JP2018141158A - Insulation resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulation resin material that is high in dimensional stability and low in warpage.SOLUTION: An insulation resin material comprises thermosetting resin, inorganic filler and polymer resin with a glass transition temperature of 30°C or less, where a content of the inorganic filler is 50-95 mass% relative to the nonvolatile component 100 mass% of the insulation resin material.SELECTED DRAWING: None

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 or a wafer level chip size package using the insulating resin material.

  Insulating resin materials used for circuit boards such as printed wiring boards and wafer level chip size packages are required to have a low elastic modulus in order to suppress board warpage. For example, Patent Document 1 discloses a thermosetting resin composition containing a specific linear modified polyimide resin and a thermosetting resin as a low elastic modulus thermosetting resin composition. 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 poor. Because circuit boards are exposed to various environments such as low temperatures such as room temperature and high temperatures such as reflow, if the linear thermal expansion coefficient is high and dimensional stability is poor, the insulating resin material in the circuit board repeatedly expands and contracts. The cracks are caused by the distortion. As a technique for keeping the linear thermal expansion coefficient low, a method of blending a large amount of an inorganic filler into an insulating resin material is known. However, when a large amount of an inorganic filler is blended with the insulating resin material, the elastic modulus of the insulating resin material is increased, which makes it difficult to suppress warpage. At present, no practical insulating resin material that satisfies the requirements of both low elastic modulus and low linear thermal expansion coefficient is necessarily satisfactory.

JP 2006-37083 A

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

  In order to solve the above problems, as a result of intensive studies by the present inventors, 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 was found that an increase in the elastic modulus was suppressed, and an insulating resin material excellent in both characteristics of a low elastic modulus and a low linear thermal expansion coefficient was 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 less, wherein the content of the inorganic filler is 100% by mass of the nonvolatile component of the insulating resin material An insulating resin material, which is 50 to 95% by mass.
[2] The linear thermal expansion coefficient at 25 ° C to 150 ° C of the cured product of the insulating resin material 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 a cured product of the insulating resin material has an elastic modulus at 25 ° C. of 0.5 to 14 GPa.
[3] The linear thermal expansion coefficient at 25 ° C to 150 ° C of the cured product of the insulating resin material 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 at 25 ° C. of 0.5 to 6 GPa.
[4] When the linear expansion coefficient at 25 ° C to 150 ° C of the cured product of the insulating resin material 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 ≦ B−A ≦ 15.
[5] When the linear expansion coefficient at 25 ° C to 150 ° C of the cured product of the insulating resin material 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 ≦ B−A ≦ 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 nonvolatile 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 polymer resin has a number average molecular weight of 8000 to 20000.
[12] The insulating resin material according to any one of [1] to [11], wherein the polymer resin has at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a siloxane skeleton.
[13] The insulating resin material according to 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 nonvolatile component of the insulating resin material.
[15] An adhesive film in which the insulating resin material according to any one of [1] to [14] is formed 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-shaped 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 thermally curing the layer. The sheet-like cured product according to [16], wherein the amount is 0 to 5 mm.
[18] A printed wiring board using the insulating resin material according to any one of [1] to [14].
[19] A printed wiring board having a conductor layer 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, an insulating resin material having high dimensional stability and low warpage is provided.

[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. Further, if necessary, a curing accelerator, other components, etc. May be included. Details are described below.

(A) Thermosetting resin Although it does not specifically limit as a thermosetting resin used for this invention, An epoxy resin, a phenol-type resin, cyanate ester resin, a benzoxazine-type resin etc. are mentioned. Among these, it is preferable to use an epoxy resin in terms of improving plating adhesion.

  Although it does not specifically limit as an epoxy resin, It is preferable to contain the epoxy resin which has a 2 or more epoxy group in 1 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, naphthy Ren ether type epoxy resin, glycidyl amine 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 butadiene structure, alicyclic Epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc. It is. 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 resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, and epoxy resins having a butadiene structure. Moreover, an epoxy resin can reduce an elasticity modulus more by containing a liquid epoxy resin, and can make curvature small. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When using a liquid epoxy resin as an epoxy resin, when the whole epoxy resin is 100 parts by mass, the liquid epoxy resin is preferably 60 to 100 parts by mass, more preferably 75 to 100 parts by mass, and further 85 to 100 parts by mass. preferable.

  The phenolic 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”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and the like. Examples of the naphthalene skeleton-containing phenol resin include “NHN”, “CBN” and “GPH” manufactured by Nippon Kayaku Co., Ltd .; “SN170”, “SN180”, “SN190”, “manufactured by Nippon Steel Chemical Co., Ltd.” SN475 ”,“ SN485 ”,“ SN495 ”,“ SN375 ”and“ SN395 ”;“ EXB9500 ”manufactured by DIC Corporation; Examples of the triazine skeleton-containing phenolic curing agent include “LA3018”, “LA7052”, “LA7054”, and “LA1356” manufactured by DIC Corporation.

  Although there is no restriction | limiting in particular as cyanate ester resin, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type) And the like) and cyanate ester resins, and prepolymers in which these are partially triazines. Specific examples of the cyanate ester resin include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol Novolac, cle Examples thereof include polyfunctional cyanate resins derived from urenovolak, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partly triazines, etc. These may be used alone or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolac type polyfunctional cyanate ester resins (manufactured by Lonza Japan Co., Ltd., PT30S, cyanate equivalent 124), and some or all of bisphenol A dicyanate are triazines and trimers. And a prepolymer (Lonza Japan Co., Ltd., BA230S, cyanate equivalent 232), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan Co., Ltd., DT-4000, DT-7000) and the like.

  Examples of the benzoxazine-based resin include “Ba type benzoxazine” and “Bm type benzoxazine” manufactured by Shikoku Kasei Co., Ltd.

  The content of the thermosetting resin is preferably 1 to 15% by mass, more preferably 2 to 13% by mass, and still more preferably 3 to 11% by mass with respect to 100% by mass of the nonvolatile component of the insulating resin material.

(B) Inorganic filler The insulating resin material of this invention can reduce a linear thermal expansion coefficient by containing an 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, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, and fused silica and spherical silica are more preferable, and spherical fused silica is more preferable from the viewpoint of enhancing filling properties. preferable. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd.

  The average particle size of the inorganic filler is not particularly limited, but it is necessary to reduce the roughness to enable fine wiring formation after the roughening treatment on the surface of the insulating layer, and the via shape by laser processing is good. From the viewpoint of becoming, it 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, even more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the resin composition is a resin varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is further more preferable, and 0.1 μm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  In order to reduce the linear thermal expansion coefficient of the cured product, the content of the inorganic filler is 50% by mass or more with respect to 100% by mass of the nonvolatile component in the insulating resin material. Since the insulating resin material of the present invention can maintain a low elastic modulus even when the linear thermal expansion coefficient 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 increased. On the other hand, it is 95% by mass or less with respect to 100% by mass of the nonvolatile component in the insulating resin material from the viewpoint of preventing the cured product from becoming brittle and reducing the roughness of the surface of the insulating layer after the roughening treatment. Is 90 mass% or less.

  The inorganic filler is preferably surface-treated with a surface treatment agent. Specifically, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, and an acrylate silane. One or more surface treatments selected from a series coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, a vinyl silane coupling agent, a silane coupling agent, an organosilazane compound and a titanate coupling agent More preferably, the surface treatment is performed with an agent. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyl Acrylate silane coupling agents such as triethoxysilane and 3-methacryloxypropyldiethoxysilane, and isocyanates such as 3-isocyanatopropyltrimethoxysilane Silane coupling agents, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacloxy Silane coupling agents such as propyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexa Phenyldisilazane, trisilazane, cyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n- Cutyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3 -Organosilazan compounds such as dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n-butyl titanate dimer, titanium-i-propoxy Octylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis Dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) Titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triiso Stearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryl isostearoyl titanate, Examples thereof include titanate coupling agents such as isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tri (N-amidoethyl / aminoethyl) titanate. Of these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred, and aminosilane coupling agents are more preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by 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 enhanced.

  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. As a dry method, an inorganic filler is charged in a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, followed by further stirring and classification with a sieve. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed 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 is performed by filtration, drying, and sieving. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. Furthermore, an integral blend method in which a surface treating 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. In addition, the polymer resin having a glass transition temperature of 30 ° C. or lower hardly changes the linear thermal expansion coefficient in a wide temperature range of 25 ° C. to 220 ° C., and can suppress the difference in the linear thermal expansion coefficient of the cured product. For this reason, the glass transition temperature is more preferably 20 ° C. or less, and further preferably 10 ° C. or less. Although the lower limit of the glass transition temperature is not particularly limited, it 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, or a siloxane skeleton. Resin. Among these, 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 from the viewpoint of more flexibility and adhesion, and further heat resistance and compatibility. A polymer having at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a siloxane skeleton, and at least one skeleton selected from an amide skeleton, an imide skeleton, and a urethane skeleton. A resin is more preferable. More preferred are a polymer resin having a butadiene skeleton, an imide skeleton and a urethane skeleton, a polymer resin having an acrylic skeleton, and a polymer resin having an imide skeleton and a siloxane skeleton. Moreover, in the polymer resin having a butadiene skeleton, it is preferable that the content of the butadiene skeleton in the polymer resin is 45 to 90% by mass (preferably 60 to 80% by mass). In the polymer resin having a siloxane skeleton, the siloxane skeleton content in the polymer is preferably 40 to 80% by mass (preferably 50 to 75% by mass).

  Here, the measurement of the glass transition temperature of the polymer resin can be performed as follows. A polymer resin is applied on a PET film, and the solvent is dried by heating at 180 ° C. for 90 minutes to obtain a film shape. The film is cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis is performed by a tensile load method using “EXSTAR TMA / SS6000” manufactured by SII Nano Technology Co., Ltd. . Specifically, after the test piece is mounted on the apparatus, the test piece is continuously measured twice 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, still more preferably in the range of 1500 to 60000, and in the range of 5000 to 40000. It is even more preferable that it is in the range of 8000 to 20000. By setting the number average molecular weight within this range, compatibility and flexibility in the insulating resin material can be achieved. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is 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. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Specific examples include polymer resins having a butadiene skeleton (“G-1000”, “G-3000”, “GI-1000”, “GI-3000” manufactured by Nippon Soda Co., Ltd.), manufactured by Idemitsu Petrochemical Co., Ltd. “R-45EPI”, “PB3600” manufactured by Daicel Chemical Industries, Ltd., “Epofriend AT501”, “Ricon130”, “Ricon142”, “Ricon150”, “Ricon657”, “Ricon130MA” manufactured by Clay Valley), 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 "," AS- "manufactured by Negami Kogyo Co., Ltd. 000E "," ME-2000 "), and the like.

  In order to lower 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 more preferably 5% by mass or more with respect to 100% by mass of the nonvolatile component in the insulating resin material. 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, it is preferably 30% by mass or less, and 25% by mass or less with respect to 100% by mass of the nonvolatile component in the insulating resin material. More preferred is 20% by mass or less.

(D) Curing Accelerator The insulating resin material of the present invention can efficiently cure the thermosetting resin by further containing a curing accelerator. Although it does not specifically limit as a hardening accelerator, An imidazole type hardening accelerator, an amine type hardening accelerator, a guanidine type hardening accelerator, a phosphonium type hardening accelerator etc. are mentioned.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 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-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine 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-benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl-imidazoline, etc. imidazole compounds of and imidazole compounds and adducts such as with epoxy resin.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. And amine compounds such as (5,4,0) -undecene (hereinafter abbreviated as DBU).

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like.

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

  When using a hardening accelerator, it becomes like this. Preferably it is 0.5-5 mass parts with respect to 100 mass parts of thermosetting resins, More preferably, it is 1-3 mass parts.

(E) Other components The insulating resin material of the present invention can be blended with other components as necessary within a range not impairing the effects of the present invention. Other components include silicon powder, nylon powder, fluorine powder, organic fillers such as rubber particles, thickeners such as Orben and Benton, silicone-based, fluorine-based and polymer-based antifoaming or leveling agents, thiazole , Triazole, silane coupling agent and other adhesion-imparting agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds , Nitrogen compounds, silicone flame retardants, flame retardants such as metal hydroxides, and the like.

  The insulating resin material of the present invention is appropriately mixed with the above components 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. Moreover, it can adjust also as a resin varnish by adding an organic solvent.

  In the insulating resin material of the present invention, it is possible to exhibit excellent performance of reducing warpage while enhancing the dimensional stability of the cured product, and thus the insulating resin material is thermoset. It is preferable to use it as a sheet-like cured product. It should be noted that the sheet-like cured product is not limited as long as the insulating resin material is thermally cured in the form of a sheet, and what is 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 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. in order to enhance dimensional stability. -32 ppm / ° C is preferred. The upper limit of the linear thermal expansion coefficient at 25 ° C to 150 ° C is more preferably 25 ppm / ° C or less, further preferably 20 ppm / ° C or less, still more preferably 15 ppm / ° C or less, and particularly preferably 10 ppm / ° C or less. On the other hand, the lower limit value of the linear thermal expansion coefficient 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, and the like. Further, the upper limit value of the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is more preferably 30 ppm / ° C. or less, further preferably 25 ppm / ° C. or less, still more preferably 20 ppm / ° C. or less, and particularly preferably 15 ppm / ° C. or less. On the other hand, the lower limit value of the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is not particularly limited, and may be 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 has a linear expansion at 25 ° C. to 150 ° C. at 25 ° C. to 150 ° C. and 150 ° C. to 220 ° C. in order to further reduce dimensional stability by reducing the difference in linear thermal expansion coefficient. When the coefficient is A (ppm / ° C.) and the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is B (ppm / ° C.), 0 ≦ B−A ≦ 15 is preferable. More preferably, 0 ≦ B−A ≦ 12, still more preferably 0 ≦ B−A ≦ 9, still more preferably 0 ≦ B−A ≦ 6, and particularly preferably 0 ≦ B−A ≦ 4. It is.

  The cured product of the insulating resin material of the present invention preferably has an elastic modulus at 25 ° C. of 0.5 to 14 GPa 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, still more 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.

  About the curvature amount of the sheet-like hardened | cured material of this invention, it confirms as follows. A circular silicon wafer having a thickness of 100 μm and a diameter of 100 mm is prepared, and an insulating resin material is formed on the silicon wafer and thermally cured 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 one end from above the cured product with the silicon wafer on a flat desk at room temperature (25 ° C.). Then, the amount of warpage can be obtained by measuring the distance between the edge of the silicon wafer on the diagonal and the flat desk. The amount of warpage of the laminate at 25 ° C. is preferably 0 to 5 mm.

  Although it does not specifically limit as a form of the insulating resin material of this invention, It is suitable to apply to circuit boards, such as an adhesive film, a printed wiring board, and a wafer level chip size package. Although the insulating resin material of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, it is generally preferred industrially to be used in the form of an adhesive film.

[Adhesive film]
The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, a resin varnish in which an insulating resin material is dissolved in an organic solvent, and this resin varnish is applied to a support using a die coater or the like. By drying the organic solvent by heating or blowing hot air to form a resin composition layer on the support, it can be produced as 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 carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent (residual solvent amount) in the resin composition layer is 1 to 10% by mass or less, preferably 2 to 6% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an 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, More preferably, it is ˜60 μm.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint of versatility, a plastic film is preferable, and a PET film is more preferable. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers, Preferably it is 5-20 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

[Printed wiring 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 for producing a printed wiring board using the adhesive film produced as described above will be described.

  First, the adhesive film is laminated (laminated) on one side or both sides of the inner circuit board using a vacuum laminator. Examples of the substrate used for the inner 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. In addition, an inner layer circuit board means here that the conductor layer (circuit) patterned was formed in the single side | surface or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the inner layer circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when 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 pressed 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. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  After laminating the adhesive film on the inner layer circuit board, after cooling to near room temperature, if the support is peeled off, it 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 preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary. Similar to the thickness of the resin composition layer formed in the adhesive film, the insulating layer preferably has a thickness of 10 to 200 μm, more preferably 15 to 100 μm from the viewpoint of thinning, and 20 to 60 μm. Further preferred.

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

  Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet-type roughening treatment, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order. It is 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 performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU (ABUTEC Japan). 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 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 permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  The arithmetic average 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 BEIKO INSTRUMENTS Co., Ltd.), the Ra value can be obtained from a numerical value obtained with a measurement range of 121 μm × 92 μm by a VSI contact mode and a 50 × lens. .

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is 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 further 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 pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages A printed wiring board can also be formed. As described above, in the present invention, since the dimensional stability is high and the warpage 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, a thin board, etc. Even when laminated, the dimensional stability is high and the warpage is small, so that it can be more suitably 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 excellent in 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, and can be roughly divided into a fan-in structure and a fan-out structure. The thickness of the silicon wafer is preferably 50 to 150 μm and 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 may be mentioned.
(1) A step of forming circuits and electrode pads 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 off the support, drilling, 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 as necessary.
(5) A step of forming solder balls on the rewiring layer.
(6) A step of performing dicing.

As an example of the manufacturing method of the wafer level chip size package of another fan-in structure, the method described in the patent 3618330 is mentioned, for example, The method including the following processes is mentioned.
(1) A step of creating a silicon wafer on which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed.
(2) A step of forming a columnar electrode on the upper surface of the electrode pad portion on the silicon wafer.
(3) A step of bonding the adhesive film of the present invention from the columnar electrode surface side, curing, peeling the support, and forming an insulating layer.
(4) A step of appropriately polishing and removing the upper surface portion of the insulating layer and 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) A step of performing dicing.

An example of a method for manufacturing a fan-out wafer level chip size package using the adhesive film manufactured as described above includes a method including the following steps.
(1) A step of dicing a silicon wafer to create chip pieces.
(2) A step of fixing the chip pieces on the support substrate through a film.
(3) A step of laminating the adhesive film of the present invention from the chip piece side.
(4) A step of curing the film, peeling off the support, drilling, performing a desmear treatment, and forming a rewiring layer by electroless plating and electrolytic plating.
(5) The process of laminating | stacking a film further as needed.
(6) A step of forming solder balls on the rewiring layer.

As an example of the manufacturing method of the wafer level package of another fanout structure, the method described in Unexamined-Japanese-Patent No. 2005-167191 is mentioned, for example, The method including the following processes is mentioned.
(1) A step of creating a silicon wafer on which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed.
(2) A step of creating semiconductor chip pieces through dicing.
(3) A process of widely arranging and fixing the semiconductor chips via the film on the support in such a positional relationship 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 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 the insulating layer using a photoresist and forming a solder ball on the electrode pad.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention at all. In addition, the “part” described below means “part by mass”.

[Production of polymer resin A]
In a reaction vessel, 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%: Nippon Soda Co., Ltd.), ipzol 23.5 g of 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added and the reaction was carried out for about 3 hours. The reaction was then cooled to room temperature before 8.96 g benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g triethylenediamine, and ethyl diglycol. 40.4 g of acetate (manufactured by Daicel Chemical Industries, 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 at 2250 cm ⁻¹ was confirmed by FT-IR. Confirming 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 through 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 structure part: 50 / (50 + 4.8 + 8.96) × 100 = 78.4% by mass

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

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

Example 3
Spherical silica surface-treated with the phenylaminosilane coupling agent of Example 1 (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) (manufactured by Admatechs Co., Ltd., “SO-C2”, average particle size 0.5 μm) ), A spherical silica surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C5” manufactured by Admatechs Co., Ltd., average particle size 1.6 μm) An adhesive film was obtained in the same manner as in Example 1 except for changing to.

Example 4
Spherical silica surface-treated with the phenylaminosilane coupling agent of Example 2 (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) (manufactured by Admatechs Co., Ltd., “SO-C2”, average particle size 0.5 μm) ), A spherical silica surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C5” manufactured by Admatechs Co., Ltd., average particle size 1.6 μm) The adhesive film was obtained like Example 2 except having changed into.

[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]
40.3 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation), 0.5 part of imidazole derivative (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd.), 30 parts of MEK, liquid naphthalene Type epoxy resin (epoxy equivalent 151, DIC Corporation, "HP4032" 10 parts, solid naphthalene type epoxy resin (epoxy equivalent 250, DIC Corporation, "HP6000" 42.5 parts, phenoxy resin solution (Japan Epoxy) “YX-6554” manufactured by Resin Co., Ltd., 14 parts of a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass, glass transition temperature of 120 ° C., phenol novolac resin (phenolic hydroxyl group equivalent 105, manufactured by DIC Corporation), “TD2090” MEK varnish with non-volatile content of 60 mass%) 75 parts, Feni 625 parts of spherical silica (manufactured by Admatechs, “SO-C2”, average particle size of 0.5 μm) surface-treated with an aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) is mixed. A resin varnish was prepared by uniformly dispersing with a high-speed rotary mixer, and an adhesive film was obtained in the same manner as in Example 1.

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

[Evaluation of warpage]
On the PET film, the resin varnish described in Examples 1 to 4 and Comparative Example 1 was applied 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 thermoset. The adhesive resin composition layer was formed to produce an adhesive film. This adhesive film (80 μm) is bonded to a silicon wafer (100 μm) with a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.), heat treated at 180 ° C. for 90 minutes, and warped. The presence or absence of was observed. The edge of the wafer after the above treatment was pressed, and the distance between the wafer edge on the opposite side of the pressed portion and the ground was taken as the amount of warpage. A case where the amount of warpage was 0 to 5 mm was evaluated as “◯”, and a case where the amount of warpage was greater than 5 mm was evaluated as “x”. The results are shown in Table 1.

(Measurement 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 thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on 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 linear thermal expansion coefficient from 25 ° C. to 150 ° C. and the average linear thermal expansion coefficient from 150 ° C. to 220 ° C. in the second measurement were calculated.

[Evaluation of dimensional stability]
The above-mentioned 25 ° C. to 150 ° C. average linear thermal expansion coefficient of 30 ppm / ° C. or less and 150 ° C. to 220 ° C. average linear thermal expansion coefficient of 32 ppm / ° C. The average linear thermal expansion coefficient from 30 to 150 ° C. is greater than 30 ppm / ° C., or the average linear thermal expansion coefficient from 150 to 220 ° C. is greater than 32 ppm / ° C. A sample having an average linear thermal expansion coefficient of greater than 100 ppm / ° C or an average linear thermal expansion coefficient of 200 ppm / ° C from 150 ° C to 220 ° C was evaluated as "x".

[Measurement of arithmetic average roughness (Ra) and peel strength]
(1) Substrate treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminate [copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES] on both sides of MEC CZ8100 The copper surface was roughened by dipping in
(2) Lamination of adhesive film The above-mentioned adhesive film was laminated on both surfaces of a laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
(3) Curing of resin composition The PET film was peeled off from the laminated adhesive film, and the resin composition was cured at 180 ° C for 30 minutes to form an insulating layer.
(4) Roughening treatment The laminate on which the insulating layer is formed is immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 5 minutes at 60 ° C., and then roughened. As a solution, it is immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 5 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. It was immersed in Reduction Sholysin Securigant P at 40 ° C. for 5 minutes. The laminated board after the roughening treatment was used as an evaluation board 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, annealing was performed at 180 ° C. for 60 minutes. The laminated board after plating was used as an evaluation board B.
(6) Measurement of arithmetic average roughness (Ra) Using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Beeco Instruments Inc.), a measurement range of 121 μm × 92 μm can be obtained with a VSI contact mode and a 50 × lens. Ra value was calculated | required by the numerical value. And it measured by calculating | requiring the average value of 10 points | pieces.
(7) Measurement of peel strength A conductor layer of evaluation board B is cut with a 10 mm width and a length of 100 mm, and one end is peeled off to grasp the grip (TSE, Inc., Autocom type tester AC -50C-SL), and 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 linear thermal expansion coefficient is low, the dimensional stability is excellent, and the warpage is also suppressed. On the other hand, in Comparative Example 1, since the content of the inorganic filler is small, the warpage is reduced, but the dimensional stability is inferior. In addition, it can be seen that Reference Example 1 does not use a polymer resin having a glass transition temperature of 30 ° C. or lower, causes warping, and has high dimensional stability.

  By using the insulating resin material of the present invention, an insulating resin material having high dimensional stability and small warpage can be provided.

Claims (21)

An insulating resin material comprising a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30 ° C. or lower,
The content of the inorganic filler is 50 to 95% by mass with respect to 100% by mass of the nonvolatile component of the insulating resin material.
Insulating resin material. The cured product of the insulating resin material has a coefficient of linear thermal expansion at 25 ° C. to 150 ° C. of 3 to 30 ppm / ° C. and a coefficient of linear thermal expansion at 150 ° C. to 220 ° C. of 5 to 32 ppm / ° C.
The elastic modulus at 25 ° C. of the cured product of the insulating resin material is 0.5 to 14 GPa.
The insulating resin material according to claim 1. 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 to 220 ° C. of 5 to 15 ppm / ° C.,
The cured product of the insulating resin material has an elastic modulus at 25 ° C. of 0.5 to 6 GPa.
The insulating resin material according to claim 1 or 2.   When the linear expansion coefficient at 25 ° C. to 150 ° C. of the cured product of the insulating resin material is A (ppm / ° C.) and the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is B (ppm / ° C.), 0 ≦ B The insulating resin material according to claim 1, wherein −A ≦ 15.   When the linear expansion coefficient at 25 ° C. to 150 ° C. of the cured product of the insulating resin material is A (ppm / ° C.) and the linear thermal expansion coefficient at 150 ° C. to 220 ° C. is B (ppm / ° C.), 0 ≦ B The insulating resin material according to claim 1, wherein −A ≦ 4.   The insulating resin material according to claim 1, wherein the thermosetting resin is an epoxy resin.   The insulating resin material according to claim 1, wherein the thermosetting resin is a liquid epoxy resin.   The insulating resin material according to any one of claims 1 to 7, wherein a content of the thermosetting resin is 1 to 15% by mass with respect to 100% by mass of a nonvolatile component of the insulating resin material.   The insulating resin material according to claim 1, wherein the inorganic filler is silica.   The insulating resin material according to claim 1, wherein the polymer resin has a number average molecular weight of 300 to 100,000.   The insulating resin material of any one of Claims 1-10 whose number average molecular weights of the said polymer resin are 8000-20000.   The insulating resin material according to claim 1, wherein the polymer resin has at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a siloxane skeleton.   The insulating resin material according to claim 1, wherein the polymer resin has a butadiene skeleton, an imide skeleton, and a urethane skeleton.   The insulating resin material according to claim 1, wherein a content of the polymer resin is 1 to 30% by mass with respect to 100% by mass of a nonvolatile component of the insulating resin material.   An adhesive film formed by layering the insulating resin material according to claim 1 on a support.   The sheet-like hardened | cured material formed by thermosetting the insulating resin material of any one of Claims 1-14.   The amount of 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 claims 1 to 14 on a silicon wafer and thermally curing the layer is 0. Sheet-like cured product that is ˜5 mm.   The printed wiring board formed using the insulating resin material of any one of Claims 1-14.   A printed wiring board having a conductor layer formed on the sheet-like cured product according to claim 16.   A wafer level chip size package using the insulating resin material according to claim 1.   18. A wafer level chip size package in which a conductor layer is formed on the sheet-like cured product according to claim 16 or 17.