TWI618096B - Insulating resin material - Google Patents

Abstract

The problem to be solved by the present invention is to provide an insulating resin material having high dimensional stability and small warpage at the time of hardening.

The solution of the present invention is an insulating resin material containing a thermosetting resin, an inorganic filler, and an insulating resin material of a polymer resin having a glass transition temperature of 30 ° C or less, and a nonvolatile component in the insulating resin material. The mass%, the content of the inorganic filler is 50 to 95% by mass.

Description

Insulating resin material

The present invention relates to an insulating resin material. More specifically, the present invention relates to a circuit board using a printed wiring board of the insulating resin material, a wafer level wafer size package, or the like.

In an insulating resin material for a circuit board for a printed wiring board, a wafer level wafer size package, or the like, in order to suppress warpage of the substrate, a material having a low modulus of elasticity is required. For example, Patent Document 1 discloses a thermosetting resin composition containing a thermosetting resin composition of a specific linear modified polyimide resin and a thermosetting resin as a cured product having a low modulus of elasticity. However, such an insulating resin material having a low modulus of elasticity generally has a problem that the linear thermal expansion coefficient becomes high and the dimensional stability is poor. The circuit substrate is exposed to various conditions such as low temperature at room temperature, high temperature such as soldering, etc., if the coefficient of thermal expansion of the wire is high and the dimensional stability is poor, the insulating resin material in the circuit substrate repeatedly expands and contracts, resulting in The resulting substrate is distorted to cause cracks. As a method of suppressing the coefficient of thermal expansion of the wire, a method of blending a large amount of an inorganic filler into an insulating resin material is known. However, if a large amount of inorganic filler is blended in the insulating resin material, the elasticity of the insulating resin material is obtained. The modulus becomes high, and it is difficult to suppress the warpage of the substrate. Therefore, the practical insulating resin material which satisfies the requirements of both the low elastic modulus and the low linear thermal expansion coefficient is not necessarily satisfactory.

[Previous Technical Literature] [Patent Literature]

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

In view of the above circumstances, the problem to be solved by the present invention is to provide an insulating resin material having high dimensional stability and small warpage at the time of hardening.

In order to solve the above problems, the inventors of the present invention have repeatedly conducted intensive review, and as a result, 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, Also, the increase in the elastic modulus of the insulating resin material is suppressed, and an insulating resin material having excellent characteristics of both the low elastic modulus and the low linear thermal expansion coefficient can be obtained.

That is, the present invention includes the following contents.

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

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

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

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

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

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

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

[8] The insulating resin material as described in [1], wherein the insulating resin is relative to the insulating resin The nonvolatile content in the material is 100% by mass, and the content of the thermosetting resin is 1 to 15% by mass.

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

[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 one or more kinds of skeletons selected from the group consisting of a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a decane skeleton.

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

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

[15] A film which is formed by forming a layer of an insulating resin material according to any one of [1] to [14] on a support.

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

[17] The sheet-like cured product according to any one of [1] to [14], wherein the insulating resin material according to any one of [1] to [14] is formed on a tantalum wafer and thermally cured. When the sheet-like cured product is formed on the wafer, the amount of warpage at 25 ° C is 0 to 5 mm.

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

[19] A printed wiring board obtained by forming a conductor layer on the sheet-like cured product according to [16].

[20] A printed wiring board obtained by forming a conductor layer on the sheet-like cured product according to [17].

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

[22] A wafer level wafer size package in which a conductor layer is formed on a sheet-like cured product as described in [16].

[23] A wafer level wafer size package in which a conductor layer is formed on a sheet-like cured product as described in [17].

The present invention provides an insulating resin material which has high dimensional stability and small warpage at the time of hardening.

[Formation of the Invention] [insulating resin material]

The insulating resin material of the present invention contains a thermosetting resin, an inorganic filler, and a resin composition of a polymer resin having a glass transition temperature of 30 ° C or lower, and may further contain a curing accelerator, other components, and the like as necessary. The following description is detailed.

(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 resin, and benzo. Resin or the like. Among them, in order to improve the adhesion of the plating, it is preferred to use an epoxy resin.

The epoxy resin is not particularly limited, and preferably contains an epoxy resin having two or more epoxy groups in one molecule. Specific examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, and phenol novolak epoxy resin. Tributyl catechol epoxy resin, naphthalene epoxy resin, naphthyl ether epoxy resin, epoxy propyl amine epoxy resin, epoxy propyl ester epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, bismuth type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, An epoxy resin containing a spiro ring, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, or the like. These may be used in combination of one type or two or more types.

Among these, as the epoxy resin, it is preferably made 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. One or more selected from the group. Further, since the epoxy resin contains a liquid epoxy resin, the elastic modulus of the cured product can be further reduced, and the warpage at the time of curing can be reduced. 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 ° C. Furthermore, the aromatic epoxy described in the present invention A resin is an epoxy resin which has an aromatic ring structure in its molecule. In the case of using a liquid epoxy resin as the epoxy resin, when the total amount of the epoxy resin is 100 parts by mass, it is preferred to use 60 to 100 parts by mass of the liquid epoxy resin, and more preferably 75 to 100 parts by mass. It is especially good to use 85~100 parts by mass. As an example of the commercially available epoxy resin, "jER828EL" (liquid bisphenol A type epoxy resin, epoxy equivalent 180) manufactured by Mitsubishi Chemical Co., Ltd., and "HP4032" manufactured by DIC (liquid) are used. Naphthalene type epoxy resin, epoxy equivalent 151), and the like.

The phenolic resin is not particularly limited, and examples thereof include a phenol novolak resin, a phenol resin containing a biphenyl skeleton, a phenol resin containing a naphthalene skeleton, and three Skeleton phenolic resin, etc. As the phenol novolak resin, for example, "TD2090" manufactured by DIC Co., Ltd., or the like can be given. Examples of the phenol resin containing a biphenyl skeleton include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Minghe Chemical Co., Ltd. Examples of the phenol resin containing a naphthalene skeleton include "NHN", "CBN" and "GPH" manufactured by Nippon Kayaku Co., Ltd., and "SN170", "SN180" and "SN190" manufactured by Nippon Steel Chemical Co., Ltd. "SN475", "SN485", "SN495", "SN375" and "SN395", DIC (share) system "EXB9500", etc. As containing three Examples of the phenolic curing agent of the skeleton include "LA3018", "LA7052", "LA7054", and "LA1356" manufactured by DIC Corporation.

The cyanate resin is not particularly limited, and examples thereof include a novolac type (phenol novolak type, an alkylphenol novolak type, etc.) cyanate resin, a dicyclopentadiene type cyanate resin, and a double. a phenolic type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate resin, and a part thereof Prepolymers and the like. Specific examples of the cyanate resin include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene)), and 4 , 4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2 , 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane , 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) a bifunctional cyanate resin such as ether, a phenol novolac, a cresol novolak, a polyfunctional cyanate resin derived from a phenol resin containing a dicyclopentadiene structure, or the like, and a cyanate resin thereof through a part of three Prepolymers and the like. These may be used alone or in combination of two or more. Examples of the commercially available cyanate resin include a phenol novolac type polyfunctional cyanate resin (PT30S manufactured by LONZA Japan Co., Ltd., cyanate equivalent 124), and a part of bisphenol A dicyanate. Or all three A prepolymer which is a terpolymer (BA230S manufactured by LONZA Co., Ltd., cyanate equivalent 232), and a dicyclopentadiene structure containing a cyanate resin (DT-4000 manufactured by LONZA Japan Co., Ltd.) , DT-7000) and so on.

Benzo The resin is, for example, "Ba-type benzo" manufactured by Shikoku Chemicals Co., Ltd. "Bm type benzophenone "Wait.

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

(b) Inorganic filler

The insulating resin material of the present invention can reduce the linear thermal expansion coefficient by containing an inorganic filler. The inorganic filler is not particularly limited, and examples thereof include vermiculite, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitriding. Boron, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate and calcium zirconate. Among them, it is preferably an amorphous vermiculite, a crushed vermiculite, a molten vermiculite, a crystalline vermiculite, a synthetic vermiculite, a hollow vermiculite, a globular vermiculite or the like, and is preferably improved from the viewpoint of improving the filling property. It is a molten vermiculite or a globular vermiculite, and is preferably a spherical molten vermiculite. These may be used alone or in combination of two or more. Examples of the commercially available spherical fused vermiculite include "SO-C5", "SO-C2", and "SO-C1" manufactured by ADMATECHS.

The average particle diameter of the inorganic filler is not particularly limited. However, after roughening the surface of the insulating layer, in order to form fine wiring, it is necessary to have a low roughness and to cause laser processing. The viewpoint of the shape of the through hole is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, still more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the resin composition is made into a resin varnish, the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and the workability is lowered. It is particularly preferably 0.05 μm or more, more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle diameter of the above inorganic filler can be measured by a laser diffraction ‧ scattering method based on the Mie scattering theory. Specifically, by laser diffraction scattering In the particle size distribution measuring apparatus, the particle size distribution of the inorganic filler is determined on a volume basis, and the median diameter is determined as the average particle diameter. The measurement sample is preferably an inorganic filler which is ultrasonically dispersed in water. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba, Ltd. 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 reduce the linear thermal expansion coefficient of the cured product. In the insulating resin material of the present invention, since the elastic modulus can be maintained even if the linear thermal expansion coefficient is increased, the content of the inorganic filler can be increased to 60% by mass or more, 70% by mass or more, or 80% by mass or more. On the other hand, from the point of preventing the hardened material from becoming brittle and the surface of the insulating layer after the roughening treatment to be low in roughness, the content of the inorganic filler is 100% by mass relative to the nonvolatile content in the insulating resin material. It is preferably 95% by mass or less, more preferably 90% by mass or less.

The inorganic filler is preferably surface-treated with a surface treatment agent, and specifically, for example, more preferably an amine decane-based coupling agent, an epoxy decane-based coupling agent, a mercapto decane-based coupling agent, or a styrene-based decane-based coupling agent. One or more selected from the group consisting of an acrylate decane coupling agent, an isocyanate decane coupling agent, a thiodecane coupling agent, a vinyl decane coupling agent, a decane coupling agent, an organic decane compound, and a titanate coupling agent The surface treatment agent is surface treated. Thereby, the dispersibility or moisture resistance of the inorganic filler can be improved.

Specific examples of the coupling agent include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldiethoxymethyldecane, and N- Phenyl-3-aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N -Amino decane coupling agent such as -(2-aminoethyl)-3-aminopropyldimethoxymethyl decane, 3-glycidoxypropyltrimethoxydecane, 3-epoxy Propoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyl(dimethoxy)methylnonane, propylene oxide Epoxy decane coupling agent such as butyl trimethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-mercaptopropyltrimethoxy decane, 3-mercapto group a decyl decane coupling agent such as propyl triethoxy decane, 3-mercaptopropyl methyl dimethoxy decane, 11-fluorenyl undecyltrimethoxy decane, or the like, styrene-based trimethoxy decane or the like Vinyl decane coupling agent, 3-propenyloxypropyl trimethoxy decane, 3-methyl Propylene methoxypropyltrimethoxydecane, 3-methylpropenyloxypropyldimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropene oxime Acrylate decane coupling agent such as propyl diethoxy decane, isocyanate decane coupling agent such as 3-isocyanate propyl trimethoxy decane, bis(triethoxydecylpropyl) disulfide, double a thiononane coupling agent such as (triethoxydecylpropyl) tetrasulfide, methyltrimethoxydecane, octadecyltrimethoxydecane, phenyltrimethoxydecane, methacryloxypropane Trimethoxy decane, imidazolium, three a decane coupling agent such as decane or tert-butyltrimethoxydecane, hexamethyldiazepine, 1,3-divinyl-1,1,3,3-tetramethyldioxane, and six Phenyldioxane, triazane, cyclotriazane, octamethylcyclotetraazane, hexabutyldiazepine, hexaoctyldioxane, 1,3-diethyl Tetramethyldiazepine, 1,3-di-n-octyltetramethyldiazide, 1,3-diphenyltetramethyldiazepine, 1,3-dimethyltetraphenyl Indole, 1,3-diethyltetramethyldiazepine, 1,1,3,3-tetraphenyl-1,3-dimethyldiazepine, 1,3-dipropyl An organic sulfonium compound such as tetramethyldiazepine, hexamethylcyclotriazane, dimethylaminotrimethylsulfazane or tetramethyldiazepine, tetra-n-butyl titanate Dimer, titanium isopropoxyoctene glycolate, tetra-n-butyl titanate, titanium octene glycolate, diisopropoxy titanium bis(triethanolamine), dihydroxy titanium dilactate, Dihydroxybis(ammonium lactate) titanium, bis(dioctyl phosphate) ethylene titanate, bis(dioctyl phosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate , Tetra-n-butyl acid ester, tetrakis(2-ethylhexyl) titanate, tetraisopropyl bis(dioctyl phosphate) titanate, tetraoctyl bis(phosphonium phosphite) titanate, Tetrakis(2,2-diallyloxymethyl-1-butyl)bis(decyltridecyl)phosphite titanate, isopropyl succinyl titanate, isopropyl triiso Propyl phenyl titanate, isopropyl triisostearyl decyl titanate, isopropyl isostearyl decyl bis decyl decyl titanate, isopropyl dimethyl propylene decyl isostearyl Mercapto titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl dodecyl benzene sulfonate titanate, isopropyl tris(dioctyl phosphate) titanate A titanate coupling agent such as isopropyl tris(N-nonylaminoethyl ‧ amine ethyl) titanate or the like. Among these, an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, and an organic decane compound are preferable, and an amino decane coupling agent is preferable. As an example of a commercial product, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-) "Aminopropyltrimethoxydecane", "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

After the inorganic filler is surface-treated with a surface treating agent, it is preferably added to the resin composition. At this time, the dispersibility of the inorganic filler can be further improved.

The surface treatment method is not particularly limited, and examples thereof include a dry method or a wet method. As a dry method, an inorganic filler is added to a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, and further stirred, and classified by a sieve. Then, the surface treatment agent and the inorganic filler are dehydrated and condensed by heating to obtain an inorganic filler surface-treated with a surface treatment agent. As a wet method, a surface treatment agent is added while stirring the slurry of the inorganic filler and the organic solvent, and after stirring, filtration, drying, and sieving are carried out. Then, the surface treatment agent and the inorganic filler are dehydrated and condensed by heating to obtain an inorganic filler surface-treated with a surface treatment agent. Further, an integral blending method of adding a surface treating agent to the resin composition can also be used.

(c) Polymer resin with a glass transition temperature of 30 ° C or less

In the insulating resin material of the present invention, by containing a polymer resin having a glass transition temperature of 30 ° C or lower, the elastic modulus of the cured product can be lowered, and the peeling strength between the conductor layer and the insulating layer can be improved. Further, in the polymer resin having a glass transition temperature of 30 ° C or less, the linear thermal expansion coefficient is not easily changed in a wide temperature range of 25 ° C to 220 ° C, and the linear thermal expansion coefficient of the hardened material which can be depressed is poor. Therefore, the glass transition temperature is more preferably 20 ° C or lower, and particularly preferably 10 ° C or lower. The lower limit of the glass transition temperature is not particularly limited , but generally above -30 °C.

The polymer resin having a glass transition temperature of 30° C. or lower is not particularly limited, and examples thereof include a butadiene skeleton, a guanamine skeleton, a quinone imine skeleton, an acetal skeleton, a carbonate skeleton, an ester skeleton, and an amine group. A polymer resin such as a formate skeleton, an acrylic skeleton or a siloxane skeleton. Among them, from the viewpoint of more flexibility and adhesion, it is preferred to use a polymer resin having one or more kinds of skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a siloxane skeleton. Further, in order to improve heat resistance and compatibility, it is more preferable to have one or more kinds of skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a decane skeleton, and have a ruthenium skeleton and a ruthenium skeleton. A polymer resin of one or more kinds of skeletons selected from an amine skeleton and a urethane skeleton. More preferably, it is a polymer resin having a butadiene skeleton, a quinone imine skeleton, and a urethane skeleton, a polymer resin having an acrylic skeleton, and a polymer resin having a quinone imine skeleton and a siloxane skeleton. Further, in the polymer resin having a butadiene skeleton, the content of the butadiene skeleton in the polymer resin is preferably from 45 to 90% by mass (more preferably from 60 to 80% by mass). In the polymer resin having a siloxane skeleton, the content of the siloxane skeleton in the polymer is preferably 40 to 80% by mass (more preferably 50 to 75% by mass).

Here, the measurement of the glass transition temperature of the above polymer resin can be carried out as follows. The polymer resin was applied onto a PET film, and heated at 180 ° C for 90 minutes to dry the solvent to have a film shape. The film was cut into test pieces having a width of about 5 mm and a length of about 15 mm, and a thermomechanical analyzer SII Nano Technology Co., Ltd. "EXSTAR" was used. TMA/SS6000", thermomechanical analysis by tensile weighting. Specifically, after the test piece was attached to the above apparatus, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C/min, and Tg was calculated from the second measurement.

The number average molecular weight of the above polymer resin is preferably in the range of 300 to 100,000, more preferably in the range of 800 to 80,000, particularly preferably in the range of 1,500 to 60,000, and more preferably in the range of 5,000 to 40,000, particularly preferably 8000. The scope of 20000. By setting the number average molecular weight to this range, compatibility or flexibility in the insulating resin material can be achieved. Further, the number average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). For the number average molecular weight measured by the GPC method, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. can be used. As a column, chloroform or the like was used as a mobile phase, and the column temperature was measured at 40 ° C, and was calculated using a calibration curve of standard polystyrene.

Specific examples include a polymer resin having a butadiene skeleton ("G-1000", "G-3000", "GI-1000", "GI-3000" manufactured by Nippon Soda Co., Ltd., and Idemitsu Petrochemical "R-45EPI" system, "PB3600" and "Epofriend AT501" made by DAICEL Chemical Industry Co., Ltd., "Ricon130", "Ricon142", "Ricon150", "Ricon 657" and "Ricon130MA" manufactured by Gray Valley Co., Ltd. A polymer resin having a butadiene skeleton and a polyimine skeleton (polymer resin described in JP-A-2006-37083) and a polymer resin having an acrylic skeleton ("Ag-" manufactured by Nagase Chemtex Co., Ltd. P3", "SG-600LB" "SG-280", "SG-790", "SG-K2", "SN-50", "AS-3000E" and "ME-2000").

In order to reduce the elastic modulus of the cured product, the content of the polymer resin is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass based on 100% by mass of the nonvolatile component in the insulating resin material. More than % by mass. On the other hand, the content of the polymer resin is preferably 30% by mass based on 100% by mass of the nonvolatile component in the insulating resin material, from the viewpoint of producing a uniform cured product without impairing the compatibility of the resin varnish. The mass% or less is more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

(d) hardening accelerator

The insulating resin material of the present invention can efficiently 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, an lanthanum-based curing accelerator, and an lanthanum-based curing accelerator.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidin trimellitate, 1-cyanoethyl-2-phenylimidazole Triammonium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxyl Methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl An imidazole compound such as imidazoline or 2-phenylimidazoline, an adduct of an imidazole compound and an epoxy resin, or the like.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-tri (two). An amine compound such as methylaminomethyl)phenol or 1,8-diazabicyclo[5.4.0]-7-undecene (hereinafter abbreviated as DBU).

Examples of the oxime-based hardening accelerator include cyanogen, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-tolyl) fluorene, and dimethyl group. Anthracene, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1, 5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1- Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like.

Examples of the oxime-based hardening accelerator include triphenylphosphine, lanthanum borate, tetraphenylphosphonium tetraphenyl borate, n-butyl fluorene tetraphenyl borate, and tetrabutyl citrate. -methylphenyl)triphenylphosphonium thiocyanate, four Phenylguanidine 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, per 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 needed within the range not impairing the effects of the present invention. Examples of other components include organic fillers such as strontium powder, nylon powder, fluorine powder, and rubber particles, tackifiers such as Orben and Benton, and polyfluorene-based and fluorine-based compounds. , a defoaming agent or a leveling agent for a polymer system, an adhesion imparting agent such as a thiazole system, a triazole system or a decane coupling agent, a phthalocyanine blue, a phthalocyanine green, an iodine green, a bisazo yellow, a carbon black, or the like. A coloring agent, an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxygenated flame retardant, a flame retardant such as a metal hydroxide, and the like.

The insulating resin material of the present invention can be suitably mixed by the above-mentioned components, and if necessary, by a mixing means such as a three-roller, a ball mill, a bead mill, a sand mill, or the like, or a super mixer or a planetary mixer. The means are prepared by mixing or mixing. Further, an organic solvent may be further added to prepare a resin varnish.

Although the insulating resin material of the present invention improves the dimensional stability of the cured product, it is excellent in performance for reducing the warpage of the cured product, and therefore it is suitable to use a sheet-like cured product which is obtained by thermally hardening the insulating resin material. . Furthermore, the so-called flaky cured material is as long as it is an insulating resin material. The material may be heat-hardened into a sheet, and the laminate may be a sheet-like cured product.

In order to improve the dimensional stability of the cured product, the cured product of the insulating resin material of the present invention has a linear thermal expansion coefficient of 3 to 30 ppm/° C. at 25° C. to 150° C., and a linear thermal expansion coefficient of 5° at 150° C. to 220° C. 32 ppm / ° C is preferred. The upper limit of the linear thermal expansion coefficient at 25 ° C to 150 ° C is preferably 25 ppm / ° C or less, more preferably 20 ppm / ° C or less, particularly preferably 15 ppm / ° C or less, particularly preferably 10 ppm / ° C or less. On the other hand, the lower limit of the linear thermal expansion coefficient at 25 ° C to 150 ° C is not particularly limited, and is 3 ppm / ° C or more, 4 ppm / ° C or more, 5 ppm / ° C or more. Further, the upper limit of the linear thermal expansion coefficient at 150 ° C to 220 ° C is more preferably 30 ppm / ° C or less, particularly preferably 25 ppm / ° C or less, more preferably 20 ppm / ° C or less, and particularly preferably 15 ppm / ° C or less. On the other hand, the lower limit of the linear thermal expansion coefficient at 150 ° C to 220 ° C is not particularly limited, and is 5 ppm / ° C or more, 6 ppm / ° C or more, 7 ppm / ° C or more.

The cured product of the insulating resin material of the present invention further increases the dimensional stability of the cured product in order to reduce the linear thermal expansion coefficient in the range of 25 ° C to 150 ° C and 150 ° C to 220 ° C, and will be at 25 ° C to 150 ° C. The coefficient of linear expansion is taken as A (ppm/°C), and when the coefficient of linear thermal expansion at 150 ° C to 220 ° C is taken as B (ppm / ° C), it is preferably 0 ≦ BA ≦ 15, more preferably 0 ≦ BA ≦ 12, It is especially good for 0≦BA≦9, especially for 0≦BA≦6, and especially for 0≦BA≦4.

In the cured product of the insulating resin material of the present invention, the elastic modulus at 25 ° C is preferably 0.5 to 14 GPa in order to reduce the warpage of the cured product. At 25 ° C The upper limit of the elastic modulus is more preferably 12 GPa or less, particularly preferably 10 GPa or less, particularly preferably 8 GPa or less, and particularly preferably 6 GPa or less. On the other hand, the lower limit of the elastic modulus at 25 ° C is not particularly limited, and is 1 GPa or more, 2 GPa or more, and 3 GPa or more.

The amount of warpage of the sheet-like cured product of the present invention was confirmed as follows. A circular tantalum wafer having a thickness of 100 μm and a diameter of 100 mm was prepared, and a layer of an insulating resin material was formed on the tantalum wafer to be thermally cured to form a sheet-like cured product on the tantalum wafer. Next, a laminate having a sheet-like cured product formed on the tantalum wafer is placed at a room temperature (25 ° C) on a flat table so that the tantalum wafer becomes the lower surface, and the hardened object is pressed against the end with a finger. . The amount of warpage of the laminate can be determined by measuring the distance between the end of the tantalum wafer on the diagonal and the flat table. The amount of warpage of the laminate at 25 ° C is preferably 0 to 5 mm.

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

[Next film]

The adhesive film of the present invention can be prepared by dissolving an insulating resin material in an organic solvent, for example, by dissolving an insulating resin material in an organic solvent, and applying the resin varnish to a support by using a die coater or the like. The organic solvent is dried by heating or hot air blowing or the like, and by forming a resin composition layer on the support, it is possible to manufacture an insulating tree formed on the support. A film of the layer of the lipid material.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol B. Acetate such as acid ester, cellulolytic agent, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene or xylene, dimethylformamide, dimethylacetamide, N a guanamine-based solvent such as methylpyrrolidone or the like. The organic solvent may be used in combination of two or more kinds.

The drying condition is not particularly limited, and 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, and is dried. Although it varies depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, the varnish containing 30 to 60% by mass of the organic solvent may be dried at 50 to 150 ° C for about 3 to 10 minutes to form a resin. Composition layer.

The thickness of the resin composition layer formed in the film is preferably more than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the resin composition layer preferably has a thickness of 10 to 200 μm, and more preferably 15 to 100 μm from the viewpoint of film formation. Good for 20~60μm.

Examples of the support include a film of a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, or a polyethylene terephthalate (hereinafter referred to as "PET") or polyethylene naphthalate. Various plastic films such as ester film, polycarbonate film, and polyimide film. Further, a release paper, a metal foil such as a copper foil or an aluminum foil, or the like can be used. Among them, from the viewpoint of versatility, a plastic film is preferred, and a PET film is more preferred. For the support and the following The protective film can also be subjected to a surface treatment such as matting treatment or corona treatment. Further, the mold release treatment can be carried out by using a release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent. The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

The protective film of the support can be further laminated on the surface of the resin composition layer where the support is not adhered. The thickness of the protective film is not particularly limited and is, for example, 1 to 40 μm, preferably 5 to 20 μm. By laminating the protective film, adhesion or damage to the surface of the resin composition layer by waste or the like can be prevented. The film can then be wound into a cylindrical shape 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, and a thin substrate. An example of a method of manufacturing a printed wiring board using the adhesive film manufactured as described above will be described.

First, a film is laminated (laminated) on one or both sides of the inner layer circuit substrate using a vacuum laminator. Examples of the substrate used for the inner layer circuit board 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 as used herein refers to a conductor layer (circuit) formed by patterning on one surface or both surfaces of the substrate as described above. Further, in the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, one or both sides of the outermost layer of the multilayer printed wiring board are patterned. The conductor layer (circuit) is also included in the inner layer circuit substrate as referred to herein. Further, the surface of the conductor layer may be subjected to a roughening treatment in advance by a blackening treatment, copper etching or the like.

In the above-mentioned lamination, when the adhesive film has a protective film, after the protective film is removed, the adhesive film and the circuit substrate are preheated as needed, and the film is laminated on the circuit board while being pressed and heated. In the adhesive film of the present invention, a method of laminating on a circuit substrate under reduced pressure by vacuum lamination is preferably employed. The conditions for the lamination are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably 1 to 11 kgf/cm ² (9.8 × 10 ^{4 ).} ~107.9×10 ⁴ N/m ² ), the pressure-bonding time (lamination time) is preferably 5 to 180 seconds, and it is preferred to carry out lamination under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type by a roll. The vacuum lamination system can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum press machine manufactured by Nichigo-Morton Co., Ltd., a vacuum press laminator made by a machine manufacturer, and a dry roll coater manufactured by Hitachi Industrial Co., Ltd. , Hitachi AIC (share) vacuum laminator and so on.

After laminating the film on the inner layer circuit board, the film is cooled to room temperature, and then peeled off, and the resin composition is thermally cured to form a cured product, which is an inner layer circuit board. An insulating layer is formed thereon. The conditions of the heat curing can be appropriately selected according to the kind and content of the resin component in the resin composition, and are preferably 150 ° C to 220 ° C, 20 minutes to 180 minutes, more preferably 160 ° C to 210 ° C, 30 Choose from a range of ~120 minutes. After forming the insulating layer, the support is not peeled off before hardening When necessary, the support may be peeled off as needed. The thickness of the insulating layer is preferably 10 to 200 μm in thickness, similarly to the thickness of the resin composition layer formed in the film, and more preferably 15 to 100 μm, particularly preferably 20 from the viewpoint of film formation. ~60μm.

Next, the insulating layer formed on the inner layer circuit substrate is subjected to a hole drilling process to form a through hole and a through hole. The hole drilling process can be performed by well-known methods such as drilling, laser, plasma, etc., and can be combined as needed, but the laser drilling process such as carbon dioxide laser and YAG laser is the most common. Methods. When the support is not peeled off before the hole processing, the support is peeled off from this.

Next, the surface of the insulating layer is roughened. In the case of the dry roughening treatment, a plasma treatment or the like may be mentioned, and in the case of the wet roughening treatment, the swelling treatment by the swelling liquid, the roughening treatment by the oxidizing agent, and the like may be mentioned in the order of the wet roughening treatment. The method of neutralization treatment with liquid. The wet roughening treatment method is preferable in that the anchor in the through hole is removed while the anchor having irregularities is formed on the surface of the insulating layer. The swelling treatment by the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably, immersing at 55 to 70 ° C for 8 to 15 minutes). The swelling solution may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution. Examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swellable liquid include, for example, a swell-impregnated Securiganth P (Swelling Dip Securiganth P) manufactured by ATOTECH Co., Ltd., and a Schilling Dip Securiganth SBU (Swelling Dip Securiganth SBU). The oxidizing agent is etched by oxidizing the insulating layer at 60 to 80 ° C. The solution is carried out for 10 to 30 minutes (preferably, immersion at 70 to 80 ° C for 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably from 5 to 10% by weight. The commercially available oxidizing agent is, for example, an alkaline permanganic acid solution such as Concentrate Compact CP or Dosing Solution Securiganth P manufactured by ATOTECH Japan Co., Ltd. The insulating layer is immersed in the neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably immersed at 35 to 45 ° C for 3 to 8 minutes) by a neutralization treatment of the neutralizing liquid. The neutralization liquid is preferably an acidic aqueous solution, and a commercially available product is ATOTECH Japan's Reduction Solution Securigand P.

The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably from 220 to 1,000 nm, more preferably from 300 to 800 nm, from the viewpoint of the point of formation of the fine wiring and the stability of the peel strength. Specifically, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by VEECO Instruments Co., Ltd.), the Ra value can be obtained by a value obtained by a measurement range of 121 μm × 92 μm by a VSI contact mode and a 50-fold lens.

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

The peeling 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 particularly preferably 0.7 kgf/cm or more. The upper limit 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 subsequent pattern, for example, a subtractive method, a semi-additive method, or the like, which is well known in the art, may be used, and by repeating the above-described series of steps several times, a plurality of layers may be formed with an additional layer. Multilayer printed wiring board. In the present invention, the cured product has high dimensional stability and a small warpage of the cured product, and is applicable to a printed wiring board such as a rigid circuit board, a flexible circuit board, a single-sided laminated board, or a thin substrate. In particular, even if a plurality of layers are laminated, since the size of the cured product is high in stability and the warpage of the cured product is small, it is more suitable as an additional layer of the multilayer printed wiring board.

[Wafer Level Wafer Size Package]

By the insulating resin material of the present invention, a wafer level wafer size package excellent in dimensional stability and low warpage can be produced. The insulating resin material can be laminated on both sides of the wafer level wafer size package, or laminated on one side. In the wafer level wafer size package, various configurations are examined, which can be roughly classified into a fan-in structure and a fan-out structure. The thickness of the germanium wafer is preferably from 50 to 150 μm, more preferably from 80 to 120 μm, from the viewpoint of film formation.

As an example of a method of manufacturing a wafer level wafer size package using a bonding film manufactured as described above, a method including the following steps is exemplified.

(1) The step of forming a circuit and an electrode pad on the wafer.

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

(3) A step of curing the film, peeling off the support, performing opening, performing desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.

(4) Repeat the steps (2) and (3) above the wiring layer as needed.

(5) A step of forming a solder ball on the rewiring layer.

(6) The step of cutting.

An example of a method of manufacturing a wafer-level wafer-size package of another fan-in structure is, for example, a method described in Japanese Patent No. 3618330, and a method including the following steps.

(1) A step of fabricating a circuit element having a specified function and forming a plurality of electrode pads electrically connected to the circuit element.

(2) A step of forming a columnar electrode on the electrode pad portion on the wafer.

(3) A step of bonding the adhesive film of the present invention to the surface of the columnar electrode surface to be cured, peeling off the support, and forming an insulating layer.

(4) A step of suitably grinding and removing the insulating layer and the upper surface of the columnar electrode to expose the upper surface of the columnar electrode.

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

(6) The step of cutting.

An example of a method of manufacturing a wafer level wafer size package using a bonding film manufactured as described above to fabricate a fan-out structure includes the following steps method.

(1) The step of cutting the wafer and making individual wafers.

(2) a step of fixing individual wafer sheets to a support substrate via a film.

(3) A step of laminating the adhesive film of the present invention from the individual sheet side of the wafer.

(4) A step of hardening a film, peeling off the support, performing opening, performing desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.

(5) The step of laminating the film as needed.

(6) A step of forming a solder ball on the rewiring layer.

An example of a method of manufacturing a wafer-level wafer-size package of another fan-out structure is, for example, a method described in JP-A-2005-167191, and a method including the following steps.

(1) A step of fabricating a circuit element having a specified function and forming a plurality of electrode pads electrically connected to the circuit element.

(2) A step of forming individual wafers of semiconductor wafers by dicing.

(3) A step of widely arranging and fixing the semiconductor wafer via the film on the support in such a manner that the distance between the semiconductor wafers has a sufficient space for forming a fan-out ball array in a subsequent step.

(4) A step of laminating the adhesive film of the present invention from the side of the semiconductor wafer to be fixed to fill the semiconductor wafer.

(5) curing the film, peeling off the support, etching the insulating layer on the pad of the semiconductor wafer, forming an opening, and forming a conductive layer in the opening Step.

(6) Using a photoresist, a fan-out pattern and an electrode are formed on the insulating layer, and a solder ball is formed on the electrode pad.

[Examples]

Hereinafter, the present invention will be described in more detail by way of the examples and comparative examples. In addition, the "parts" described below mean "parts by mass".

[Manufacture of Polymer Resin A]

G-3000 (2-functional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq., solid content 100 wt%: manufactured by Nippon Soda Co., Ltd.) 50 g mixed in a reaction vessel Ipzole 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 g and dibutyltin laurate (0.005 g) were uniformly dissolved. When it was uniform, the temperature was raised to 50 ° C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) was further added while stirring, and the reaction was carried out for about 3 hours. Next, after cooling the reaction mixture to room temperature, diphenyl ketone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g / eq.) 8.96 g, triethylene glycol diamine 0.07 g and ethyl digan were added thereto. 40.4 g of alcohol acetate (manufactured by DAICEL Chemical Industry Co., Ltd.) was heated to 130 ° C while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm ^-1 was confirmed by FT-IR. The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and after the reaction product was cooled to room temperature, it was filtered through a 100-mesh filter cloth to obtain a quinone imine skeleton, a urethane skeleton, and a butadiene skeleton. Polymer resin A.

Viscosity: 7.5Pa ‧ (25 ° C, E-type viscometer)

Acid value: 16.9 mgKOH/g

Solid content: 50% by mass

Number average molecular weight: 13723

Glass transfer temperature: -10 ° C

The content of the polybutadiene structural portion was 50/(50 + 4.8 + 8.96) × 100 = 78.4% by mass.

[Example 1]

40 parts of mixed liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "JER828EL" manufactured by Mitsubishi Chemical Corporation), imidazole derivative (2P4MZ manufactured by Shikoku Kasei Co., Ltd.), 2-phenyl-4 -1 part of methylimidazole), 260 parts of polymer resin A, 300 parts of MEK, liquid naphthalene type epoxy resin (epoxy equivalent 151, 20 parts of "HP4032" made by DIC), phenylamino decane system 920 parts of spherical vermiculite ("SO-C2" manufactured by ADMATECHS Co., Ltd., average particle size 0.5 μm) treated by a coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and uniformly dispersed by a high-speed rotary mixer In order to produce a resin varnish, a polyethylene terephthalate film (thickness: 38 μm, hereinafter abbreviated as "PET film") was applied by a die so that the thickness of the dried resin composition layer was 40 μm. The cloth was coated and dried at 80 to 120 ° C (average 100 ° C) for 7 minutes to obtain a film.

[Embodiment 2]

54 parts of a mixed liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "JER828EL" manufactured by Mitsubishi Chemical Corporation), 1 part of an imidazole derivative ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd.), polymer resin A 400 parts, 300 parts of MEK, liquid naphthalene type epoxy resin (epoxy equivalent 151, 20 parts of "DIC403" made by DIC), phenylamino decane-based coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573") 920 parts of spherical vermiculite ("SO-C2" manufactured by ADMATECHS Co., Ltd., average particle diameter: 0.5 μm), which was surface-treated, and uniformly dispersed by a high-speed rotary mixer to produce a resin varnish. In the same manner as in Example 1, a film was obtained.

[Example 3]

A spherical vermiculite ("DMA-C2" manufactured by ADMATECHS Co., Ltd.) having a phenylamino decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) of Example 1 has an average particle diameter of 0.5. Μm) was changed to a spheroidal vermiculite ("SO-C5" manufactured by ADMATECHS Co., Ltd., average particle size 1.6 μm) which was surface-treated with a phenylamino decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). A film of the adhesive film was obtained in the same manner as in Example 1 except for the above.

[Example 4]

A spherical vermiculite ("DMA-C2" manufactured by ADMATECHS Co., Ltd.) having a surface area of a phenylamino decane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") of Example 2, average particle diameter 0.5 μm) changed to phenylamino decane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573" In the same manner as in Example 2 except that the spherical vermiculite ("SO-C5" manufactured by ADMATECHS Co., Ltd., average particle diameter: 1.6 μm) was surface-treated.

[Comparative Example 1]

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

[Reference Example 1]

40.3 parts of a mixed liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "jer828EL" manufactured by Mitsubishi Chemical Corporation), 0.5 parts of an imidazole derivative ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd.), and 30 parts of MEK. 10 parts of liquid naphthalene type epoxy resin (epoxy equivalent 151, "HP4032" made by DIC), 42.5 parts of solid naphthalene type epoxy resin (epoxy equivalent 250, "HP6000" manufactured by DIC) Phenoxy resin solution (made by Nippon Epoxy Resin Co., Ltd., "YX6954", a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass, glass transfer temperature of 120 ° C), 14 parts, phenol novolak resin (phenol A hydroxyl group equivalent of 105, DIC (shares), "TD2090", 60% by mass of MEK varnish, 75 parts by weight, and a phenylamino decane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 625 parts of a surface-treated spherical vermiculite ("SO-C2" manufactured by ADMATECHS Co., Ltd., average particle diameter: 0.5 μm) was uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Then, a film of the adhesive film was obtained in the same manner as in Example 1.

[Measurement of elastic modulus]

The above-mentioned adhesive film was thermally cured at 180 ° C for 90 minutes to obtain a flaky cured product. Next, the PET film was peeled off, and the tensile modulus of the cured product was measured by a Tensilon universal testing machine (manufactured by A&D Co., Ltd.) in accordance with Japanese Industrial Standards (JIS K7127), and the elastic modulus of the cured product was measured.

[evaluation of warping]

On the PET film, the resin varnish described in Examples 1 to 4 and Comparative Example 1 was applied to a thickness of 80 μm, coated with a die coater, and dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a PET varnish. The thermosetting resin is composed of a layer, and a film is produced. The batch film (80 μm) was bonded to a tantalum wafer (100 μm) by a batch type vacuum pressure laminator MVLP-500 (manufactured by Kosei Seisakusho Co., Ltd., and the film was baked at 180 ° C for 90 minutes. Heat treatment (thermal hardening), and observe whether the hardened material is warped. The end portion of the wafer after the above treatment is pressed, and the distance between the end portion of the wafer on the opposite side of the pressed portion and the ground is regarded as the amount of warpage. When the amount of warpage is 0 to 5 mm, it is evaluated as "○", and when the amount of warpage is greater than 5 nm, "x" is evaluated. The results are shown in Table 1.

[Determination of linear thermal expansion coefficient]

The adhesive film was thermally cured at 190 ° C for 90 minutes to obtain a film-like cured product. The cured product was cut into a test piece having a width of 5 mm and a length of 15 mm, and subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (Thermo Plu s TMA8310) manufactured by RIGAKU. After the test piece was attached to the above apparatus, the load was measured at a load of 1 g and a temperature increase rate of 5 ° C/min. The measurement was continuously performed twice under the conditions. The average linear thermal expansion coefficient at 25 ° C to 150 ° C and the average linear thermal expansion coefficient at 150 ° C to 220 ° C in the second measurement were calculated.

[Evaluation of dimensional stability]

The above average linear thermal expansion coefficient at 25 ° C to 150 ° C is 30 ppm / ° C or less, and the average linear thermal expansion coefficient of 32 ppm / ° C or less at 150 ° C to 220 ° C is evaluated as "○", and the above is at 25 ° C to 150 ° C. The average linear thermal expansion coefficient is greater than 30 ppm/° C. or the average linear thermal expansion coefficient at 150 ° C to 220 ° C is greater than 32 ppm / ° C. The average thermal expansion coefficient at 25 ° C to 150 ° C is greater than 100 ppm / ° C or The average linear thermal expansion coefficient of 150 ° C to 220 ° C was more than 200 ppm / ° C and was evaluated as "X".

[Measurement of arithmetic mean roughness (Ra) and peel strength] (1) Base treatment of laminate

The glass cloth substrate epoxy resin double-sided copper-clad laminate [copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Co., Ltd. R5715ES] was immersed in the CZ8100 manufactured by MEC Co., Ltd. to perform copper surface. Coarse processing.

(2) followed by lamination of the film

The above-mentioned adhesive film was laminated on both surfaces of the laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Konica Minolta Seisakusho Co., Ltd.). The laminate was depressurized for 30 seconds to have a gas pressure of 13 hPa or less, and then pressure-bonded at 30 seconds, 100 ° C, and a pressure of 0.74 MPa.

(3) Hardening of resin composition

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

(4) roughening treatment

The laminate in which the insulating layer was formed was immersed in a Swelling Dip Securigand P containing diethylene glycol monobutyl ether in ATOTECH Japan Co., Ltd. at 60 ° C for 5 minutes. Subsequently, it was immersed in a crude solution of ATOTECH Japan Co., Ltd., Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80 ° C for 5 minutes. Finally, it was immersed in a neutralizing solution of ATOTECH Japan's Reduction Solution Securigand P at 40 ° C for 5 minutes. This roughened laminate was used as the evaluation substrate A.

(5) Plating by semi-additive 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 an electroless copper plating solution. Next, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 180 ° C for 60 minutes. This plated laminate was used as the evaluation substrate B.

(6) Determination of arithmetic mean roughness (Ra)

Using a non-contact surface roughness meter ("WYKO NT3300" manufactured by VEECO Instruments Co., Ltd.), the Ra value was obtained from a value obtained by measuring a range of 121 μm × 92 μm by a VSI contact mode and a 50-fold lens. Then, it was measured by obtaining an average value of 10 points.

(7) Determination of peel strength

A slit having a width of 10 mm and a length of 100 mm was introduced into the conductor layer of the evaluation substrate B, and one end thereof was peeled off, and the holder was grasped by a jig (TSE, Autocom type tester AC-50C-SL), and measured at room temperature. The load (kgf/cm) at a speed of 50 mm/min when peeling 35 mm in the vertical direction.

As is clear from the results shown in Table 1, in Examples 1 to 4, the linear thermal expansion coefficient was low and the dimensional stability was excellent, and the warpage at the time of hardening was also suppressed. On the other hand, in Comparative Example 1, since the content of the inorganic filler was small, the warpage at the time of curing was reduced, but the dimensional stability was poor. Further, in Reference Example 1, a polymer resin having a glass transition temperature of 30 ° C or less was not used, and it was found that warpage occurred at the time of curing, and dimensional stability was also large.

[Industry use possibility]

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

Claims (22)

An insulating resin material containing a thermosetting resin, an inorganic filler, and an insulating resin material of a polymer resin having a glass transition temperature of 30° C. or lower, and the inorganic filler is 100% by mass based on the nonvolatile component in the insulating resin material. The content of the material is 50 to 95% by mass, and the coefficient of linear expansion of the cured material of the insulating resin material at 25 ° C to 150 ° C is regarded as A (ppm / ° C), and the coefficient of thermal expansion of the wire at 150 ° C to 220 ° C is regarded as When B (ppm / ° C), 0 ≦ BA ≦ 15. An insulating resin material containing a thermosetting resin, an inorganic filler, and an insulating resin material of a polymer resin having a glass transition temperature of 30° C. or lower, and the inorganic filler is 100% by mass based on the nonvolatile component in the insulating resin material. The content of the material is 50 to 95% by mass, and the polymer resin has one or more kinds of skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a decane skeleton. The insulating resin material according to claim 1 or 2, wherein the cured resin material has a linear thermal expansion coefficient of 3 to 30 ppm/° C. at 25° C. to 150° C., and a linear thermal expansion coefficient of 5° at 150° C. to 220° C. At 32 ppm/° C., the cured product of the above-mentioned insulating resin material has an elastic modulus at 25 ° C of 0.5 to 14 GPa. The insulating resin material according to claim 1 or 2, wherein the cured resin material has a linear thermal expansion coefficient of 3 to 10 ppm/° C. at 25° C. to 150° C., and a linear thermal expansion coefficient of 5° at 150° C. to 220° C. At 15 ppm/° C., the cured resin of the above-mentioned insulating resin material has an elastic modulus at 25 ° C of 0.5 to 6 GPa. The insulating resin material according to claim 2, wherein the linear expansion coefficient of the hardened material of the insulating resin material at 25 ° C to 150 ° C is regarded as A (ppm / ° C), and the coefficient of thermal expansion of the wire at 150 ° C to 220 ° C is regarded as When B (ppm / ° C), 0 ≦ BA ≦ 15. The insulating resin material according to claim 1 or 2, wherein the linear expansion coefficient of the hardened material of the insulating resin material at 25 ° C to 150 ° C is regarded as A (ppm / ° C), and the linear thermal expansion coefficient at 150 ° C to 220 ° C When B (ppm/°C), 0≦BA≦4. The insulating resin material according to claim 1 or 2, wherein the thermosetting resin-based epoxy resin is used. The insulating resin material according to claim 1 or 2, wherein the thermosetting resin is a liquid epoxy resin. The insulating resin material according to claim 1 or 2, wherein the content of the thermosetting resin is from 1 to 15% by mass based on 100% by mass of the nonvolatile component in the insulating resin material. The insulating resin material according to claim 1 or 2, wherein the inorganic filler is a vermiculite. The insulating resin material according to claim 1 or 2, wherein the polymer resin has a number average molecular weight of 300 to 100,000. The insulating resin material according to claim 1 or 2, wherein the polymer resin has a number average molecular weight of 8,000 to 20,000. The insulating resin material according to claim 1, wherein the polymer resin has one or more kinds of skeletons selected from the group consisting of a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a decane skeleton. The insulating resin material according to claim 1 or 2, wherein the polymer resin has a butadiene skeleton, a quinone imine skeleton, and a urethane skeleton. The insulating resin material according to claim 1 or 2, wherein the content of the polymer resin is from 1 to 30% by mass based on 100% by mass of the nonvolatile component in the insulating resin material. An adhesive film formed by forming a layer of an insulating resin material according to any one of claims 1 to 15 on a support. A sheet-like cured product obtained by thermally hardening an insulating resin material according to any one of claims 1 to 15. A sheet-like cured product obtained by forming a layer on a tantalum wafer and thermally hardening the insulating resin material according to any one of claims 1 to 15 to form a sheet-like cured product on the tantalum wafer. The amount of warpage at 25 ° C is 0 to 5 mm. A printed wiring board formed by forming a conductor layer on a sheet-like cured product as claimed in claim 17. A printed wiring board formed by forming a conductor layer on a sheet-like cured product as claimed in claim 18. A wafer level wafer size package in which a conductor layer is formed on a sheet-like cured material as claimed in claim 17. A wafer level wafer size package in which a conductor layer is formed on a sheet-like cured material as claimed in claim 18.