JP6860038B2 - Insulating resin material - Google Patents

Description

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

The insulating resin material used for circuit boards such as printed wiring boards and wafer level chip size packages is required to have a low elastic modulus in order to suppress the warp of the board. 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. However, such an insulating resin material having a low elastic modulus generally has a problem that the linear thermal expansion coefficient is high and the dimensional stability is inferior. Since the circuit board is exposed to various environments such as low temperature such as room temperature and high temperature such as reflow, if the linear thermal expansion coefficient is high and the dimensional stability is inferior, the insulating resin material in the circuit board repeatedly expands and contracts. , The distortion causes cracks. As a method of suppressing the coefficient of linear thermal expansion to a low level, a method of blending a large amount of an inorganic filler with an insulating resin material is known. However, when a large amount of inorganic filler is mixed with the insulating resin material, the elastic modulus of the insulating resin material becomes high, and it becomes difficult to suppress the warp. At present, practical insulating resin materials that satisfy the requirements of both low elastic modulus and low coefficient of linear thermal expansion are not always satisfactory.

Japanese Unexamined Patent Publication No. 2006-37083

In view of the above points, an object to be solved by the present invention is to provide an insulating resin material having high dimensional stability and small warpage.

As a result of diligent studies by the present inventors in order to solve the above problems, surprisingly, a large amount of inorganic filler was blended in an insulating resin material containing a thermosetting resin and a specific polymer resin. Even in this case, it has been found that an increase in elastic modulus is suppressed and an insulating resin material having excellent characteristics of both 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 containing 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 100% by mass of the non-volatile component of the insulating resin material. An insulating resin material that is 50 to 95% by mass.
[2] The linear thermal expansion coefficient of the cured product of the insulating resin material at 25 ° C. to 150 ° C. is 3 to 30 ppm / ° C., and the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is 5 to 32 ppm / ° C. The insulating resin material according to [1], wherein the cured product of the insulating resin material has an elastic modulus of 0.5 to 14 GPa at 25 ° C.
[3] The linear thermal expansion coefficient of the cured product of the insulating resin material at 25 ° C. to 150 ° C. is 3 to 10 ppm / ° C., and the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is 5 to 15 ppm / ° C. The insulating resin material according to [1] or [2], wherein the cured product of the insulating resin material has an elastic modulus of 0.5 to 6 GPa at 25 ° C.
[4] When the linear expansion coefficient of the cured product of the insulating resin material at 25 ° C to 150 ° C is A (ppm / ° C) and the linear thermal expansion coefficient at 150 ° C to 220 ° C is B (ppm / ° C). The insulating resin material according to any one of [1] to [3], wherein 0 ≦ BA ≦ 15.
[5] When the linear expansion coefficient of the cured product of the insulating resin material at 25 ° C to 150 ° C is A (ppm / ° C) and the linear thermal expansion coefficient at 150 ° C to 220 ° C is B (ppm / ° C). The insulating resin material according to any one of [1] to [4], wherein 0 ≦ BA ≦ 4.
[6] The insulating resin material according to any one of [1] to [5], wherein the thermosetting resin is an epoxy resin.
[7] The insulating resin material according to any one of [1] to [6], wherein the thermosetting resin is a liquid epoxy resin.
[8] The insulating resin material according to any one of [1] to [7], wherein the content of the thermosetting resin is 1 to 15% by mass with respect to 100% by mass of the non-volatile component of the insulating resin material.
[9] The insulating resin material according to any one of [1] to [8], wherein the inorganic filler is silica.
[10] The insulating resin material according to any one of [1] to [9], wherein the polymer resin has a number average molecular weight of 300 to 100,000.
[11] The insulating resin material according to any one of [1] to [10], wherein the number average molecular weight of the polymer resin is 8000 to 20000.
[12] The insulating resin material according to any one of [1] to [11], wherein the polymer resin has one or more skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton.
[13] The insulating resin material according to any one of [1] to [12], wherein the polymer resin has a butadiene skeleton, an imide skeleton and a urethane skeleton.
[14] The insulating resin material according to any one of [1] to [13], wherein the content of the polymer resin is 1 to 30% by mass with respect to 100% by mass of the non-volatile component of the insulating resin material.
[15] An adhesive film formed by forming a layer of the insulating resin material according to any one of [1] to [14] on a support.
[16] A sheet-like cured product obtained by thermosetting the insulating resin material according to any one of [1] to [14].
[17] Warpage at 25 ° C. when a sheet-like cured product is formed on a silicon wafer by forming a layer of the insulating resin material according to any one of [1] to [14] on a silicon wafer and heat-curing the material. The sheet-like cured product according to [16], wherein the amount is 0 to 5 mm.
[18] A printed wiring board made of the insulating resin material according to any one of [1] to [14].
[19] A printed wiring board in which a conductor layer is formed on the sheet-like cured product according to [16] or [17].
[20] A wafer level chip size package using the insulating resin material according to any one of [1] to [14].
[21] A wafer-level chip size package in which a conductor layer is formed on the sheet-like cured product according to [16] or [17].

According to the present invention, there is provided an insulating resin material having high dimensional stability and small warpage.

[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 ° C. or lower, and if necessary, a curing accelerator, other components, etc. May include. Details will be described below.

(A) Thermosetting Resin Examples of the thermosetting resin used in the present invention include, but are not limited to, epoxy resins, phenolic resins, cyanate ester resins, benzoxazine resins and the like. Of these, it is preferable to use an epoxy resin in terms of improving plating adhesion.

The epoxy resin is not particularly limited, but preferably contains an epoxy resin having two or more epoxy groups in one molecule. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthic Lene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic Examples thereof include a type epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, and a halogenated epoxy resin. These may be used alone or in combination of two or more.

Among these, it is preferable to use one or more selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, and epoxy resin having a butadiene structure. Further, since the epoxy resin contains a liquid epoxy resin, the elastic modulus can be further lowered and the warpage can be reduced. As the liquid epoxy resin, an aromatic epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C. is preferable. The 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, when the entire epoxy resin is 100 parts by mass, the liquid epoxy resin is preferably 60 to 100 parts by mass, preferably 75 to 100 parts by mass, and further 80 to 100 parts by mass. preferable.

The phenol-based resin is not particularly limited, and examples thereof include a phenol novolac resin, a biphenyl skeleton-containing phenol resin, a naphthalene skeleton-containing phenol resin, and a triazine skeleton-containing phenol resin. Examples of the phenol novolac resin include "TD2090" manufactured by DIC Corporation. Examples of the biphenyl skeleton-containing phenol resin include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd. Examples of the naphthalene skeleton-containing phenol resin include "NHN", "CBN" and "GPH" manufactured by Nippon Steel Corporation; "SN170", "SN180", "SN190" and "SN190" manufactured by Nippon Steel Chemical Corporation. "SN475", "SN485", "SN495", "SN375" and "SN395"; "EXB9500" manufactured by DIC Corporation; and the like. Examples of the triazine skeleton-containing phenolic curing agent include "LA3018", "LA7052", "LA7054", and "LA1356" manufactured by DIC Corporation.

The cyanate ester resin is not particularly limited, but is a novolak type (phenol novolac type, alkylphenol novolak type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type). Etc.) Cyanate ester resins and prepolymers in which these are partially triazined. Specific examples of the cyanate ester resin include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disicanate, hexafluorobisphenol A disicianate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak, cresol novolak, phenolic resins containing a dicyclopentadiene structure, and prepolymers in which these cyanate resins are partially triazine. These are used alone or in combination of two or more. As commercially available cyanate ester resins, phenol novolac type polyfunctional cyanate ester resin (manufactured by Ronza Japan Co., Ltd., PT30S, cyanate equivalent 124), and a part or all of bisphenol A disocyanate are triazined. Examples thereof include prepolymers (manufactured by Ronza Japan Co., Ltd., BA230S, cyanate equivalent 232), cyanate ester resins containing a dicyclopentadiene structure (manufactured by Ronza Japan Co., Ltd., DT-4000, DT-7000). ..

Examples of the benzoxazine-based resin include "BA-type benzoxazine" and "B-m-type benzoxazine" manufactured by Shikoku Chemicals Corporation.

The content of the thermosetting resin is preferably 1 to 15% by mass, more preferably 2 to 13% by mass, still more preferably 3 to 11% by mass, based on 100% by mass of the non-volatile component of the insulating resin material.

(B) Inorganic filler The insulating resin material of the present invention can reduce the coefficient of linear thermal expansion by containing the inorganic filler. The inorganic filler is not particularly limited, but silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium. Examples thereof include barium acid acid, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, fused silica and spherical silica are more preferable from the viewpoint of improving filling property, and spherical fused silica is further preferable. preferable. These may be used alone or in combination of two or more. Examples of commercially available spherical molten silica include "SOC2" and "SOC1" manufactured by Admatex Co., Ltd.

The average particle size of the inorganic filler is not particularly limited, but the via shape by laser processing is good from the viewpoint that it is necessary to make the roughness low in order to enable the formation of fine wiring after the roughening treatment of the surface of the insulating layer. From the viewpoint of the above, 5 μm or less is preferable, 3 μm or less is more preferable, 2 μm or less is further preferable, 1 μm or less is further preferable, 0.8 μm or less is particularly preferable, and 0.6 μm or less is particularly preferable. On the other hand, when the resin composition is a resin varnish, 0.01 μm or more is preferable, 0.03 μm or more is more preferable, and 0. 05 μm or more is further preferable, 0.07 μm or more is further preferable, and 0.1 μm or more is particularly preferable. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, LA-950 or the like manufactured by HORIBA, Ltd. can be used.

The content of the inorganic filler is 50% by mass or more with respect to 100% by mass of the non-volatile 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 a low elastic modulus even if the coefficient of linear thermal expansion is increased, the content of the inorganic filler is 60% by mass or more, 70% by mass or more, and 80% by mass or more. Can be enhanced. On the other hand, from the viewpoint of preventing the cured product from becoming brittle and making the surface of the insulating layer after the roughening treatment low in roughness, it is preferably 95% by mass or less with respect to 100% by mass of the non-volatile component in the insulating resin material. Is 90% by mass or less.

The inorganic filler is preferably surface-treated with a surface treatment agent, and specifically, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a styrylsilane-based coupling agent, and an acrylatesilane. One or more surface treatments selected from system-based coupling agents, isocyanatesilane-based coupling agents, sulfidesilane-based coupling agents, vinylsilane-based coupling agents, silane-based coupling agents, organosilazane compounds, and titanate-based coupling agents. It is more preferable to surface-treat with an agent. Thereby, the dispersibility and moisture resistance of the inorganic filler can be improved.

Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane. , N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane and other aminosilane-based coupling agents, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Propylsilane-based coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane and other mercaptosilane-based coupling agents, Styrylsilane-based coupling agents such as p-styryltrimethoxysilane, 3-acrylicoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, An acrylatesilane-based coupling agent such as 3-methacryloxypropyldiethoxysilane, an isocyanatesilane-based coupling agent such as 3-isocyandiapropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, and bis (triethoxysilylpropyl) tetra. Propylsilane-based coupling agents such as sulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, metachlorixpropyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane and other silane-based couplings. Agents, Hexamethyl disilazane, 1,3-divinyl-1,1,3,3-Tetramethyl disilazane, Hexaphenyl disilazane, Trisilazane, Cyclotrisilazane, Octamethylcyclotetrasilazane, Hexabutyl disilazane, Hexaoctyl Disilazan, 1,3-diethyltetramethyldisilazan, 1,3-di-n − Octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazan, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1, Organosilazan compounds such as 3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n-butyl titanate dimer, titanium-i- Propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxytitanium bis (triethanolamineate), dihydroxytitanium bislactate, dihydroxybis (ammonium lactate) titanium, bis (dioctylpyrophosphate) ethylene titanate , Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphate) titanate, tetraoctylbis (dioctyl phosphate) Ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyltricylphenyl titanate, isopropyltriisostearoyl titanate, isopropylisostearoyl Titanates such as diacrylic titanate, isopropyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amideethyl / aminoethyl) titanate Coupling agents and the like can be mentioned. Among these, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, and organosilazane compounds are preferable, and aminosilane-based coupling agents are more preferable. Commercially available products include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. −31 ”(hexamethyldisilazane) and the like.

The inorganic filler surface-treated with the surface treatment agent is preferably added to the resin composition after the inorganic filler is surface-treated with the surface treatment agent. In this case, the dispersibility of the inorganic filler can be further improved.

The surface treatment method for the inorganic filler surface-treated with the surface treatment agent is not particularly limited, and examples thereof include a dry method and a wet method. In the dry method, an inorganic filler is charged into a rotary mixer, an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, and then the mixture is further stirred and classified by a sieve. Then, it can be obtained by dehydrating and condensing the surface treatment agent and the inorganic filler by heating. As a wet method, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, classification by filtration, drying and sieving is performed. Then, it can be obtained by dehydrating and condensing the surface treatment agent and the inorganic filler by heating. Further, an integral blending method in which a surface treatment agent is added to the resin composition is also possible.

(C) Polymer resin having a glass transition temperature of 30 ° C. or less The insulating resin material of the present invention can reduce the elastic modulus of a cured product by containing a polymer resin having a glass transition temperature of 30 ° C. or less. Furthermore, the peel 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 lower, the linear thermal expansion coefficient does not easily change in a wide temperature range of 25 ° C. to 220 ° C., and the difference in the linear thermal expansion coefficient of the cured product can be suppressed to a low level. Therefore, the glass transition temperature is more preferably 20 ° C. or lower, further preferably 10 ° C. or lower. The lower limit 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 ° C. or lower is not particularly limited, but is a polymer 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, a siloxane skeleton, or the like. Resin is mentioned. Among them, from the viewpoint of having more flexibility and adhesion, it is preferable to use a polymer resin having one or more skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton, and further heat resistance and compatibility. A polymer having one or more skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton and a siloxane skeleton, and one or more skeletons selected from an amide skeleton, an imide skeleton and a urethane skeleton. Resin is more preferred. More preferably, the polymer resin has 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. Further, in the polymer resin having a butadiene skeleton, the content of the butadiene skeleton in the polymer resin is preferably 45 to 90% by mass (preferably 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 (preferably 50 to 75% by mass).

Here, the glass transition temperature of the polymer resin can be measured as follows. A polymer resin is applied onto a PET film and heated at 180 ° C. for 90 minutes to dry the solvent and form a film shape. The film is cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis is performed by a thermomechanical weighting method using the thermomechanical analyzer "EXSTAR TMA / SS6000" manufactured by SI Nanotechnology Co., Ltd. .. Specifically, after the test piece is attached to the apparatus, the test piece is measured twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min, and Tg is calculated from the second measurement.

The number average molecular weight of the polymer resin is preferably in the range of 300 to 100,000, more preferably in the range of 800 to 80,000, further preferably in the range of 1500 to 60,000, and in the range of 5000 to 40,000. It is even more preferably in the range of 8000 to 20000. By setting the number average molecular weight in this range, compatibility and flexibility in the insulating resin material can be achieved at the same time. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is obtained by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804 L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

Specific examples include polymer resins having a butadiene skeleton (manufactured by Nippon Soda Co., Ltd. "G-1000", "G-3000", "GI-1000", "GI-3000", manufactured by Idemitsu Petrochemical Co., Ltd. "R-45EPI", "PB3600" manufactured by Daicel Chemical Industry Co., Ltd., "Epofriend AT501", "Ricon130" manufactured by Clay Valley, "Ricon142", "Ricon150", "Ricon657", "Ricon130MA"), butadiene skeleton And a polymer resin having a polyimide skeleton (described in JP-A-2006-37083), a polymer resin having an acrylic skeleton ("SG-P3", "SG-600LB", "SG" manufactured by Nagase ChemteX Corporation). 280 ”,“ SG-790 ”,“ SG-K2 ”,“ SN-50 ”manufactured by Negami Kogyo Co., Ltd.,“ AS-3000E ”,“ ME-2000 ”) and the like.

The content of the polymer resin is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass or more with respect to 100% by mass of the non-volatile component in the insulating resin material in order to lower the elastic modulus of the cured product. Is more preferable. On the other hand, from the viewpoint of enabling the production of a uniform cured product without impairing the compatibility of the resin varnish, 30% by mass or less is preferable, and 25% by mass or less is preferable with respect to 100% by mass of the non-volatile component in the insulating resin material. More preferably, it is more preferably 20% by mass or less.

(D) Curing Accelerator The insulating resin material of the present invention can efficiently cure a 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, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, Examples thereof include an imidazole compound such as 2-phenylimidazolin and an adduct of an imidazole compound and an epoxy resin.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,5) -Amine compounds such as undecene (hereinafter abbreviated as DBU) and the like can be mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.

Examples of phosphonium-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiosianate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like.

When a curing accelerator is used, it is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the thermosetting resin.

(E) Other components The insulating resin material of the present invention may contain other components as necessary, as long as the effects of the present invention are not impaired. Other components include organic fillers such as silicon powder, nylon powder, fluorine powder, and rubber particles, thickeners such as Orben and Benton, silicone-based, fluorine-based, and polymer-based defoaming agents or leveling agents, and thiazole. Adhesion-imparting agents such as phthalocyanines, triazoles, and silane coupling agents, colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, and carbon black, organophosphorus flame retardants, and organonitrogen-containing phosphorus compounds. , Nitrogen compounds, silicone-based flame retardants, flame retardants such as metal hydroxides, and the like.

In the insulating resin material of the present invention, the above components are appropriately mixed, and if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by doing. Further, it can be adjusted as a resin varnish by further adding an organic solvent.

In the insulating resin material of the present invention, the insulating resin material is thermally cured because it is possible to exhibit excellent performance that warpage can be reduced while improving the dimensional stability of the cured product. It is suitable to be used as a sheet-like cured product. The sheet-like cured product may be a sheet-like cured product as long as the insulating resin material is thermally cured into a sheet-like shape, and the one laminated on the circuit board is also a sheet-like cured product.

The cured product of the insulating resin material of the present invention 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 at 150 ° C. to 220 ° C. in order to improve dimensional stability. It is preferably ~ 32 ppm / ° C. The upper limit of the coefficient of linear thermal expansion from 25 ° C. to 150 ° C. is more preferably 25 ppm / ° C. or lower, further preferably 20 ppm / ° C. or lower, further preferably 15 ppm / ° C. or lower, and particularly preferably 10 ppm / ° C. or lower. On the other hand, the lower limit of the coefficient of linear thermal expansion at 25 ° C. to 150 ° C. is not particularly limited, and is 3 ppm / ° C. or higher, 4 ppm / ° C. or higher, 5 ppm / ° C. or higher, or the like. The upper limit of the coefficient of linear thermal expansion from 150 ° C. to 220 ° C. is more preferably 30 ppm / ° C. or lower, further preferably 25 ppm / ° C. or lower, further preferably 20 ppm / ° C. or lower, and particularly preferably 15 ppm / ° C. or lower. On the other hand, the lower limit of the coefficient of linear thermal expansion from 150 ° C. to 220 ° C. is not particularly limited, and may be 5 ppm / ° C. or higher, 6 ppm / ° C. or higher, 7 ppm / ° C. or higher, or the like.

The cured product of the insulating resin material of the present invention expands linearly at 25 ° C. to 150 ° C. and at 150 ° C. to 220 ° C. in order to reduce the difference in coefficient of linear thermal expansion and further improve dimensional stability. When the coefficient is A (ppm / ° C.) and the coefficient of linear thermal expansion from 150 ° C. to 220 ° C. is B (ppm / ° C.), it is preferably 0 ≦ BA ≦ 15. More preferably 0 ≦ BA ≦ 12, even more preferably 0 ≦ BA ≦ 9, even more preferably 0 ≦ BA ≦ 6, and particularly preferably 0 ≦ BA ≦ 4. Is.

The cured product of the insulating resin material of the present invention preferably has an elastic modulus of 0.5 to 14 GPa at 25 ° C. in order to reduce warpage. The upper limit of the elastic modulus at 25 ° C. is more preferably 12 GPa or less, further preferably 10 GPa or less, further 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, 3 GPa or more, or the like.

The amount of warpage of the sheet-shaped cured product of the present invention is confirmed as follows. A circular silicon wafer having a thickness of 100 μm and a diameter of 100 mm is prepared, a layer of an insulating resin material is formed on the silicon wafer, and the material is thermoset to form a sheet-like cured product on the silicon wafer. Next, the laminate in which the sheet-like cured product is formed on the silicon wafer is pressed at room temperature (25 ° C.) with a finger on one end of the cured product with the silicon wafer facing down on a flat desk. Then, the amount of warpage can be obtained by measuring the distance between the diagonal end of the silicon wafer and the flat desk. 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, but it is preferably 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 varnished state to form an insulating layer, but industrially, it is generally preferable to use it in the form of an adhesive film.

[Adhesive film]
For the adhesive film of the present invention, a resin varnish in which an insulating resin material is dissolved in an organic solvent is prepared by a method known to those skilled in the art, and the resin varnish is applied to a support using a die coater or the like, and further. By drying the organic solvent by heating, blowing hot air, or the like to form a resin composition layer on the support, it is possible to produce an adhesive film in which the insulating resin material is layered on the support. ..

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitol such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, 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 resin composition layer is dried so that the content of the organic solvent (residual solvent amount) is 1 to 10% by mass or less, preferably 2 to 6% by mass or less. Although it depends on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, the resin composition layer is formed by drying the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater 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 μm, the resin composition layer preferably has a thickness of 10 to 200 μm, more preferably 15 to 100 μm from the viewpoint of thinning, and 20 ~ 60 μm is more preferable.

Examples of the support include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride, a polyester film such as polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), a polyethylene naphthalate, a polycarbonate film, and a polyimide film. Various plastic films can be mentioned. Further, a paper pattern, a metal foil such as a copper foil or an aluminum foil may be used. Among them, a plastic film is preferable, and a PET film is more preferable, from the viewpoint of versatility. The support and the protective film described later may be subjected to surface treatment such as mud treatment and corona treatment. Further, the mold release treatment may be performed with a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, or a fluororesin-based mold release agent. The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

A protective film similar to the support can be further laminated on the surface of the resin composition layer where the support is not in close contact. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm, preferably 5 to 20 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can also be rolled up and stored.

[Printed circuit board]
Examples of the printed wiring board of the present invention include a rigid circuit board, a flexible circuit board, a single-area layer board, and a thin board. An example of a method of manufacturing a printed wiring board using the adhesive film manufactured as described above will be described.

First, the adhesive film is laminated on one side or both sides of the inner layer circuit board 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, a heat-curable polyphenylene ether substrate, and the like. Here, the inner layer circuit board means a circuit board in which a patterned conductor layer (circuit) is formed on one side or both sides of the substrate as described above. Further, in a multi-layer printed wiring board in which conductor layers and insulating layers are alternately laminated, one or both sides of the outermost layer of the multi-layer printed wiring board is a conductor layer (circuit) in which a pattern is processed. It is included in the inner layer circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like.

In the above lamination, if the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressurized and heated to the circuit board. Laminate. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure (lamination pressure) is preferably 1 to 11 kgf / cm ² (9.8 ×). 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the crimping time (lamination time) is preferably 5 to 180 seconds, and the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the laminating method may be a batch method or a continuous method using a roll. Vacuum laminating can be done using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nichigo Morton Co., Ltd., vacuum pressurized laminators manufactured by Meiki Seisakusho Co., Ltd., roll-type dry coaters manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like can be mentioned.

After laminating the adhesive film on the inner layer circuit board, it is cooled to around room temperature, then peeled off when the support is peeled off, and the resin composition is thermoset to form a cured product on the inner layer circuit board. An insulating layer can be formed. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, and more preferably 160 ° C. to 210. It is selected in the range of 30 to 120 minutes at ° C. If the support is not peeled off after forming the insulating layer and before curing, it can be peeled off here if necessary. The thickness of the insulating layer is preferably 10 to 200 μm, more preferably 15 to 100 μm, and 20 to 60 μm from the viewpoint of thinning, similar to the thickness of the resin composition layer formed in the adhesive film. More preferred.

Next, the insulating layer formed on the inner layer circuit board is drilled to form via holes and through holes. The drilling can be performed by, for example, a known method such as a drill, a laser, or a plasma, or a combination of these methods if necessary, but the most common drilling is a laser such as a carbon dioxide laser or a YAG laser. The method. If the support is not peeled off before the drilling process, it will be peeled off here.

Next, the surface of the insulating layer is roughened. In the case of dry roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet roughening treatment, swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent and neutralization treatment with a neutralizing liquid can be performed in this order. Be done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor 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 ° C. for 5 to 20 minutes (preferably 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling solution include an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Security P (Swelling Dip Security P) and Swelling Dip Security SBU (Swelling Dip Security SBU) manufactured by Atotech Japan Co., Ltd. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Atotech Japan Co., Ltd.'s Concentrate Compact CP and Dozing Solution Security P. The neutralization treatment with a neutralizing solution is carried out by immersing in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably 35 to 45 ° C. for 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include Reduction Solusin Securigant 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 forming fine wiring and stabilizing the peel strength. Specifically, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments), the Ra value can be obtained from the numerical value obtained with the measurement range set to 121 μm × 92 μm by the VSI contact mode and the 50x lens. ..

Then, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used. Examples of wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and a method of forming a conductor layer only by electroless plating. Be done.

The peel strength between the conductor layer and the insulating layer is preferably 0.5 kgf / cm or more, more preferably 0.6 kgf / cm or more, and even more 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 for forming a pattern thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used, and by repeating the above-mentioned series of steps a plurality of times, a multi-layered structure in which build-up layers are laminated in multiple stages can be used. A printed wiring board can also be formed. As described above, in the present invention, since the dimensional stability is high and the warp is small, it can be suitably used for a printed wiring board such as a rigid circuit board, a flexible circuit board, a single area layer board, and a thin board, and particularly in multiple stages. Since it has high dimensional stability and small warpage even when laminated on a board, it can be more preferably used as a build-up layer of a multilayer printed wiring board.

[Wafer level chip size package]
By using the insulating resin material of the present invention, a wafer-level chip size package having excellent dimensional stability and low warpage can be produced. The insulating resin material may be laminated on both sides of the wafer level chip size package, or may be laminated on one side. Various structures have been devised for the wafer level chip size package, which can be roughly classified into a fan-in structure and a fan-out structure. The thickness of the silicon wafer is preferably 50 to 150 μm, more preferably 80 to 120 μm from the viewpoint of thinning.

As an example of a method of manufacturing a wafer level chip size package having a fan-in structure using the adhesive film manufactured as described above, a method including the following steps can be mentioned.
(1) A process of forming a circuit or 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, drilling holes, performing desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.
(4) A step of repeating (2) and (3) from above the rewiring layer, if necessary.
(5) A step of forming a solder ball on the rewiring layer.
(6) Step of dicing.

As an example of another method for manufacturing a wafer level chip size package having a fan-in structure, for example, the method described in Japanese Patent No. 3618330 can be mentioned, and a method including the following steps can be mentioned.
(1) A step of producing a circuit element having a predetermined function and a silicon wafer on which a plurality of electrode pads electrically connected to the circuit element are formed.
(2) A step of forming a columnar electrode on the upper surface of an electrode pad portion on a silicon wafer.
(3) A step of adhering the adhesive film of the present invention from the columnar electrode surface side, curing the film, peeling the support, and forming an insulating layer.
(4) A step of appropriately polishing 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 upper surface of the exposed columnar electrode.
(6) Step of dicing.

As an example of a method of manufacturing a wafer level chip size package having a fan-out structure using the adhesive film manufactured as described above, a method including the following steps can be mentioned.
(1) A process of dicing a silicon wafer to prepare individual chips.
(2) A step of fixing individual chip pieces on a support substrate via a film.
(3) A step of laminating the adhesive film of the present invention from one side of each chip.
(4) A step of curing a film, peeling a support, drilling a hole, performing a desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.
(5) A step of further laminating films as needed.
(6) A step of forming a solder ball on the rewiring layer.

As an example of another method for manufacturing a wafer level package having a fan-out structure, for example, the method described in JP-A-2005-167191 can be mentioned, and a method including the following steps can be mentioned.
(1) A step of producing a circuit element having a predetermined function and a silicon wafer on which a plurality of electrode pads electrically connected to the circuit element are formed.
(2) A process of producing a semiconductor chip piece through dicing.
(3) A step of widely arranging and fixing semiconductor chips via a film on a support in a positional relationship such that the distance between the semiconductor chips has a sufficient space for forming a fan-out ball array in a later step. ..
(4) A step of laminating the adhesive film of the present invention so as to fill the space between the semiconductor chips from the surface side on which the semiconductor chips are fixed.
(5) A step of curing the adhesive film, peeling off the support, etching the insulating layer on the pad of the semiconductor chip, forming an opening, and forming a 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 an electrode pad.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these do not limit the present invention in any way. The "part" described below means a "part by mass".

[Manufacturing 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 100 wt%: manufactured by Nippon Soda Co., Ltd.) and ipsol in a reaction vessel. 23.5 g of 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became 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 added with further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product is cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol are added to the reaction product. 40.4 g of acetate (manufactured by Daicel Chemical Industry Co., Ltd.) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered with a 100-mesh filter cloth 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 mgKOH / g
Solid content: 50% by mass
Number average molecular weight: 13723
Glass transition temperature: -10 ° C
Content of polybutadiene structural part: 50 / (50 + 4.8 + 8.96) x 100 = 78.4% by mass

[Example 1]
Liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation) 40 parts, imidazole derivative (manufactured by Shikoku Kasei Co., Ltd., "2P4MZ") 1 part, polyimide resin A 260 parts, MEK 300 parts, liquid Spherical silica (Admatex) surface-treated with naphthalene-type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032", 20 parts, phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573")) 920 parts of "SO-C2" manufactured by Co., Ltd., average particle size 0.5 μm) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, a polyethylene terephthalate film (thickness 38 μm) was prepared. , Hereinafter abbreviated as "PET film"), coated with a die coater so that the thickness of the resin composition layer after drying is 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 7 minutes. , Obtained an adhesive film.

[Example 2]
Liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation) 54 parts, imidazole derivative (manufactured by Shikoku Kasei Co., Ltd., "2P4MZ") 1 part, polyimide resin A 400 parts, MEK 300 parts, liquid Spherical silica (Admatex) surface-treated with naphthalene-type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032", 20 parts, phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573")) 920 parts of "SO-C2" manufactured by Co., Ltd., average particle size 0.5 μm) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Then, the resin varnish was bonded in the same manner as in Example 1. I got a film.

[Example 3]
Spherical silica (manufactured by Admatex Co., Ltd., "SO-C2", average particle size 0.5 μm) surface-treated with the phenylaminosilane-based coupling agent of Example 1 (manufactured by Shinetsu Chemical Industry Co., Ltd., “KBM573”). ) Is surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573"), spherical silica (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm). An adhesive film was obtained in the same manner as in Example 1 except that the film was changed to.

[Example 4]
Spherical silica (manufactured by Admatex Co., Ltd., "SO-C2", average particle size 0.5 μm) surface-treated with the phenylaminosilane-based coupling agent of Example 2 (manufactured by Shinetsu Chemical Industry Co., Ltd., “KBM573”). ) Is surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573"), spherical silica (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm). An adhesive film was obtained in the same manner as in Example 2 except that the film was changed to.

[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.

[Reference Example 1]
Liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation) 40.3 parts, imidazole derivative (manufactured by Shikoku Kasei Co., Ltd., "2P4MZ") 0.5 parts, MEK 30 parts, liquid naphthalene Type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032" 10 parts, solid naphthalene type epoxy resin (epoxy equivalent 250, manufactured by DIC Co., Ltd., "HP6000" 42.5 parts, phenoxy resin solution (Japan Epoxy) Resin Co., Ltd. "YX-6954", mixed solution of MEK with a non-volatile content of 30% by mass and cyclohexanone, glass transition temperature 120 ° C., 14 parts, phenol novolac resin (phenolic hydroxyl group equivalent 105, manufactured by DIC Co., Ltd., 75 parts of MEK varnish with a non-volatile content of 60% by mass of "TD2090", spherical silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573") (manufactured by Admatex Co., Ltd., 625 parts of "SO-C2" (average particle size 0.5 μm) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Then, an adhesive film was obtained in the same manner as in Example 1.

[Measurement of elastic modulus]
The adhesive film was heat-cured at 180 ° C. for 90 minutes to obtain a sheet-like cured product. Next, the PET film was peeled off, and a tensile test was performed on the cured product with a Tencilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with the Japanese Industrial Standards (JIS K7127), and the elastic modulus was measured.

[Evaluation of warpage]
The resin varnishes of Examples 1 to 4 and Comparative Example 1 are applied onto a PET film with a die coater so as to have a thickness of 80 μm, dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes, and heat-cured. An adhesive film was produced by forming a sex resin composition layer. This adhesive film (80 μm) is attached to a silicon wafer (100 μm) with a batch type vacuum pressurizing laminator MVLP-500 (manufactured by Meiki Seisakusho Co., Ltd., trade name), heat-treated at 180 ° C. for 90 minutes, and warped. The presence or absence of was observed. The end of the wafer after the above treatment was pressed, and the distance between the wafer end on the opposite side of the pressed portion and the ground was defined as the amount of warpage. Those having a warp amount of 0 to 5 mm were evaluated as "◯", and those having a warp amount larger than 5 mm were evaluated as "x". The results are shown in Table 1.

[Measurement of coefficient of linear thermal expansion]
The adhesive film was heat-cured at 190 ° 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 a tensile weighting method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Co., Ltd. After the test piece was attached to the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average coefficient of linear thermal expansion from 25 ° C. to 150 ° C. and the average coefficient of linear thermal expansion from 150 ° C. to 220 ° C. in the second measurement were calculated.

[Evaluation of dimensional stability]
Those having an average coefficient of linear thermal expansion of 30 ppm / ° C or less from 25 ° C to 150 ° C and an average coefficient of linear thermal expansion of 32 ppm / ° C or less from 150 ° C to 220 ° C are designated as “◯”, and the above 25 ° C. If the average coefficient of linear thermal expansion from 150 ° C to 150 ° C is larger than 30 ppm / ° C, or the average coefficient of linear thermal expansion from 150 ° C to 220 ° C is larger than 32 ppm / ° C, it is defined as “Δ”, and the above 25 ° C to 150 ° C. Those having an average coefficient of linear thermal expansion larger than 100 ppm / ° C. or an average coefficient of linear thermal expansion of 150 ° C. to 220 ° C. larger than 200 ppm / ° C. were evaluated as “x”.

[Measurement of Arithmetic Mean Roughness (Ra) and Peel Strength]
(1) Base treatment of laminated board Glass cloth base material Epoxy resin double-sided copper-clad laminated board [copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.] on both sides CZ8100 manufactured by MEC Co., Ltd. The copper surface was roughened by immersing it in.
(2) Laminating of Adhesive Film The adhesive film was laminated on both sides of a laminated board using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho Co., Ltd., trade name). Lamination was carried out by reducing the pressure for 30 seconds to an atmospheric pressure of 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
(3) Curing of Resin Composition The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under the conditions of 180 ° C. for 30 minutes to form an insulating layer.
(4) Roughing treatment The laminated board on which the insulating layer was formed was immersed in a swollen liquid, Atotech Japan Co., Ltd.'s diethylene glycol monobutyl ether-containing Swelling Dip Securigan P, at 60 ° C. for 5 minutes, and then roughened. As a liquid, soak in Atotech Japan Co., Ltd.'s Concentrate Compact P (an aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) at 80 ° C. for 5 minutes, and finally as a neutralizing liquid, Atotech Japan Co., Ltd. It was immersed in reduction sholysin securigant P at 40 ° C. for 5 minutes. The laminated board after this roughening treatment was designated 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 an electroless plating solution 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, the annealing treatment was performed at 180 ° C. for 60 minutes. The laminated plate after plating was used as the evaluation substrate B.
(6) Measurement of Arithmetic Mean Roughness (Ra) Using a non-contact surface roughness meter (“WYKO NT3300” manufactured by Becoin Sturments), the measurement range can be obtained as 121 μm × 92 μm with a VSI contact mode and a 50x lens. The Ra value was calculated from the numerical value. Then, it was measured by obtaining the average value of 10 points.
(7) Measurement of peel strength Make a notch in the conductor layer of the evaluation substrate B with a width of 10 mm and a length of 100 mm, and peel off one end of the grip tool (TSE Co., Ltd., Autocom type testing machine AC). The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature 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 was low, the dimensional stability was excellent, and the warpage was suppressed. On the other hand, in Comparative Example 1, since the content of the inorganic filler is small, the warp is reduced, but the dimensional stability is inferior. Further, it can be seen that Reference Example 1 does not use a polymer resin having a glass transition temperature of 30 ° C. or lower, which causes warpage and high dimensional stability.

By using the insulating resin material of the present invention, it has become possible to provide an insulating resin material having high dimensional stability and small warpage.

Claims (17)

An insulating resin material containing a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30 ° C. or less and having one or more skeletons selected from a butadiene skeleton, a carbonate skeleton, and a siloxane skeleton.
The thermosetting resin is an epoxy resin,
When the whole epoxy resin is 100 parts by mass, the liquid epoxy resin is 60 to 100 parts by mass.
The number average molecular weight of the polymer resin is 8000 to 20000.
An insulating resin material (excluding an insulating resin material containing aluminum hydroxide) in which the content of the inorganic filler is 50 to 95% by mass with respect to 100% by mass of the non-volatile component of the insulating resin material. An insulating resin material containing a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30 ° C. or less, a butadiene skeleton , and an imide skeleton and a urethane skeleton.
The thermosetting resin is an epoxy resin,
When the whole epoxy resin is 100 parts by mass, the liquid epoxy resin is 60 to 100 parts by mass.
The number average molecular weight of the polymer resin is 300 to 60,000 .
An insulating resin material (excluding an insulating resin material containing aluminum hydroxide) in which the content of the inorganic filler is 50 to 95% by mass with respect to 100% by mass of the non-volatile component of the insulating resin material. An insulating resin material containing a thermosetting resin, silica, and a polymer resin having a glass transition temperature of 30 ° C. or less and having one or more skeletons selected from a butadiene skeleton, a carbonate skeleton, and a siloxane skeleton.
The thermosetting resin is an epoxy resin,
When the whole epoxy resin is 100 parts by mass, the liquid epoxy resin is 60 to 100 parts by mass.
The number average molecular weight of the polymer resin is 300 to 60,000 .
An insulating resin material (excluding an insulating resin material containing aluminum hydroxide) having a silica content of 50 to 95% by mass with respect to 100% by mass of a non-volatile component of the insulating resin material. The insulating resin material according to claim 1 or 2 , wherein the inorganic filler is silica. The insulating resin material according to any one of claims 2 to 4, wherein the polymer resin has a number average molecular weight of 8000 to 20000. The insulating resin material according to any one of claims 1, 3 to 5 , wherein the polymer resin has a butadiene skeleton, and further has an imide skeleton and a urethane skeleton. The insulating resin material according to any one of claims 1 to 6, wherein the glass transition temperature of the polymer resin is 20 ° C. or lower. The insulating resin material according to any one of claims 1 to 7, wherein the content of the butadiene skeleton in the polymer resin is 45 to 90% by mass. The insulating resin material according to any one of claims 1, 3 to 8, wherein the content of the siloxane skeleton in the polymer resin is 40 to 80% by mass. The insulating resin material according to any one of claims 1 to 9 , wherein the content of the polymer resin is 1 to 30% by mass with respect to 100% by mass of the non-volatile component of the insulating resin material. An adhesive film obtained by forming a layer of the insulating resin material according to any one of claims 1 to 10 on a support. A sheet-like cured product obtained by thermosetting the insulating resin material according to any one of claims 1 to 10. A sheet-like cured product is formed on a silicon wafer by forming a layer of the insulating resin material according to any one of claims 1 to 10 on a silicon wafer having a thickness of 100 μm and a diameter of 100 mm at a thickness of 80 μm and heat-curing the material. A sheet-like cured product having a warp amount of 0 to 5 mm at 25 ° C. A printed wiring board using the insulating resin material according to any one of claims 1 to 10. A printed wiring board in which a conductor layer is formed on the sheet-like cured product according to claim 12 or 13. A wafer level chip size package using the insulating resin material according to any one of claims 1 to 10. Wafer level chip size package in which a conductor layer is formed on the sheet-like cured product according to claim 12 or 13.