KR102125687B1 - Insulating resin material - Google Patents

Abstract

[PROBLEMS] The technical problem to be achieved by the present invention is to provide an insulating resin material having high dimensional stability and small warpage during curing.
[Solutions] 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 50 to 95% by mass relative to 100% by mass of the nonvolatile component in the insulating resin material Phosphorus insulating resin material.

Description

Insulation resin material {INSULATING RESIN MATERIAL}

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

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

Patent Document 1: Japanese Patent Application Publication No. 2006-37083

In view of the above phenomena, a technical problem to be achieved by the present invention is to provide an insulating resin material having high dimensional stability and low warpage during curing.

In order to solve the above problem, as a result of repeated studies by the present inventors, surprisingly, even when a large amount of inorganic fillers are blended in an insulating resin material containing a thermosetting resin and a specific polymer resin, the elastic modulus of the insulating resin material It has been found that the rise is suppressed and an insulating resin material excellent in both properties of low elastic modulus and low linear thermal expansion coefficient can be obtained.

That is, the present invention includes the following contents.

[1] An insulating resin material 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 50 to 95% by mass relative to 100% by mass of the nonvolatile component in the insulating resin material , Insulating resin material.

[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, and the insulating resin The insulating resin material according to [1], wherein the cured product of the material has an elastic modulus of 0.5 to 14 GPa at 25°C.

[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, and the insulating resin The insulating resin material according to [1], wherein the cured product of the material has an elastic modulus of 0.5 to 6 GPa at 25°C.

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

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

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

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

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

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

[10] The insulating resin material according to [1], wherein the number average molecular weight of the polymer resin is 300 to 100000.

[11] The insulating resin material according to [1], wherein the number average molecular weight of the polymer resin is 8000 to 20000.

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

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

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

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

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

[17] The amount of warpage at 25°C when a sheet-like cured product is formed on a silicon wafer is 0 to 0 by layering the insulating resin material according to any one of [1] to [14] on a silicon wafer and heat-curing it. The sheet-like cured product according to [16], which is 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 having a conductor layer formed on the sheet-like cured product according to [16].

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

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

[22] A wafer-level chip size package in which a conductor layer is formed on the sheet-like cured product according to [16].

[23] A wafer-level chip size package in which a conductor layer is formed on the sheet-like cured product according to [17].

The present invention provides an insulating resin material having high dimensional stability and low warpage during curing.

(Insulation 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 less, and may contain a curing accelerator, other components, and the like, if necessary. It will be described in detail below.

(a) Thermosetting resin

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

Although it does not specifically limit as an epoxy resin, It is preferable to contain the epoxy resin which has 2 or more epoxy groups in 1 molecule. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, Naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure And epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethyrol type epoxy resins, and halogenated epoxy resins. These may be used alone or in combination of two or more.

Among them, it is preferable to use at least one selected from the group consisting of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, naphthalene-type epoxy resin, and epoxy resin having a butadiene structure. In addition, the epoxy resin can further lower the elastic modulus of the cured product by containing the liquid epoxy resin, thereby reducing the warpage during curing. As the liquid epoxy resin, an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20°C is preferable. In addition, the aromatic epoxy resin referred to in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When the liquid epoxy resin is used as the epoxy resin, when the total amount of the epoxy resin is 100 parts by mass, it is preferable to use 60 to 100 parts by mass of the liquid epoxy resin, preferably 75 to 100 parts by mass, and 85 to 100 It is more preferable to use parts by mass. Examples of commercially available epoxy resins include ``jER828EL'' manufactured by Mitsubishi Chemical Corporation (liquid bisphenol A type epoxy resin, epoxy equivalent 180), ``HP4032'' manufactured by DIC Corporation (liquid naphthalene type epoxy resin, epoxy equivalent 151) And the like.

The phenolic resin is not particularly limited, and examples thereof include a phenol novolak resin, a biphenyl skeleton-containing phenol resin, a naphthalene skeleton-containing phenol resin, and a triazine skeleton-containing phenol resin. As a phenol novolak resin, DIC Corporation "TD2090" etc. are mentioned, for example. 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 Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375" and "SN395" manufactured by Shinnitetsu Chemical Co., Ltd.; "ICB9500" 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.

Although there is no restriction|limiting in particular as a cyanate ester resin, For example, a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type (bisphenol And cyanate ester resins such as A type, bisphenol F type, and bisphenol S type), and prepolymers in which they are partially triazine. As specific examples of the cyanate ester resin, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylene bis (2, 6-dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis( 4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4 -Cyanate phenyl) Difunctional cyanate resins such as thioether and bis(4-cyanatephenyl) ether, polyfunctional cyanate resins derived from phenol novolac, cresol novolac, phenol resin containing dicyclopentadiene structure, etc. And prepolymers in which these cyanate resins are partially triazined. These may be used alone or in combination of two or more. As examples of commercially available cyanate ester resins, some or all of phenol novolac-type polyfunctional cyanate ester resins (manufactured by Longja Japan Co., Ltd., PT30S, cyanate equivalent weight 124), bisphenol A dicyanates are triazineized, and 3 Prepolymer which became a monomer (manufactured by Longja Japan Co., Ltd., BA230S, cyanate equivalent 232), cyanate ester resin containing a dicyclopentadiene structure (manufactured by Longja Japan Co., Ltd., DT-4000, DT-7000). have.

Examples of the benzoxazine-based resin include "B-a type benzoxazine" and "B-m type benzoxazine" manufactured by Shikoku Chemical Co., Ltd., and the like.

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

(b) inorganic filler

The insulating resin material of the present invention can lower the coefficient of linear thermal expansion by containing an inorganic filler. The inorganic filler is not particularly limited, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, And strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silicas such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are preferable, and from the viewpoint of improving filling properties, fused silica and spherical silica are more preferable, and spherical melting Silica is even more preferred. These may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SO-C5", "SO-C2" and "SO-C1" manufactured by Adomartex Co., Ltd.

Although the average particle diameter of an inorganic filler is not specifically limited, From the viewpoint that it is necessary to make it a low illuminance in order to enable fine wiring formation after the roughening process of the surface of an insulating layer, and the via by laser processing (via) From the viewpoint of improving the shape, 5 µm or less is preferable, 3 µm or less is more preferable, 2 µm or less is more preferable, 1 µm or less is even more preferable, and 0.8 µm or less is particularly preferable. , 0.6 µm or less is particularly preferred. On the other hand, in the case where the resin composition is a resin varnish, from the viewpoint of preventing the viscosity of the varnish from rising and handling property being lowered, the average particle diameter of the inorganic filler is preferably 0.01 µm or more, and more preferably 0.03 µm or more. And more preferably 0.05 µm or more, still more preferably 0.07 µm or more, and particularly preferably 0.1 µm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured by making it an average particle diameter. As the measurement sample, one in which an inorganic filler is 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 Horibasakusho Co., Ltd. can be used.

The content of the inorganic filler is preferably 50% by mass or more with respect to 100% by mass of the nonvolatile component in the insulating resin material in order to lower the coefficient of linear thermal expansion of the cured product. The insulating resin material of the present invention can maintain the elastic modulus low even when the coefficient of linear thermal expansion is increased, so the content of the inorganic filler can be increased to 60% by mass or more, 70% by mass or more, or 80% by mass or more. On the other hand, the content of the inorganic filler is preferably 95% by mass or less with respect to 100% by mass of the nonvolatile component in the insulating resin material, in that the cured product is prevented from falling off and the surface of the insulating layer after roughening treatment is made to have low illumination. , 90% by mass or less is more preferable.

It is preferable to surface-treat the inorganic filler with a surface treatment agent, specifically, for example, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a styrylsilane-based coupling agent, an acrylatesilane-based Surface treatment with at least one surface treatment agent selected from 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 do. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved.

Examples of specific coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-methylamino Aminosilane-based coupling agents such as propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, 3 -Glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, glycine Epoxysilane-based coupling agents such as cydylbutyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxy Mercaptosilane-based coupling agents such as silane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane, styrylsilane-based coupling agents such as p-styryl trimethoxysilane, 3-acrylic Oxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiethoxysilane, etc. Acrylate silane coupling agents, isocyanate silane coupling agents such as 3-isocyanate propyl trimethoxysilane, sulfide silanes such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide System coupling agents, silane systems such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, and t-butyltrimethoxysilane Coupling agent, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, octamethylcyclotetrasila Glass, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldi Silazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyl disilazane, 1,3- Dipropyltetramethyldisilazane, hexamethylcyclotrisil Organosilazane compounds such as razan, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n-butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium Octylene glycolate, diisopropoxytitanium bis (triethanol aminate), dihydroxy titanium bislactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (di Octylpyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra(2-ethylhexyl) titanate, tetraisopropylbis(dioctyl phosphate) titanate, Tetraoctylbis(ditridecylphosphate)titanate, tetra(2,2-diaryloxymethyl-1-butyl)bis(ditridecyl)phosphate titanate, isopropyltrioctanoyl titanate, isopropyltricumylphenyl Titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl And titanate-based coupling agents such as tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, and isopropyl tri(N-amideethyl·aminoethyl) titanate. Among these, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, and an organosilazane compound are preferable, and an aminosilane-based coupling agent is more preferable. Examples of commercial products include "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd. (3-glycidoxypropyl trimethoxysilane) and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3-mercaptopropyl trimethoxysilane). , Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane), Shin-Etsu "SZ-31" (hexamethyldisilazane) manufactured by Kagaku Kogyo Co., Ltd.; and the like.

It is preferable to add an inorganic filler to a resin composition after surface-treating it with a surface treating agent. In this case, the dispersibility of the inorganic filler can be further improved.

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

(c) a polymer resin having a glass transition temperature of 30°C or less

The insulating resin material of the present invention can contain a polymer resin having a glass transition temperature of 30°C or lower, thereby reducing the elastic modulus of the cured product, and further improving the peel strength of the conductor layer and the insulating layer. In addition, the polymer resin having a glass transition temperature of 30° C. or less can hardly change the coefficient of linear thermal expansion in a wide temperature range of 25° C. to 220° C., and can suppress the variation in the coefficient of linear thermal expansion of the cured product low. For this reason, the glass transition temperature is more preferably 20°C or lower, and even more preferably 10°C or lower. 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 less is not particularly limited, but polymer resins having a butadiene skeleton, an amide skeleton, an imide skeleton, an acetal skeleton, a carbonate skeleton, an ester skeleton, a urethane skeleton, an acrylic skeleton or a siloxane skeleton are mentioned. have. Among these, it is preferable to use a polymer resin having one or more skeletons selected from butadiene skeleton, carbonate skeleton, acrylic skeleton and siloxane skeleton from the viewpoint of more flexibility and adhesion, further improving heat resistance and compatibility. In, polymer resins having at least one skeleton selected from butadiene skeleton, carbonate skeleton, acrylic skeleton and siloxane skeleton, and at least one skeleton selected from amide skeleton, imide skeleton and urethane skeleton are more preferred. More preferably, it is a polymer resin having a butadiene skeleton, an imide skeleton and a urethane skeleton, a polymer resin having an acrylic skeleton, and a polymer resin having an imide skeleton and a siloxane skeleton. In addition, 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 mass% (preferably 60 to 80 mass%). In the polymer resin having a siloxane skeleton, it is preferable that the content of the siloxane skeleton in the polymer is 40 to 80% by mass (preferably 50 to 75% by mass).

Here, the measurement of the glass transition temperature of the polymer resin can be carried out as follows. The polymer resin is applied onto the PET film, and the solvent is dried by heating at 180° C. for 90 minutes to obtain a film shape. The film was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and the thermomechanical analysis was performed by a tensile weighting method using "EXSTAR TMA/SS6000" manufactured by SIA Inno Technology Co., Ltd. Specifically, after attaching the test piece to the device, two measurements were continuously made under the measurement conditions of 1 g load and 5°C/min heating rate, and Tg was calculated from the second measurement.

The number average molecular weight of the polymer resin is preferably in the range of 300 to 100000, more preferably in the range of 800 to 80000, more preferably in the range of 1500 to 60000, and even more preferably in the range of 5000 to 40000 And it is particularly preferable to be 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. In addition, the number average molecular weight in this invention is measured by 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/ manufactured by Showa Denko Corporation as a column. K-804L can be measured using a chloroform or the like as a mobile phase at a column temperature of 40°C, and calculated using a standard polystyrene calibration curve.

As a specific example, a polymer resin having a butadiene skeleton (manufactured by Nippon Soda Co., Ltd. "G-1000", "G-3000", "GI-1000", "GI-3000", manufactured by Idemitsu Seki Yukagaku Co., Ltd." R-45EPI, manufactured by Daisel Chemical Co., Ltd., ``PB3600'', ``Epo Friend AT501'', Claybare Co., Ltd. ``Ricon130'', ``Ricon142'', ``Ricon150'', ``Ricon657'', ``Ricon130MA''), A polymer resin having a butadiene skeleton and a polyimide skeleton (polymer resin described in Japanese Unexamined Patent Publication No. 2006-37083), a polymer resin having an acrylic skeleton ("SG-P3" manufactured by Nagase Chemtex Co., Ltd., "SG-600LB , "SG-280", "SG-790", "SG-K2", "SN-50", "AS-3000E", "ME-2000" manufactured by Negami Kogyo Co., Ltd., 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 even more preferably 5% by mass or more with respect to 100% by mass of the nonvolatile component in the insulating resin material. desirable. On the other hand, from the viewpoint of enabling production of a uniform cured product without impairing the compatibility of the resin varnish, the content of the polymer resin is preferably 30% by mass or less with respect to 100% by mass of the nonvolatile component in the insulating resin material. , 25% by mass or less is more preferable, and 20% by mass or less is more preferable.

(d) curing accelerator

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

As the imidazole-based curing accelerator, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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 trimeritate, 1-cyanoethyl-2-phenylimidazole Trimerate, 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-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid addition Water, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole, and 2-phenylimidazoline, and imidazole compounds and epoxy resins And adducts.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylamino methyl)phenol, and 1,8. And amine compounds such as -diazabicyclo[5.4.0]-7-undecene (hereinafter abbreviated as DBU).

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tril)guanidine, dimethylguanidine, and diphenylguanidine , Trimethylguanidine, 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-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-(o-tril) biguanide, and the like.

Examples of the phosphonium-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, (4-methylphenyl) And triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, and butyl triphenyl phosphonium thiocyanate.

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

(e) Other ingredients

To the insulating resin material of the present invention, other components can be blended as necessary within a range that does not impair the effects of the present invention. As other components, for example, organic fillers such as silicone powder, nylon powder, fluorine powder, and rubber particles, thickeners such as Orben and Benton, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, thiazole-based, triazole-based, Adhesion imparting agents such as silane coupling agents, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black and other coloring agents, organophosphorous flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon flame retardants, metal hydroxides Flame retardants such as and the like.

The insulating resin material of the present invention is appropriately mixed with the above components, and if necessary, kneading means such as three rolls, ball mills, bead mills, sand mills, or agitation such as a super mixer, a planetary mixer, etc. It can be prepared by kneading or mixing by means. Moreover, it can also prepare as a resin varnish by adding an organic solvent further.

Since the insulating resin material of the present invention can exhibit excellent performance of reducing curvature of the cured product while increasing the dimensional stability of the cured product, it is suitable to use it as a sheet-like cured product obtained by thermosetting the insulating resin material. Do. In addition, the cured sheet-like material only needs to be heat-cured on an insulating resin material, and a cured sheet-like material is also laminated on a circuit board.

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 150°C to 220°C to increase the dimensional stability of the cured product. It is preferable that it is 32 ppm/degreeC. The upper limit of the linear thermal expansion coefficient at 25°C to 150°C is more preferably 25 ppm/°C or less, more preferably 20 ppm/°C or less, even more preferably 15 ppm/°C or less, and particularly preferably 10 ppm/°C or less. Meanwhile, the lower limit of the linear thermal expansion coefficient at 25°C to 150°C is not particularly limited, and is 3 ppm/°C or higher, 4 ppm/°C or higher, 5 ppm/°C or higher. Further, the upper limit of the linear thermal expansion coefficient at 150°C to 220°C is more preferably 30 ppm/°C or less, more preferably 25 ppm/°C or less, even more preferably 20 ppm/°C or less, and particularly preferably 15 ppm/°C or less Do. On the other hand, the lower limit of the linear thermal expansion coefficient at 150°C to 220°C is not particularly limited, and is 5 ppm/°C or higher, 6 ppm/°C or higher, 7 ppm/°C or higher.

The cured product of the insulating resin material of the present invention has a coefficient of linear expansion at 25°C to 150°C in order to further increase the dimensional stability of the cured product by reducing the fluctuation of the coefficient of linear thermal expansion at 25°C to 150°C and also at 150°C to 220°C. When A is set to A (ppm/°C) and the coefficient of linear thermal expansion at 150°C to 220°C is set to B (ppm/°C), it is preferable to set 0≤BA≤15. More preferably, 0≤B-A≤12, more preferably 0≤B-A≤9, even more preferably 0≤B-A≤6, particularly preferably 0≤B-A≤4.

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 curvature of the cured product. The upper limit of the elastic modulus at 25°C is more preferably 12 GPa or less, more preferably 10 GPa or less, even more preferably 8 GPa or less, and particularly preferably 6 GPa or less. On the other hand, the lower limit of the elastic modulus at 25°C is not particularly limited, and is 1 GPa or more, 2 GPa or more, and 3 GPa or more.

The curvature amount of the sheet-like cured product of the present invention is confirmed as follows. A sheet-shaped cured product is formed on a silicon wafer by preparing a circular silicon wafer having a thickness of 100 µm and a diameter of 100 mm, and forming an insulating resin material on the silicon wafer by thermal curing. Next, the layered product on which the sheet-shaped cured product is formed on the silicon wafer is placed at a room temperature (25°C) with the silicon wafer down on a flat table, and one end of the cured product is pressed firmly with a finger. Then, the amount of warpage of the laminate can be determined by measuring the distance between the diagonal silicon wafer end and the flat tabletop. The amount of warpage at 25°C of the laminate is preferably 0 to 5 mm.

Although it does not specifically limit as the 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, or a wafer level chip size package. The insulating resin material of the present invention may be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is generally preferred to use it 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, the resin varnish is applied to a support using a die coater or the like, and heated again. Alternatively, by drying the organic solvent by hot air spraying or the like to form a resin composition layer on the support, the insulating resin material can be produced as an adhesive film layered on the support.

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

Drying conditions are not particularly limited, and the content of the organic solvent to the resin composition layer (residual solvent amount) is, for example, 1 to 10% by mass or less, and preferably dried to 2 to 6% by mass or less. The amount of the organic solvent in the varnish differs depending on the boiling point of the organic solvent, but for example, 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, a resin composition layer can be formed. have.

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

As the support, for example, films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyester films such as polyethylene naphthalate, polycarbonate And various plastic films such as films and polyimide films. Moreover, you may use release paper or metal foils, such as copper foil and aluminum foil. Especially, from a versatility point, a plastic film is preferable and a PET film is more preferable. The support and the protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. Moreover, you may perform a mold release process with a mold release agent, such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluorine resin mold release agent. Although the thickness of the support is not particularly limited, 10 to 150 μm is preferable, and 25 to 50 μm is more preferable.

On the surface where the support of the resin composition layer is not in close contact, a protective film conforming to the support can be further laminated. 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, adhesion or damage to the surface of the resin composition layer, such as dust, can be prevented. The adhesive film can also be wound and stored in a roll shape.

(Printed wiring board)

Examples of the printed wiring board of the present invention include rigid circuit boards, flexible circuit boards, single-sided laminated boards, and thin-walled boards. An example of a method of manufacturing a printed wiring board using the adhesive film prepared as described above will be described.

First, the adhesive film is laminated (laminated) on one side or both sides of the inner layer circuit board using a vacuum laminator. As a board|substrate used for an inner layer circuit board, a glass epoxy board|substrate, a metal board|substrate, a polyester board|substrate, a polyimide board|substrate, BT resin board|substrate, thermosetting type polyphenylene ether board|substrate etc. are mentioned, for example. In addition, the inner-layer circuit board means that a conductor layer (circuit) patterned is formed on one or both surfaces of the substrate as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). Is included. Moreover, roughening treatment may be previously performed on the surface of the conductor layer by blackening treatment, copper etching, or the like.

In the above-mentioned laminate, when the adhesive film has a protective film, after the protective film is removed, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is laminated to the circuit board while pressing and heating. In the adhesive film of the present invention, a method of laminating to a circuit board under reduced pressure by a vacuum lamination method is suitably used. The conditions of the laminate are not particularly limited, but for example, the compression temperature (laminate temperature) is preferably 70 to 140°C, and the compression pressure (laminate pressure) is preferably 1 to 1lkgf/cm ² (9.8×10 ⁴⁾ It is preferably from 107.9 x 10 ⁴ N/m ² ), the pressing time (laminate time) is preferably 5 to 180 seconds, and it is preferable to laminate under reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the method of lamination may be a batch type or a continuous type in a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurized laminator manufactured by Mekise Sakusho, a roll-type dry coater manufactured by Hitachi Industries, and Hitachi ACC Co., Ltd. And a manufacturing vacuum laminator.

After the adhesive film is laminated to the inner-layer circuit board, after cooling to room temperature, when the support is peeled off, the insulation layer can be formed on the inner-layer circuit board by peeling off and thermosetting the resin composition to form a cured product. The conditions of the thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 20 to 180 minutes at 150°C to 220°C, more preferably 30 to 120 at 160°C to 210°C. It is selected in the range of minutes. After forming the insulating layer, if the support is not peeled off before curing, the support may be peeled off as necessary. The thickness of the insulating layer is preferably 10 to 200 μm, similar to the thickness of the resin composition layer formed in the adhesive film, and from the viewpoint of thinning, 15 to 100 μm is more preferable, and 20 to 60 μm This is more preferred.

Next, a through hole is formed in the insulating layer formed on the inner layer circuit board to form via holes and through holes. The drilling may be performed by known methods such as, for example, drilling, laser, plasma, or a combination of these methods as necessary, but drilling by lasers such as carbon dioxide gas lasers and YAG lasers is the most. This is the usual method. If the support is not peeled before drilling, the support is peeled here.

Next, roughening treatment is performed on the surface of the insulating layer. Plasma treatment etc. are mentioned in the case of a dry conditioning treatment, and in the case of a wet conditioning treatment, the method of performing the swelling treatment with a swelling liquid, the conditioning treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid in this order is mentioned. Can. The wet roughening treatment is preferable in that it is possible to remove smear in the via hole 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). An alkali solution, a surfactant solution, etc. are mentioned as a swelling liquid, Preferably it is an alkali solution, As an alkali solution, sodium hydroxide solution, potassium hydroxide solution, etc. are mentioned, for example. Examples of commercially available swelling solutions include Swelling Dip Securiganth P (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., and Swelling Dip Securiganth SBU (SBU). Can be lifted. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer at 60 to 80°C for 10 to 30 minutes (preferably at 15 to 25 minutes at 70 to 80°C) and immersing it in an oxidizing agent solution. Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include solutions of alkaline permanganic acid such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and dosing solution SECURIGANS P. The neutralization treatment with the neutralization solution is performed by immersing in the neutralization solution at 30 to 50°C for 3 to 10 minutes (preferably at 35 to 45°C for 3 to 8 minutes). An acidic aqueous solution is preferable as the neutralizing solution, and, for example, a commercially available product, a reduction solution SECURIGANGS P manufactured by Atotech Japan Co., Ltd. is mentioned.

The arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 220 to 1000 nm, and more preferably 300 to 800 nm, from the viewpoint of fine wiring formation and stabilization of peel strength. Specifically, using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bcoins Instruments), the Ra value can be determined by the numerical value obtained by setting the measurement range to 121 μm×92 μm with a VSI contact mode and a 50-fold lens. have.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used, for example. Examples of the 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. Can.

The peel strength of the conductor layer and the insulating layer is preferably 0.5 kgf/cm or more, more preferably 0.6 kgf/cm or more, and 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, a semi-additive method, or the like known to those skilled in the art can be used. By repeating the series of steps a plurality of times, the multi-layered build-up layer is stacked in multiple stages. A printed wiring board can also be formed. As described above, in the present invention, since the dimensional stability of the cured product is high and the cured product is small, it can be suitably used for printed wiring boards such as rigid circuit boards, flexible circuit boards, single-sided laminated boards, and thin substrates. Even if the dimensional stability of the cured product is high and the cured product has little warpage, 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 properties 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. Although various structures are devised in the wafer level chip size package, it can be largely 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 prepared as described above, a method including the following steps is exemplified.

(1) Process of forming circuit and electrode pad on silicon wafer.

(2) The process of laminating the adhesive film of the present invention on a silicon wafer.

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

(4) The process of repeating (2) and (3) further on this redistribution layer as needed.

(5) Process of forming solder ball on redistribution layer.

(6) Process of dicing.

As an example of the manufacturing method of the wafer level chip size package of another fan-in structure, the method described in Japanese Patent No. 3618330 is mentioned, for example, and the method including the following processes is mentioned.

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

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

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

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

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

(6) Process 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 prepared as described above, a method including the following steps is exemplified.

(1) A process of dicing a silicon wafer and producing a chip reorganization.

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

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

(4) The process of hardening a film, peeling a support body, perforating, performing a desmear process, and forming a redistribution layer by electroless plating and electrolytic plating.

(5) The process of laminating|stacking a film further as needed.

(6) Process of forming solder ball on redistribution layer.

As an example of the manufacturing method of the wafer level chip size package of another fan-out structure, the method of Unexamined-Japanese-Patent No. 2005-167191 is mentioned, for example, The method containing the following process is mentioned.

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

(2) Process of manufacturing semiconductor chip reorganization through dicing.

(3) A process in which a semiconductor chip is widely positioned and fixed through a film on a support in a positional relationship in which a distance between semiconductor chips has sufficient space to form a fan-out ball array in a subsequent step.

(4) The process of laminating the adhesive film of the present invention so as to fill the semiconductor chips on the side where 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) Process of forming a fanout pattern and an electrode on an insulating layer using a photoresist, and forming a solder ball on the electrode pad.

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but these are not intended to limit the present invention. In addition, "part" described below means "part by mass".

(Production of Polymer Resin A)

50 g of G-3000 (bifunctional hydroxyl group terminal polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g/eq., solid content 100 wt%: manufactured by Nippon Soda Co., Ltd.) in the reaction vessel and , Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Seki Yukagaku Co., Ltd.) 23.5 g, 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. The temperature was raised to 50°C in a homogeneous place, and while stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added to react for about 3 hours. Subsequently, after the reaction was cooled to room temperature, it was added to 8.96 g of benzophenone tetracarboxylic acid anhydride (acid anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyl diglycol acetate (Diecel Chemical Co., Ltd.) 40.4 g of Kogyo Co., Ltd. was added, the temperature was raised to 130° C. while stirring, and reaction was performed for about 4 hours. The disappearance of 2250 cm ^-1 NCO peak was confirmed by FT-IR. Considering the disappearance of the NCO peak, it was regarded as the end point of the reaction, the reaction was cooled to room temperature, and then filtered with a 100 mesh filter cloth to obtain a polymer resin A having an imide skeleton, urethane skeleton, butadiene skeleton.

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

Acid value: 16.9mgKOH/g

Solid content: 50% by mass

Number average molecular weight: 13723

Glass transition temperature: -10℃

The content ratio of the polybutadiene structural part: 50/(50+4.8+8.96)×100=78.4 mass%.

[Example 1]

40 parts of liquid bisphenol-A epoxy resin (epoxy equivalent 180, manufactured by Mitsubishi Chemical Corporation, ``jER828EL''), imidazole derivative (Shikoku Chemical Co., Ltd., ``2P4MZ'', 2-phenyl-4-methylimida Sol) 1 part, polymer resin A 260 parts, MEK 300 parts, liquid naphthalene type epoxy resin (epoxy equivalent 151, DIC Co., Ltd., ``HP4032'' 20 parts, phenyl aminosilane coupling agent (Shin Etsuka Chemical Co., Ltd.) 920 parts of spherical silica ("SO-C2", manufactured by Adomatex Co., Ltd., average particle diameter 0.5 µm) surface-treated with Gaisha Co., Ltd. ("KBM573") were mixed and dispersed uniformly with a high-speed rotary mixer to make resin varnish. Next, on a polyethylene terephthalate film (38 µm in thickness, hereinafter abbreviated as “PET film”), the resin composition layer after drying was applied with a die coater so that the thickness was 40 µm, and was 80 to 120° C. It dried by (average 100 degreeC) for 7 minutes, and the adhesive film was obtained.

[Example 2]

Liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Co., Ltd., ``jER828EL'') 54 parts, imidazole derivatives (Shikoku Chemical Co., Ltd., ``2P4MZ'') 1 part, polymer resin A 400 parts, MEK 300 parts, liquid naphthalene-type epoxy resin (Epoxy equivalent 151, DIC Co., Ltd., ``HP4032'' 20 parts, phenyl aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., ``KBM573'') surface-treated 920 parts of spherical silica (manufactured by Adomatex Co., Ltd., "SO-C2", average particle diameter 0.5 µm) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. To obtain an adhesive film.

[Example 3]

Spherical silica surface-treated with the phenylaminosilane-based coupling agent of Example 1 ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), "SO-C2", average particle diameter 0.5 µm) With spherical silica (Adomartex Co., Ltd., ``SO-C5'', average particle diameter of 1.6 µm) surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., ``KBM573'') The adhesive film was obtained like Example 1 except having changed.

[Example 4]

Spherical silica surface-treated with the phenylaminosilane-based coupling agent of Example 2 (manufactured by Shin-Etsu Chemical Co., Ltd., ``KBM573'') (Adomatex Co., Ltd., ``SO-C2'', average particle diameter 0.5 µm) ), spherical silica surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., ``KBM573'') (manufactured by Adomatex Co., Ltd., ``SO-C5'', average particle diameter of 1.6 µm) The adhesive film was obtained like Example 2 except having 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, Mitsubishi Chemical Co., Ltd., ``jER828EL'') 40.3 parts, imidazole derivative (Shikoku Chemical Co., Ltd., ``2P4MZ'') 0.5 parts, MEK 30 parts, liquid naphthalene Type Epoxy Resin (Epoxy equivalent 151, manufactured by DIC Corporation, 10 parts ``HP4032'', solid naphthalene type epoxy resin (Epoxy equivalent 250, manufactured by DIC Corporation, 42.5 parts by ``HP6000'', phenoxy resin solution (Japan Epoxy Resin ``YX6954'', a mixed solution of MEK and cyclohexanone of 30% by mass of non-volatile content, glass transition temperature of 120°C, 14 parts, phenol novolak resin (phenolic hydroxyl group equivalent 105, manufactured by DIC Co., Ltd.) , 75 parts non-volatile content of ``TD2090'' MEK varnish), spherical silica (Adomatex Co., Ltd.) surface-treated with phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., ``KBM573'') 625 parts of the prepared, "SO-C2", average particle diameter 0.5 mu m) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish, after which an adhesive film was obtained in the same manner as in Example 1.

(Measurement of modulus of elasticity)

The adhesive film was thermally cured at 180°C for 90 minutes to obtain a cured product on a sheet. Next, the PET film was peeled off, and the tensile strength of the cured product was measured by performing a tensile test of the cured product using a Tensilon universal testing machine (manufactured by A&D, Ltd.) according to Japanese Industrial Standards (JIS K7127). Did.

(Evaluation of bending)

On the PET film, the resin varnishes described in Examples 1 to 4 and Comparative Example 1 were applied with a die coater to a thickness of 80 μm, dried at 80 to 120° C. (average 100° C.) for 6 minutes, and the layer of the thermosetting resin composition. By forming, an adhesive film was prepared. This adhesive film (80 µm) was bonded to a silicon wafer (100 µm) with a batch-type vacuum press laminator MVLP-500 (manufactured by Miki Sesakusho Co., Ltd.) and heat treated at 180°C for 90 minutes (heat curing). The cured product was observed for warpage. The end portion of the wafer after the above-described treatment was pressed, and the distance between the end portion of the wafer opposite the pressed portion and the ground was taken as the amount of warpage. It was evaluated as "○" that the amount of warpage was 0 to 5 mm, and "X" when the amount of warpage was greater than 5 mm. Table 1 shows the results.

(Measurement of coefficient of linear thermal expansion)

The adhesive film was thermally cured at 190°C for 90 minutes to obtain a cured product in the form of a film. 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 weighting method using a thermo mechanical analysis apparatus (Thermo P1us TMA8310) manufactured by Rigaku Corporation. After attaching the test piece to the device, it 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 at 25°C to 150°C in the second measurement and the average linear thermal expansion coefficient at 150°C to 220°C were calculated.

(Evaluation of Dimensional Stability)

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

(Measurement of arithmetic mean roughness (Ra) and peel strength)

(1) Treatment of the base of the laminated board

Copper surface by immersing both sides of a glass cloth-based epoxy resin double-sided copper sheet laminated sheet (copper foil thickness of 18 µm, substrate thickness of 0.3 mm, manufactured by Matsushita Electric Co., Ltd. R5715ES) in MEC Corporation CZ8100 The roughening treatment was performed.

(2) adhesive film laminate

The adhesive film was laminated on both sides of a laminate by using a batch-type vacuum press laminator MVLP-500 (manufactured by Mekise Sakusho Co., Ltd.). The lamination was performed by reducing the pressure for 30 seconds, setting the air pressure to 13 hPa or less, and then pressing for 30 seconds at 100°C and a pressure of 0.74 MPa.

(3) curing of the resin composition

The PET film was peeled from the laminated adhesive film, and the resin composition was cured under conditions of 180° C. and 30 minutes to form an insulating layer.

(4) Harmony treatment

The laminated plate on which the insulating layer was formed was immersed in a swelling solution, diethylene glycol monobutyl ether-containing swelling di-securigans P of Atotech Japan Co., Ltd. for 5 minutes at 60° C. Tekjapan Co., Ltd. Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) was immersed at 80° C. for 5 minutes, and finally, as a neutralizing solution, the reduction of Atotech Japan Co., Ltd. The solution was immersed in SECURIGANS P at 40°C for 5 minutes. The laminate after this roughening treatment was used as evaluation substrate A.

(5) Plating by semi-adity method

In order to form a circuit on the surface of the insulating layer, the evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ and then immersed in an electroless copper plating solution. Subsequently, copper sulfate electrolytic plating was performed, and a conductor layer was formed to a thickness of 30 µm. Next, annealing treatment was performed at 180°C for 60 minutes. The laminate after this plating was used as the evaluation substrate B.

(6) Measurement of arithmetic mean roughness (Ra)

Using a non-contact surface roughness meter ("WYKO NT 3300" manufactured by Vicoins Instruments), the Ra value was determined by the value obtained by setting the measurement range to 121 µm x 92 µm with a VSI contact mode and a 50-fold lens. And it measured by obtaining the average value of 10 points.

(7) Measurement of peel strength

A 10 mm wide and 100 mm long portion was cut into the conductor layer of the evaluation board B, and the end was taken out and picked up with a gripping tool (KASK, Autocomm Tester AC-50C-SL), and at room temperature. , The load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min was measured.

From the results shown in Table 1, it can be seen that in Examples 1 to 4, the coefficient of linear thermal expansion was low, the dimensional stability was excellent, and the warpage during curing was also suppressed. On the other hand, in Comparative Example 1, since the content of the inorganic filler was small, the warpage during curing was reduced, but the dimensional stability was poor. 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, and warpage occurs during curing and also has a large dimensional stability.

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

Claims (23)

An insulating resin material containing a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30°C or less and a number average molecular weight of 100000 or less,
The insulating resin material whose content of the said inorganic filler is more than 60 mass% and 95 mass% or less with respect to 100 mass% of nonvolatile components in an insulating resin material. 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 whose elastic modulus at 25 degreeC of the hardened|cured material of the said insulating resin material is 0.5-14 GPa. The method according to claim 1, wherein 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 whose elastic modulus at 25 degreeC of the hardened|cured material of the said insulating resin material is 0.5-6 GPa. The coefficient of linear expansion at 25°C to 150°C of the cured product of the insulating resin material is A (ppm/°C), and the coefficient of linear thermal expansion at 150°C to 220°C is B (ppm/°C). In one case, 0≤BA≤15, the insulating resin material. The coefficient of linear expansion at 25°C to 150°C of the cured product of the insulating resin material is A (ppm/°C), and the coefficient of linear thermal expansion at 150°C to 220°C is B (ppm/°C). In one case, 0≤BA≤4, the insulating resin material. The insulating resin material according to claim 1, wherein the thermosetting resin is an epoxy resin. The insulating resin material according to claim 1, wherein the thermosetting resin is a liquid epoxy resin. The insulating resin material according to claim 1, wherein the content of the thermosetting resin is 1 to 15% by mass relative to 100% by mass of the nonvolatile component in the insulating resin material. The insulating resin material according to claim 1, wherein the inorganic filler is silica. The insulating resin material according to claim 1, wherein the number average molecular weight of the polymer resin is 300 to 100000. The insulating resin material according to claim 1, wherein the number average molecular weight of the polymer resin is 8000 to 20000. The insulating resin material according to claim 1, wherein the polymer resin has at least one skeleton selected from butadiene skeleton, carbonate skeleton, acrylic skeleton and siloxane skeleton. The insulating resin material according to claim 1, wherein the polymer resin has a butadiene skeleton, an imide skeleton and a urethane skeleton. The insulating resin material according to claim 1, wherein the content of the polymer resin is 1 to 30 mass% with respect to 100 mass% of the nonvolatile component in the insulating resin material. An adhesive film comprising the insulating resin material according to any one of claims 1 to 14 layered on a support. A sheet-like cured product obtained by thermally curing the insulating resin material according to any one of claims 1 to 14. The amount of curvature at 25°C when the sheet-like cured product is formed on a silicon wafer is 0 to 5 mm by thermally curing the insulating resin material according to any one of claims 1 to 14 on a silicon wafer. Cured sheet. A printed wiring board made of the insulating resin material according to any one of claims 1 to 14. A printed wiring board in which a conductor layer is formed on the sheet-like cured product according to claim 16. A printed wiring board in which a conductor layer is formed on the sheet-like cured product according to claim 17. A wafer-level chip size package made of the insulating resin material according to any one of claims 1 to 14. A wafer level chip size package in which a conductor layer is formed on the sheet-like cured product according to claim 16. A wafer level chip size package in which a conductor layer is formed on the sheet-like cured product according to claim 17.