer in the opening.

(6) A step of forming a fan-out pattern and an electrode on an insulating layer using a photoresist, and forming a solder ball on the electrode pad.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto. In the following, " part " means " part by mass ".

[Preparation of Polymer Resin A]

50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content of 100 wt%: Nippon Soda Co., Ltd.) , 23.5 g of Ip Sol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Sekiyu Kagaku Kabushiki Kaisha) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. The temperature was raised to 50 占 폚 at a uniform temperature, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was further added while stirring for about 3 hours. Subsequently, the reaction product was cooled to room temperature, and then 8.96 g of benzophenonetetracarboxylic dianhydride (equivalent amount of acid anhydride = 161.1 g / eq.), 0.07 g of triethylenediamine, 0.04 g of ethyldiglycol acetate Manufactured by Kokyo Kogyo Co., Ltd.) was added, and the temperature was raised to 130 캜 with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. The reaction product was cooled to room temperature and filtered through a 100-mesh filter column to obtain a polymer resin A having an imide skeleton, a urethane skeleton, and a butadiene skeleton.

Viscosity: 7.5 Pa · s (25 ° C, E type viscometer)

Acid value: 16.9 mg KOH / g

Solid content: 50 mass%

Number average molecular weight: 13723

Glass transition temperature: -10 ° C

Content ratio of polybutadiene structure moiety: 50 / (50 + 4.8 + 8.96) x 100 = 78.4 mass%.

[Example 1]

40 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent 180, " jER828EL ", Mitsubishi Kagaku K.K.), 40 parts of an imidazole derivative (2P4MZ manufactured by Shikoku Kasei K.K., 1 part of polymer resin A, 260 parts of polymer resin A, 300 parts of MEK, 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent 151, "HP4032" manufactured by DIC Corporation), phenylamino silane coupling agent (Shin-Etsu Chemical Co., 920 parts of spherical silica ("SO-C2", manufactured by Adomatex Kabushiki Kaisha, average particle diameter 0.5 탆) surface-treated with a high-speed rotary mixer to obtain a resin varnish Next, a polyethylene terephthalate film (thickness 38 탆, hereinafter, abbreviated as "PET film") was coated with a die coater so that the thickness of the resin composition layer after drying became 40 탆, (Average 100 DEG C) for 7 minutes to obtain an adhesive film.

[Example 2]

, 54 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation), 1 part of imidazole derivative ("2P4MZ" manufactured by Shikoku Chemicals Co., Ltd.), 400 parts of Polymer Resin A, Treated with 300 parts of MEK, 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation, " HP4032 ", phenylamino silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., " KBM573 & 920 parts of spherical silica ("SO-C2", average particle diameter 0.5 μm, manufactured by Adomatex K.K.) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. To obtain an adhesive film.

[Example 3]

("SO-C2", average particle diameter 0.5 μm) surface-treated with the phenylamino silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C5", average particle size of 1.6 mu m), which had been surface-treated with a phenylaminosilane coupling agent ("KBM573", manufactured by Shin-Etsu Kakuko Kogyo K.K.) An adhesive film was obtained in the same manner as in Example 1 except that the adhesive film was changed.

[Example 4]

("SO-C2", manufactured by Adomatex Kabushiki Kaisha, average particle size of 0.5 탆) surface-treated with a phenylamino silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., ("SO-C5", average particle size of 1.6 mu m), which had been surface-treated with a phenylaminosilane coupling agent (KBM573, manufactured by Shinetsu Kagakukogyo Co., Ltd.) , An adhesive film was obtained in the same manner as in Example 2. < tb > < TABLE >

[Comparative Example 1]

An adhesive film was obtained in the same manner as in Example 1 except that the spherical silica of Example 1 was changed to 50 parts.

[Referential Example 1]

40.3 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation), 0.5 part of imidazole derivative ("2P4MZ" manufactured by Shikoku Chemicals Co., Ltd.), 30 parts of MEK, (Epoxy equivalents: 151, manufactured by DIC Corporation, "HP4032", 10 parts), solid naphthalene type epoxy resin (epoxy equivalents 250, "HP6000" manufactured by DIC Corporation, 42.5 parts, a phenoxy resin solution , 14 parts of a mixed solution of MEK and cyclohexanone in a non-volatile content of 30% by mass, glass transition temperature of 120 占 폚), a phenol novolac resin (phenolic hydroxyl group equivalent 105, manufactured by DIC Corporation) , 75 parts of MEK varnish having a nonvolatile content of 60% by mass of "TD2090"), spherical silica surface-treated with phenylamino silane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., 625 parts of "SO-C2" (average particle diameter 0.5 mu m, manufactured by NOF Corporation) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Thereafter, an adhesive film was obtained in the same manner as in Example 1 .

[Measurement of modulus of elasticity]

The adhesive film was thermally cured at 180 DEG C for 90 minutes to obtain a sheet-like cured product. Next, the PET film was peeled off, and the tensile test of the cured product was carried out by a tensile tensile tester (manufactured by A & Day Co., Ltd.) in accordance with Japanese Industrial Standards (JIS K7127) Respectively.

[Evaluation of warpage]

The resin varnish described in Examples 1 to 4 and Comparative Example 1 was applied on a PET film with a die coater so as to have a thickness of 80 占 퐉 and dried at 80 to 120 占 폚 (average 100 占 폚) for 6 minutes to obtain a thermosetting resin composition layer To prepare an adhesive film. The adhesive film (80 mu m) was bonded to a silicon wafer (100 mu m) using a batch type vacuum laminator MVLP-500 (trade name, manufactured by Mitsubishi Chemical Co., Ltd.) and subjected to heat treatment (thermal curing) at 180 DEG C for 90 minutes. To observe the warp of the cured product. The end of the processed wafer was pressed, and the distance between the end of the wafer on the opposite side of the pressed portion and the ground was defined as the amount of warping. &Quot; was evaluated as "? &Quot;, and the warp amount was greater than 5 mm. The results are shown in Table 1.

[Measurement of linear thermal expansion coefficient]

The adhesive film was thermally cured at 190 DEG C for 90 minutes to obtain a film-like cured product. The cured product was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by tensile weighting using a thermomechanical analyzer (Thermo P1us TMA8310) manufactured by Rigaku Corporation. After the test piece was mounted on the above apparatus, the test piece was continuously measured twice under the conditions of a load of 1 g and a heating rate of 5 캜 / min. An average linear thermal expansion coefficient at 25 DEG C to 150 DEG C and an average linear thermal expansion coefficient at 150 DEG C to 220 DEG C in the second measurement were calculated.

[Evaluation of dimensional stability]

The average coefficient of linear thermal expansion at 25 DEG C to 150 DEG C of 30 ppm / DEG C or lower and the coefficient of linear thermal expansion at 150 DEG C to 220 DEG C or lower is 32 ppm / DEG C or less, ° C, the average coefficient of linear thermal expansion at 30 ° C / ° C is higher than 30ppm / ° C, or the coefficient of linear thermal expansion at 150 ° C to 220 ° C is higher than 32ppm / Was evaluated as " x ", when the average coefficient of linear thermal expansion of the steel sheet was larger than 100 ppm / DEG C or the coefficient of linear thermal expansion at 150 DEG C to 220 DEG C was larger than 200 ppm / DEG C.

[Measurement of arithmetic mean roughness (Ra) and peak intensity]

(1) Underlining of laminates

Both surfaces of a glass cloth-based epoxy resin double-sided copper-clad laminate [thickness of copper foil of 18 mu m, substrate thickness of 0.3 mm, R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.] were immersed in CZ8100 manufactured by Mech Chemical Co., .

(2) Adhesive film laminate

The above-mentioned adhesive film was laminated on both sides of a laminated plate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Mitsubishi Chemical Co., Ltd.). The laminate was subjected to pressure reduction for 30 seconds to set the air pressure to 13 hPa or less, and then to press at 100 DEG C and 0.74 MPa for 30 seconds.

(3) Curing of resin composition

The PET film was peeled from the laminated adhesive film, and the resin composition was cured at 180 DEG C for 30 minutes to form an insulating layer.

(4) Harmonization processing

The laminate having the insulating layer formed thereon was immersed in a swelling dip sealer P containing diethylene glycol monobutyl ether of Atotech Japan Corporation as a swelling liquid at 60 占 폚 for 5 minutes, And immersed in Concentrate Compact P (KMnO ₄ : 60 g / L, aqueous solution of NaOH: 40 g / L) at 80 ° C for 5 minutes, and finally as a neutralization liquid, reduction of Atotech Japan Co., Solution · Immersed at 40 ° C for 5 minutes in Secure Gens P. The laminate after the coarsening treatment was used as the evaluation board A.

(5) Plating by semiadiptive method

In order to form a circuit on the surface of the insulating layer, the evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ and then immersed in electroless copper plating solution. Subsequently, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 mu m. Next, the annealing was performed at 180 캜 for 60 minutes. This laminated plate after plating was used as evaluation board B.

(6) Measurement of arithmetic mean roughness (Ra)

The Ra value was obtained by using a non-contact surface roughness meter (" WYKO NT 3300 " manufactured by Vico Instruments Inc.) with a measurement range of 121 占 퐉 92 占 퐉 with a VSI contact mode and a 50x magnification lens. Then, measurement was made by obtaining an average value of 10 points.

(7) Measurement of Peel Strength

A portion of 10 mm in width and 100 mm in length was cut into a conductor layer of the evaluation board B and the one end was separated and held with a holding tool (Kabushiki Gaishi S-II, automobile type tester AC-50C-SL) , And the load (kgf / cm) when 35 mm was peeled in the vertical direction at a rate of 50 mm / min was measured.

From the results shown in Table 1, it can be seen that in Examples 1 to 4, the coefficient of linear thermal expansion is low, dimensional stability is excellent, and warping at the time of curing is suppressed. On the other hand, in Comparative Example 1, since the content of the inorganic filler is small, warping at the time of curing is reduced, but dimensional stability is deteriorated. In addition, it can be seen that Reference Example 1 does not use a polymer resin having a glass transition temperature of 30 DEG C or lower, and warps during curing and also has high dimensional stability.

By using the insulating resin material of the present invention, it became possible to provide an insulating resin material having high dimensional stability and small warpage at the time of curing.

Claims (23)

An insulating resin material containing a thermosetting resin, an inorganic filler and a polymer resin having a glass transition temperature of 30 DEG C or lower,
Wherein the content of the inorganic filler is 50 to 95 mass% with respect to 100 mass% of the nonvolatile component in the insulating resin material. The method according to claim 1, wherein the cured product of the insulating resin material has a coefficient of linear thermal expansion of 3 to 30 ppm / DEG C at 25 DEG C to 150 DEG C and a coefficient of linear thermal expansion of 5 to 32 ppm / DEG C at 150 DEG C to 220 DEG C, Wherein the cured product of the insulating resin material has an elastic modulus at 25 캜 of 0.5 to 14 GPa. The method according to claim 1, wherein the cured product of the insulating resin material has a coefficient of linear thermal expansion of 3 to 10 ppm / 占 폚 at 25 占 폚 to 150 占 폚, a coefficient of linear thermal expansion at 150 占 폚 to 220 占 폚 of 5 to 15 ppm / Wherein the cured product of the insulating resin material has a modulus of elasticity of 0.5 to 6 GPa at 25 占 폚. 2. The method according to claim 1, wherein the coefficient of linear expansion of the cured product of the insulating resin material at 25 캜 to 150 캜 is A (ppm / 캜) and the coefficient of linear thermal expansion at 150 캜 to 220 캜 is B (ppm / In one case, 0? BA? 15. 2. The method according to claim 1, wherein the coefficient of linear expansion of the cured product of the insulating resin material at 25 캜 to 150 캜 is A (ppm / 캜) and the coefficient of linear thermal expansion at 150 캜 to 220 캜 is B (ppm / In one case, 0? BA? 4. The insulating resin material according to claim 1, wherein the thermosetting resin is an epoxy resin. The insulating resin material according to claim 1, wherein the thermosetting resin is a liquid epoxy resin. The insulating resin material according to claim 1, wherein the content of the thermosetting resin is 1 to 15% by mass with respect to 100% by mass of the nonvolatile component in the insulating resin material. The insulating resin material according to claim 1, wherein the inorganic filler is silica. The insulating resin material according to claim 1, wherein the polymer resin has a number average molecular weight of 300 to 100,000. The insulating resin material according to claim 1, wherein the polymer resin has a number average molecular weight of 8000 to 20,000. The insulating resin material according to claim 1, wherein the polymer resin has at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton. The insulating resin material according to claim 1, wherein the polymer resin has a butadiene skeleton, an imide skeleton and a urethane skeleton. The insulating resin material according to claim 1, wherein the content of the polymer resin is 1 to 30 mass% with respect to 100 mass% of the nonvolatile component in the insulating resin material. An adhesive film comprising an insulating resin material according to any one of claims 1 to 14 formed on a support. A sheet-like cured product obtained by thermally curing the insulating resin material according to any one of claims 1 to 14. An insulating resin material as set forth in any one of claims 1 to 14 is layered on a silicon wafer and thermally cured to form a sheet cured product on a silicon wafer so that the amount of warpage at 25 캜 is 0 to 5 mm Cushion over sheet. A printed wiring board comprising the insulating resin material according to any one of claims 1 to 14. A printed wiring board in which a conductive layer is formed on the sheet-like cured product according to claim 16. A printed wiring board on which a conductor layer is formed on the sheet-like cured article according to claim 17. A wafer level chip size package comprising the insulating resin material according to any one of claims 1 to 14. A wafer level chip size package in which a conductor layer is formed on the sheet-like cured product according to claim 16. A wafer level chip size package having a conductor layer formed on the sheet-like cured article according to claim 17.