JP2019011475A - Resin composition - Google Patents

Abstract

To provide a resin composition giving an insulating layer which does not cause a problem of warpage even when a thin core substrate is used.SOLUTION: The resin composition contains (A) an epoxy resin which is solid at 25°C, (B) an inorganic filler, and (C) one or more resins selected from the group consisting of functional group-containing saturated and unsaturated butadiene resins which are liquid at 25°C, functional group-containing saturated or unsaturated butadiene resins which are liquid at 25°C, and functional group-containing acrylic resins having a glass transition point of 25°C or lower. The content of the component (B) is 40 mass% or more based on 100 mass% of nonvolatile components in the resin composition. The content of the component (C) is 10-40 mass% based on 100 mass% of resin components.SELECTED DRAWING: None

Description

  The present invention relates to a novel resin composition. In more detail, this invention relates to the resin composition suitable for using for the insulating layer of a multilayer printed wiring board.

  As a manufacturing technique of a multilayer printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on a core substrate is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by curing a resin composition. As such a resin composition, it is known to use an epoxy resin composition (Patent Document 1).

  In recent years, when manufacturing a multilayer printed wiring board, an inorganic filler such as silica particles is highly blended in the resin composition in order to prevent cracks and circuit distortion due to the difference in thermal expansion between the insulating layer and the conductor layer. There is a tendency (Patent Document 2).

JP 2007-254709 A JP 2010-202865 A

  While it is desired to further reduce the thickness of the multilayer printed wiring board, the thickness of the core substrate tends to be gradually reduced. However, when a thin core substrate is used, due to insufficient rigidity of the core substrate, when the resin composition layer is laminated and cured only on one side of the core substrate, the entire laminated substrate is warped (hereinafter referred to as “warping of the warp”). May also be a problem ”).

  It is expected that the warpage problem can be alleviated by reducing the thermal expansion coefficient of the insulating layer and keeping the elastic modulus low. That is, it is expected that the problem of warpage is reduced by suppressing the thermal expansion itself of the insulating layer and relaxing the stress generated by the thermal expansion. Here, according to the recent trend of using a resin composition having a high inorganic filler content, although the thermal expansion coefficient of the obtained insulating layer is generally low, the elastic modulus is very high, so the problem of warpage is alleviated. However, measures are desired. Although it is conceivable to add a flexible component to the resin composition in order to reduce the elastic modulus of the insulating layer, in that case, the thermal expansion coefficient of the insulating layer is increased, and the problem of warpage cannot be alleviated. It is inferred.

  The subject of this invention is providing the resin composition which does not produce the problem of curvature even when it is a case where a thin core board | substrate is used.

  The present inventors have found that the above problems can be solved by using the following specific resin composition, and have completed the present invention.

  That is, the present invention includes the following contents.

[1] (A) an epoxy resin solid at 25 ° C.,
(B) inorganic filler,
(C) 1 selected from the group consisting of a functional group-containing saturated butadiene resin that is liquid at 25 ° C., a functional group-containing unsaturated butadiene resin that is liquid at 25 ° C., and a functional group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower. More than seed resin,
A resin composition comprising:
When the nonvolatile component in the resin composition is 100% by mass, the component (B) is 40% by mass or more,
The resin composition whose component (C) is 10 to 40% by mass when the resin component is 100% by mass.
[2] The resin composition according to [1], wherein the component (C) has one or more functional groups selected from the group consisting of acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups. object.
[3] The resin composition according to [1] or [2], wherein the component (A) is a bifunctional or higher-functional naphthalene skeleton epoxy resin.
[4] The resin composition according to any one of [1] to [3], further including a curing agent.
[5] The resin composition according to any one of [1] to [4], which is a resin composition for embedding a part.
[6] The resin composition according to any one of the above [1] to [5], wherein the inorganic filler has an average particle size of 10 μm or less and particles of 20 μm or more are removed by classification.
[7] A cured product obtained by curing the resin composition according to any one of [1] to [6].
[8] The cured product according to [7], wherein the glass transition temperature is 170 ° C. or higher.
[9] The cured product according to [7] or [8] above, wherein a product α × E of a linear thermal expansion coefficient (α) and an elastic modulus (E: GPa) is 150 or less.
[10] The linear thermal expansion coefficient (α) is 25 ppm or less, and the product α × E of the linear thermal expansion coefficient (α) and the elastic modulus (E: GPa) is 150 or less. 8] The cured product according to the above.
[11] A component-embedded substrate using the cured body according to any one of [7] to [10].

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where a thin core board | substrate is used, the resin composition which does not produce the problem of curvature can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin that is solid at 25 ° C., (B) an inorganic filler, (C) a saturated functional butadiene resin that is liquid at 25 ° C., and a functional group that is liquid at 25 ° C. When one or more resins selected from the group consisting of a saturated butadiene resin and a functional group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower are included, and the nonvolatile component in the resin composition is 100% by mass, (B ) Component is 40% by mass or more, and when the resin component is 100% by mass, the component (C) is 10 to 40% by mass.

  The present inventors can solve the problem of warping by using a resin composition containing the specific components (A) to (C) in the specific quantitative ratio as an insulating layer of a multilayer printed wiring board. This is what we found.

Here, as an index of warpage of a composite material formed by laminating two layers, the thermal expansion coefficient (α _com ) of the entire composite material obtained by the following Turner equation can be given. The warpage of the composite material is suppressed as the value of α _com is lower. The Turner equation is also described in, for example, Japanese Patent No. 3260340 and Japanese Patent Application Laid-Open No. 2008-186905.

For example, assume that the first layer is an insulating layer and the second layer is a core substrate. In this case, α ₂ and E ₂ are values specific to the core substrate used for manufacturing the multilayer printed wiring board. Therefore, if the film thicknesses of the insulating layer and the core substrate are determined, the α _com can be handled as a function of α ₁ and E ₁ substantially. Further, since the elastic modulus of the core substrate is generally sufficiently higher than the elastic modulus of the insulating layer (E ₂ >> E ₁ ), the contribution of the denominator when viewed as a function of α ₁ and E ₁ is limited. The α _com will depend exclusively on the product of α ₁ E ₁ .

As will be described in detail later, the resin composition of the present invention has a low coefficient of thermal expansion (α ₁ ) and elastic modulus (E ₁ ) of the cured product (insulating layer), and the product of α ₁ E ₁ is Very low. According to the conventional technical common sense, if a flexible component such as component (C) is added, the coefficient of thermal expansion will increase, and the desired effect should not be achieved. This could not have been predicted from conventional technical common sense.

  Hereinafter, the components (A) to (C) contained in the resin composition of the present invention will be described.

<(A) component>
The component (A) is an epoxy resin that is solid at 25 ° C. (hereinafter also referred to as “solid epoxy resin”).

  Solid epoxy resins include, but are not limited to, naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, A naphthylene ether type epoxy resin is exemplified, and a naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is preferable, a naphthalene type epoxy resin is more preferable, and a bifunctional or higher functional naphthalene skeleton epoxy resin is further preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710”, “EXA-7311G4S” (naphthalene type epoxy resin), “N-690” (cresol novolak type epoxy) manufactured by DIC Corporation. Resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “EXA7311”, “EXA7311-G3”, “HP6000” (naphthylene ether type epoxy resin) ), “EPPN-502H” (trisphenol epoxy resin), “NC7000L” (naphthol novolac epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type) manufactured by Nippon Kayaku Co., Ltd. Epoxy resin), manufactured by Nippon Steel Chemical Co., Ltd. “ESN475” (naphthol novolak type epoxy resin), “ESN485” (naphthol novolak type epoxy resin), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type) manufactured by Mitsubishi Chemical Corporation Epoxy resin). These substances may be used alone or in combination of two or more. Among them, it is preferable to use a combination of two or more bifunctional or more naphthalene type epoxy resins.

  (A) The epoxy equivalent of a component becomes like this. Preferably it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinking density of the cured product becomes sufficient. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The number average molecular weight (Mn) of the epoxy resin that is solid at 25 ° C. of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 2000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

  5 mass%-50 mass% are preferable, as for content of (A) component in a resin composition, 10 mass%-40 mass% are more preferable, and 15 mass%-30 mass% are more preferable.

<(B) component>
The component (B) is an inorganic filler.

  Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, and spherical silica is particularly preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Preferable spherical silica includes “SO-C2” manufactured by Admatechs Co., Ltd. and “FB-5SDC” manufactured by Denki Kagaku Kogyo Co., Ltd.

  The average particle size of the inorganic filler is preferably 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less, and even more preferably 7 μm or less, from the viewpoints of fluidity and circuit embedding. Particularly preferably, it is 6 μm or less or 5 μm or less. Although the minimum of the average particle diameter of an inorganic filler is not specifically limited, Preferably it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. Regarding the inorganic filler, it is preferable that particles of 20 μm or more are removed by classification, and it is more preferable that particles of 15 μm or more are removed. Thereby, when manufacturing a component built-in circuit board as a multilayer printed wiring board, the cavity filling property of the core substrate and the component embedding property are improved. In a preferred embodiment, the inorganic filler has an average particle diameter of 10 μm or less, and particles of 20 μm or more are removed by classification. 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 created on a volume basis with 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-500 manufactured by Horiba, Ltd. or the like can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the thermosetting resin composition layer, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable.

  The inorganic filler surface-treated with the surface treatment agent can be washed with a solvent (for example, methyl ethyl ketone (MEK)), and then the amount of carbon per unit surface area of the inorganic filler can be measured. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.

  The content of the component (B) in the resin composition of the present invention is 100% by mass of the non-volatile component in the resin composition from the viewpoint of sufficiently reducing the thermal expansion coefficient of the obtained cured product (insulating layer). In this case, it is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more. In the present invention, the content of the component (B) can be further increased while suppressing the problem of warpage. For example, the content of the component (B) in the resin composition may be increased to 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, or 75% by mass or more.

  The upper limit of the content of the component (B) in the resin composition is preferably 95% when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of the mechanical strength of the obtained cured product (insulating layer). % Or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

<(C) component>
The component (C) is one or more resins selected from the group consisting of a functional group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. and a functional group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower. is there.

  (C) The glass transition temperature (Tg) of a component is 25 degrees C or less. Although it is difficult to measure the Tg of a functional group-containing saturated and / or unsaturated butadiene resin, as understood from the fact that it is liquid at 25 ° C., if it is liquid at 25 ° C., the functional group-containing saturated and The Tg of the unsaturated butadiene resin is naturally considered to be 25 ° C. or lower. When the resin having such a low glass transition temperature is used for an insulating layer of a multilayer printed wiring board, the elastic modulus of the insulating layer tends to decrease due to the low elastic modulus of the component (C). On the other hand, it is known that such a resin having a low glass transition temperature usually increases the coefficient of thermal expansion of the insulating layer. The inventors of the present invention increase the thermal expansion coefficient of the insulating layer while maintaining the effect that the specific resin having a Tg of 25 ° C. or lower or a liquid and having a functional group reduces the elastic modulus of the insulating layer. In addition, the inventors have found that the effect of lowering the thermal expansion coefficient of the insulating layer is exhibited, and the present invention has been achieved.

  As a functional group which the resin of (C) component has, the functional group which can react with (A) component is preferable. In a preferred embodiment, the functional group of the resin of component (C) is one or more functional groups selected from the group consisting of an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. is there. Among these, as the functional group, an epoxy group and a phenolic hydroxyl group are preferable, and an epoxy group is more preferable.

  The glass transition temperature (Tg) of the component (C) is 25 ° C. or less, preferably 20 ° C. or less, more preferably 15 ° C. or less, from the viewpoint of obtaining an insulating layer having a low elastic modulus. Although the minimum of the glass transition temperature of (C) component is not specifically limited, Usually, it can be set as -15 degreeC or more.

(Functional group-containing saturated and / or unsaturated butadiene resin liquid at 25 ° C)
Examples of the functional group-containing saturated and / or unsaturated butadiene resins that are liquid at 25 ° C. include acid anhydride group-containing saturated and / or butadiene resins that are liquid at 25 ° C., and phenolic hydroxyl group-containing saturated and / or butadiene that are liquid at 25 ° C. Group consisting of resin, epoxy group-containing saturated and / or butadiene resin that is liquid at 25 ° C., isocyanate group-containing saturated and / or butadiene resin that is liquid at 25 ° C., and urethane group-containing saturated and / or butadiene resin that is liquid at 25 ° C. One or more resins selected from are preferred. Here, the “saturated and / or unsaturated butadiene resin” means a resin containing a saturated butadiene skeleton and / or an unsaturated butadiene skeleton, and in these resins, the saturated butadiene skeleton and / or the unsaturated butadiene skeleton is a main chain. Or may be contained in the side chain.

  The number average molecular weight (Mn) of the functional group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. is preferably 500 to 50,000, more preferably 1000 to 10,000, and still more preferably 2000 to 10,000. More preferably, it is 2300-10000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

  The functional group equivalent of the functional group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. is preferably 100 to 10,000, more preferably 150 to 5000, still more preferably 190 to 3000, and even more preferably. 200-2000. In addition, functional group equivalent is the mass of resin containing 1 equivalent of functional groups. For example, the epoxy equivalent of the resin can be measured according to Japanese Industrial Standard JIS K7236.

  Among them, from the viewpoint of further reducing the problem of warpage by further reducing the thermal expansion coefficient and elastic modulus of the insulating layer, the component (C) is an epoxy group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. preferable.

  The epoxy group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. is preferably a liquid saturated and / or butadiene skeleton-containing epoxy resin that is liquid at 25 ° C., and a polybutadiene skeleton-containing epoxy resin that is liquid at 25 ° C. A liquid hydrogenated polybutadiene skeleton-containing epoxy resin is more preferable. Here, the “hydrogenated polybutadiene skeleton-containing epoxy resin” refers to an epoxy resin in which at least a part of the polybutadiene skeleton is hydrogenated, and is not necessarily an epoxy resin in which the polybutadiene skeleton is completely hydrogenated. Specific examples of the polybutadiene skeleton-containing resin that is liquid at 25 ° C. and the hydrogenated polybutadiene skeleton-containing resin that is liquid at 25 ° C. include PB3600 (polybutadiene skeleton epoxy resin) manufactured by Daicel Chemical Industries, and Nagase ChemteX Corporation. FCA-061L (hydrogenated polybutadiene skeleton epoxy resin) and the like.

  The acid anhydride group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. is preferably a saturated and / or unsaturated butadiene skeleton-containing acid anhydride resin that is liquid at 25 ° C.

  The phenolic hydroxyl group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. is preferably a saturated and / or unsaturated butadiene skeleton-containing phenol resin that is liquid at 25 ° C.

  The isocyanate group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C. is preferably a saturated and / or unsaturated butadiene skeleton-containing isocyanate resin that is liquid at 25 ° C.

  As the urethane group-containing saturated and / or unsaturated butadiene resin that is liquid at 25 ° C., a saturated and / or unsaturated butadiene skeleton-containing urethane resin that is liquid at 25 ° C. is preferable.

(Functional group-containing acrylic resin with Tg of 25 ° C. or less)
The functional group-containing acrylic resin having a Tg of 25 ° C. or lower includes an acid anhydride group-containing acrylic resin having a Tg of 25 ° C. or lower, a phenolic hydroxyl group-containing acrylic resin having a Tg of 25 ° C. or lower, and an isocyanate group containing Tg of 25 ° C. or lower. One or more resins selected from the group consisting of an acrylic resin, a urethane group-containing acrylic resin having a Tg of 25 ° C. or lower, and an epoxy group-containing acrylic resin having a Tg of 25 ° C. or lower are preferred.

  The number average molecular weight (Mn) of the functional group-containing acrylic resin having a Tg of 25 ° C. or lower is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000, and still more preferably 300,000 to 900,000.

  The functional group equivalent of the functional group-containing acrylic resin having a Tg of 25 ° C. or lower is preferably 1000 to 50000, more preferably 2500 to 30000.

  Among these, an epoxy group-containing acrylic resin having a Tg of 25 ° C. or lower is preferable from the viewpoint of further reducing the thermal expansion coefficient and elastic modulus of the insulating layer to further alleviate the problem of warpage.

  The epoxy group-containing acrylic resin having a Tg of 25 ° C. or lower is preferably an epoxy group-containing acrylic ester copolymer resin having a Tg of 25 ° C. or lower. Specific examples thereof include “SG-” manufactured by Nagase ChemteX Corporation. 80H "(epoxy group-containing acrylate copolymer resin (number average molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, Tg11 ° C))," SG-P3 "(manufactured by Nagase ChemteX Corporation) ( Epoxy group-containing acrylic ester copolymer resin (number average molecular weight Mn: 850000 g / mol, epoxy value 0.21 eq / kg, Tg 12 ° C.)).

  The acid anhydride group-containing acrylic resin having a Tg of 25 ° C. or lower is preferably an acid anhydride group-containing acrylic ester copolymer resin having a Tg of 25 ° C. or lower.

  As the phenolic hydroxyl group-containing acrylic resin having a Tg of 25 ° C. or lower, a phenolic hydroxyl group-containing acrylic ester copolymer resin having a Tg of 25 ° C. or lower is preferable. Specific examples thereof include “manufactured by Nagase ChemteX Corporation” SG-790 "(epoxy group-containing acrylic ester copolymer resin (number average molecular weight Mn: 500,000 g / mol, hydroxyl value 40 mg KOH / kg, Tg-32 ° C)).

  Among them, the component (C) includes a polybutadiene skeleton epoxy resin that is liquid at 25 ° C., a hydrogenated polybutadiene skeleton epoxy resin that is liquid at 25 ° C., and an epoxy group-containing acrylic ester copolymer having a Tg of 25 ° C. or less. One or more selected are preferred.

The content of the component (C) in the resin composition of the present invention is 10% when the resin component is 100% by mass from the viewpoint of reducing the thermal expansion coefficient and elastic modulus of the insulating layer to alleviate the problem of warpage. It is -40 mass%, Preferably it is 12 mass%-35 mass%, More preferably, it is 15 mass%-32 mass%. Here, the “resin component” is a component obtained by removing (B) the inorganic filler from the resin composition. That is, in addition to the component (A) and the component (C), a resin included as a curing agent described later is also included.
In particular, when the mass of the component (A) is 100 mass%, the content of the component (C) in the resin composition is preferably 15 mass% to 80 mass%, more preferably 20 mass% to 70 mass%. is there.

  The content of the component (C) in the resin composition of the present invention is not particularly limited as long as it satisfies a relative ratio with the above resin component, but the lower limit is preferably 3% by mass or more and 5% by mass or more. The upper limit is preferably 20% by mass or less.

  In the resin composition of the present invention, the mass ratio of the component (B) to the component (C) (component (B) / component (C)) reduces the thermal expansion coefficient and elastic modulus of the insulating layer, causing warpage. From the viewpoint of relaxing, preferably it is 2 or more, more preferably 3 or more. Further, the upper limit of the mass ratio of the component (B) / the component (C) is preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less, from the viewpoint of alleviating the problem of warpage.

  The resin composition of the present invention may contain a curing agent in addition to the components (A) to (C).

  The curing agent is not particularly limited as long as it has a function of curing the resin used in the present invention. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester. System curing agent. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. Among these, in the present invention, it is preferable to use one or more curing agents selected from the group consisting of phenolic curing agents, naphthol curing agents, and active ester curing agents, and phenolic curing agents and naphthol curing agents. More preferably, two or more curing agents selected from the group consisting of an agent and an active ester curing agent are used in combination.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer (circuit wiring), a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness (peel strength) to the conductor layer, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. "LA7052", "LA7054", "LA3018", "HPC-9500", etc. manufactured by DIC Corporation.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound), phenol novola And the like.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol condensation structure, an active ester compound containing a naphthalene structure, an active ester compound containing a phenol novolac acetylated product, and an active ester compound containing a phenol novolak benzoylated product are preferred. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol condensation structure are more preferred.

  As a commercial product of an active ester curing agent, as an active ester compound having a dicyclopentadiene type diphenol condensation structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (DIC Corporation) Manufactured product), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoylated compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (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, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And the like, and the like, and the like.

  The content of the curing agent in the resin composition of the present invention is preferably a ratio of [total number of epoxy groups of component (A)]: [total number of reactive groups of curing agent]: 1: 0.2 to You may adjust so that it may become the range of 1: 2, More preferably, it is the range of 1: 0.3-1: 1.5, More preferably, it is the range of 1: 0.4-1: 1. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. The total number of epoxy groups in component (A) is the sum of the values obtained by dividing the solid content mass of each epoxy resin used as component (A) by the epoxy equivalent for all epoxy resins, and the curing agent. The total number of reactive groups is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.

  The resin composition of the present invention may further contain additives such as a curing accelerator, a thermoplastic resin, and a flame retardant as necessary.

  Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, amine adduct compounds, and tertiary amine compounds. The content of the curing accelerator is preferably used in the range of 0.05% by mass to 3% by mass when the total of the non-volatile components of the epoxy resin and the curing agent in the resin composition is 100% by mass. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

  Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and further preferably 1% by mass to 8% by mass. .

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. A thermoplastic resin may be used individually by 1 type or in combination of 2 or more types.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-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.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. You may use a phenoxy resin individually by 1 type or in combination of 2 or more types. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include electric butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., and ESREC BH series and BX series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 10% by mass.

  The resin composition of the present invention may contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and organic fillers, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, colorants, and the like. Is mentioned.

  The resin composition of the present invention may be impregnated into a sheet-like fiber base material to form a prepreg. The prepreg is obtained by impregnating the resin composition of the present invention in a sheet-like fiber base material.

The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. When used for forming an insulating layer of a multilayer printed wiring board, a thin sheet-like fiber substrate having a thickness of 50 μm or less is preferably used, and particularly a sheet-like fiber substrate having a thickness of 10 μm to 40 μm is preferable. A sheet-like fiber substrate of 10 μm to 30 μm is more preferable, and a sheet-like fiber substrate of 10 to 20 μm is more preferable. Specific examples of the glass cloth base material used as the sheet-like fiber base material include “Style 1027MS” (warp density 75/25 mm, weft density 75/25 mm, fabric weight 20 g / m ² ) manufactured by Asahi Schwer Corporation. , Thickness 19 μm), “Style 1037MS” manufactured by Asahi Schubel Co., Ltd. (warp density 70/25 mm, weft density 73/25 mm, fabric weight 24 g / m ² , thickness 28 μm), manufactured by Arisawa Manufacturing Co., Ltd. "1078" (warp density 54 / 25mm, weft density 54 / 25mm, fabric weight 48g / m ² , thickness 43μm), "1037NS" manufactured by Arizawa Seisakusho (warp density 72 / 25mm, weft Density 69/25 mm, fabric weight 23 g / m ² , thickness 21 μm), “1027NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 75/25 mm, weft density 7 5/25 mm, fabric weight 19.5 g / m ² , thickness 16 μm), “1015NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 95/25 mm, weft density 95/25 mm, fabric weight 17.5 g / m ² , thickness 15 μm), “1000NS” manufactured by Arisawa Manufacturing Co., Ltd. (warp density 85/25 mm, weft density 85/25 mm, fabric weight 11 g / m ² , thickness 10 μm), and the like. Specific examples of the liquid crystal polymer non-woven fabric include “Veculus” (weight per unit area: 6 to 15 g / m ² ) and “Vectran” manufactured by Kuraray Co., Ltd. by the melt blow method of an aromatic polyester non-woven fabric.

  The prepreg may be produced by a known method such as a hot melt method or a solvent method.

  The resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a multilayer printed wiring board) for forming an insulating layer of a multilayer printed wiring board. By forming an insulating layer of a multilayer printed wiring board using the resin composition of the present invention, an insulating layer having a low thermal expansion coefficient and elastic modulus can be realized, and the problem of warping can be remarkably improved. Among them, in the production of multilayer printed wiring boards by the build-up method, it can be suitably used as a resin composition for forming an insulating layer (resin composition for build-up insulating layers of multilayer printed wiring boards). It can be more suitably used as a resin composition for forming an insulating layer in which a conductor layer is formed by plating (a resin composition for a build-up insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating). . Moreover, since the resin composition of the present invention is excellent in fluidity and component embedding properties, it can be suitably used even when the multilayer printed wiring board is a component-embedded circuit board. That is, the resin composition of the present invention can be suitably used as a resin composition for embedding components on a component-embedded circuit board (resin composition for embedding components). The core substrate used for manufacturing the component built-in circuit board has a cavity for incorporating the component, and the cavity density tends to increase due to a demand for miniaturization of the component built-in circuit board itself. The problem of warping due to the lack of rigidity tends to become more serious, but by using the resin composition of the present invention as a resin composition for embedding a component, when using a thin core substrate with a high cavity density Even so, the problem of warping can be remarkably mitigated.

[Adhesive film]
An adhesive film can be formed using the resin composition of the present invention.

  In one embodiment, the adhesive film of the present invention includes a support and a resin composition layer bonded to the support, and the resin composition layer is made of the resin composition of the present invention.

  The adhesive film is formed, for example, by preparing a resin varnish obtained by dissolving the resin composition of the present invention in an organic solvent, applying the resin varnish on a support using a die coater, and drying the resin varnish. can do.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Examples thereof include carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  The resin varnish may be dried by a known drying method such as heating or hot air blowing. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the adhesive film is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. Can be formed.

  Examples of the support used for forming the adhesive film include a film made of a plastic material, a metal foil (copper foil, aluminum foil, etc.), and release paper. A film made of a plastic material is preferably used. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PC”). And acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

  The support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. .

  In the present invention, a commercially available product may be used as the support with a release layer. Commercially available products include, for example, “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin release agent. Or the like.

  Although the thickness of a support body is not specifically limited, Preferably it is 5 micrometers-75 micrometers, More preferably, it is 10 micrometers-60 micrometers. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  In the adhesive film of the present invention, the thickness of the resin composition layer is not particularly limited, but is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, from the viewpoint of thinning the multilayer printed wiring board. More preferably, it is 50 μm or less. The lower limit of the thickness of the resin composition layer is usually 15 μm or more.

  In the adhesive film of the present invention, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 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 be wound and stored in a roll shape, and can be used by peeling off the protective film when forming an insulating layer in the production of a multilayer printed wiring board.

[Hardened body]
The resin composition of the present invention can be cured by thermosetting.

  The conditions for thermosetting are not particularly limited, and conditions usually employed in forming an insulating layer in the production of a multilayer printed wiring board may be used.

  For example, although the thermosetting conditions vary depending on the composition of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, more preferably in the range of 170 ° C to 190 ° C). The curing time can be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

  Prior to thermosetting, the resin composition may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting, the resin composition is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes or longer (preferably 5 minutes). Preheating may be performed for ~ 150 minutes, more preferably 15 minutes to 120 minutes.

  The thermosetting is preferably performed under atmospheric pressure (normal pressure).

  The glass transition temperature (Tg) of the cured product of the present invention is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 190 ° C. or higher, even more preferably 200 ° C. or higher, particularly preferably 210 ° C. or higher or 220. It is above ℃.

  The linear thermal expansion coefficient (α) of the cured product of the present invention is preferably 25 ppm or less, more preferably 20 ppm or less, still more preferably 15 ppm or less, and even more preferably 10 ppm or less. Although the minimum of a linear thermal expansion coefficient ((alpha)) is not specifically limited, Usually, it is 1 ppm or more. In this invention, the linear thermal expansion coefficient ((alpha)) of a hardening body is 25-150 degreeC linear thermal expansion coefficient ((alpha)) of the plane direction measured by the tension mode in a thermomechanical analysis (TMA). An example of a thermomechanical analyzer that can be used for measuring the linear thermal expansion coefficient (α) of the cured product is “Thermo Plus TMA8310” manufactured by Rigaku Corporation.

  The elastic modulus (E) of the cured product of the present invention is preferably 14 GPa or less, more preferably 12 GPa or less, still more preferably 9 GPa or less, even more preferably 5 GPa or less, and particularly preferably 4 GPa or less. The lower limit of the elastic modulus (E) is not particularly limited, but is usually 1 GPa or more. In the present invention, the elastic modulus (E) of the cured product is an elastic modulus (E) measured at room temperature (20 to 30 ° C.) using an orientec universal testing machine.

  The product α × E of the linear thermal expansion coefficient (α) and the elastic modulus (E: GPa) of the cured product of the present invention is preferably 150 or less, more preferably 125 or less, still more preferably 100 or less, and even more. Preferably it is 95 or less, Especially preferably, it is 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, or 55 or less. The lower limit of the product is not particularly limited, but is usually 10 or more.

  In a preferred embodiment, the cured product of the present invention has a linear thermal expansion coefficient (α) of 25 ppm or less, and the product α × E of the linear thermal expansion coefficient (α) and the elastic modulus (E: GPa) is 150. It is as follows.

  As described above, the cured product of the present invention obtained by thermosetting a resin composition containing the specific components (A) to (C) in a specific amount ratio has a thermal expansion coefficient (α) and an elastic modulus ( E) are both low and the product α × E is very low. Accordingly, the cured body of the present invention can advantageously alleviate the problem of warping when used as an insulating layer of a multilayer printed wiring board or a component-embedded substrate.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning. In the following description, “part” means “part by mass”.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

<Evaluation of warpage>
(1) Lamination of adhesive film The adhesive film produced in the examples and comparative examples was cut into a size of 9.5 cm square, and a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) was used. It was laminated on the roughened surface of a copper foil (3EC-III, thickness 35 μm) manufactured by Mitsui Kinzoku Co., Ltd. cut into a 10 cm square.
The laminate was decompressed for 30 seconds and the pressure was reduced to 13 hPa or less, and then a metal foil with a resin composition layer was prepared by pressure bonding at 120 ° C. for 30 seconds at a pressure of 0.74 MPa, and then the PET film was peeled off. .

(2) Curing of the resin composition layer The four sides of the metal foil with the resin composition layer obtained in (1) above were attached to a 1 mm thick SUS plate with a polyimide tape so that the resin composition layer was on the top surface. The resin composition layer was cured under curing conditions of 180 ° C. for 30 minutes.

(3) Measurement of warpage Of the four sides of the metal foil with a resin composition layer obtained in (2) above, the polyimide tape on the three sides is peeled off, and the height of the highest point is obtained from the SUS plate. The value was determined. And the case where the magnitude | size of curvature was less than 1 cm was set to "(circle)", the case where it was 1 cm or more and less than 3 cm was set to "(triangle | delta)", and the case where 3 cm or more was set to "x".

<Measurement and evaluation of linear thermal expansion coefficient>
The adhesive films produced in the examples and comparative examples were applied to a polyimide film (Ube Industries, Upilex S) using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.). Laminated. The laminate was depressurized for 30 seconds to reduce the pressure to 13 hPa or less, and then pressure-bonded at 120 ° C. for 30 seconds at a pressure of 0.74 MPa. Thereafter, the PET film was peeled off, the resin composition was cured under curing conditions of 190 ° C. for 90 minutes, and the polyimide film was peeled off to obtain a cured product.
The obtained cured product sample 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 (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). went. After the sample was mounted on the apparatus, it was measured twice in succession under measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm) from 25 ° C. to 150 ° C. in the second measurement was calculated. The value of the linear thermal expansion coefficient was evaluated as “◯” when less than 20 ppm, “Δ” when 20 ppm or more and less than 25 ppm, and “×” when 25 ppm or more.

<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.

<Measurement of glass transition temperature>
The cured material sample is cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis is performed by a tensile load method using a dynamic viscoelasticity measuring device (“EXSTAR6000” manufactured by SII Nanotechnology Co., Ltd.). went. After mounting the sample on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 200 mN and a heating rate of 2 ° C./min. The glass transition temperature (° C.) was calculated from the point at which the slope of the dimensional change signal in the second measurement changed.

Example 1
<Preparation of resin varnish>
25 parts of naphthalene type tetrafunctional epoxy resin (number average molecular weight Mn: 700 g / mol, epoxy equivalent 163, “HP-4710” manufactured by DIC Corporation), naphthalene type epoxy resin (number average molecular weight Mn: 490 g / mol, epoxy equivalent) 186, 25 parts of DIC (“EXA7311-G4S”), polybutadiene skeleton-containing epoxy resin (number average molecular weight Mn: 5900 g / mol, epoxy equivalent 190, “PB3600” manufactured by Daicel Chemical Industries, Ltd.) and methyl ethyl ketone (MEK) ) 15 parts and dissolved in 15 parts of cyclohexanone with stirring. Thereto, 15 parts of a MEK solution having a solid content of 60% by weight of a triazine-containing phenol novolac resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, nitrogen content about 12% by weight), naphthol-based curing agent (hydroxyl equivalent 153) , "HPC-9500" manufactured by DIC Corporation, 25 parts by weight of MEK solution having a solid content of 60% by weight, spherical silica (average particle diameter of 4.0 µm, specific surface area of 2.4 m ² / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) 160 parts of “FB-5SDC”) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.
<Creation of adhesive film>
The resin varnish is uniformly applied by a die coater on the release-treated surface of a PET film (thickness 38 μm) treated with an alkyd mold release agent so that the thickness of the resin composition layer after drying is 40 μm. And dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain an adhesive film.

(Example 2)
Example 1 except that the polybutadiene skeleton-containing epoxy resin was replaced with a hydrogenated polybutadiene skeleton-containing epoxy resin (number average molecular weight Mn: 2650 g / mol, epoxy equivalent 1500, “FCA-061L” manufactured by Nagase ChemteX Corporation). An adhesive film was prepared in the same manner as described above.

(Example 3)
25 parts of a polybutadiene skeleton-containing epoxy resin was added to an epoxy group-containing acrylic ester copolymer (number average molecular weight Mn: 850000 g / mol, epoxy value 0.21 eq / kg, Tg 12 ° C., “SG-P3” manufactured by Nagase ChemteX Corporation) ) An adhesive film was prepared in the same manner as in Example 1 except that the content was replaced with 24.9 parts.

(Example 4)
An adhesive film was produced in the same manner as in Example 1 except that the content of spherical silica was changed to 70 parts.

(Example 5)
An adhesive film was produced in the same manner as in Example 1 except that the spherical silica content was changed to 350 parts.

(Example 6)
An adhesive film was produced in the same manner as in Example 1 except that the content of the polybutadiene skeleton-containing epoxy resin was changed to 10 parts.

(Example 7)
An adhesive film was produced in the same manner as in Example 1 except that the content of the polybutadiene skeleton-containing epoxy resin was changed to 35 parts.

(Example 8)
Except for using 350 parts of spherical silica (average particle size 0.5 μm, specific surface area 6.8 m ² / g, “SO-C2” manufactured by Admatechs Co., Ltd., treated with an aminosilane coupling agent) as spherical silica. An adhesive film was produced in the same manner as in Example 1.

Example 9
An adhesive film was prepared in the same manner as in Example 1 except that the resin varnish was adjusted as follows.
<Preparation of resin varnish>
Naphthalene-type tetrafunctional epoxy resin (number average molecular weight Mn: 700 g / mol, epoxy equivalent 163, DIC Corporation "HP-4710") 50 parts, polybutadiene skeleton-containing epoxy resin (number average molecular weight Mn: 5900 g / mol, epoxy) Equivalent 190, “PB3600” manufactured by Daicel Chemical Industries, Ltd.) 24 parts of MEK solution 24 parts was dissolved in 15 parts of methyl ethyl ketone (MEK) and 15 parts of cyclohexanone with stirring. Thereto, 18 parts of a MEK solution having a solid content of 60% by weight of a triazine-containing phenol novolac resin (hydroxyl equivalent 151, “LA3018” manufactured by DIC Corporation, nitrogen content of about 18% by weight), an active ester curing agent (functional group) 20 parts of MEK solution having an equivalent weight of 223 and a solid content of 65% by weight of “HPC-8000-65T” manufactured by DIC Corporation, spherical silica (average particle diameter of 4.0 μm, specific surface area of 2.4 m ² / g, Electrochemical Industry) 140 parts of "FB-5SDC" manufactured by Co., Ltd.) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

(Comparative Example 1)
An adhesive film was produced in the same manner as in Example 1 except that the polybutadiene skeleton-containing epoxy resin was not used and the spherical silica was changed to 120 parts.

(Comparative Example 2)
An adhesive film was produced in the same manner as in Example 1 except that the content of the polybutadiene skeleton-containing epoxy resin was changed to 5.5 parts.

(Comparative Example 3)
An adhesive film was produced in the same manner as in Example 1 except that the amount of spherical silica was changed to 40 parts.

(Comparative Example 4)
An adhesive film was prepared in the same manner as in Example 1 except that the polybutadiene skeleton-containing epoxy resin was not used and the spherical silica content was changed to 300 parts.

  The results are shown in the table below.

  Thus, according to the resin composition of this invention, curvature can fully be suppressed.

Claims (11)

(A) an epoxy resin solid at 25 ° C.,
(B) inorganic filler,
(C) selected from the group consisting of a functional group-containing saturated butadiene resin that is liquid at 25 ° C., a functional group-containing unsaturated butadiene resin that is liquid at 25 ° C., and a functional group-containing acrylic resin having a glass transition point of 25 ° C. or lower. One or more resins,
A resin composition comprising:
When the nonvolatile component in the resin composition is 100% by mass, the component (B) is 40% by mass or more,
The resin composition whose component (C) is 10 to 40% by mass when the resin component is 100% by mass.   The resin composition according to claim 1, wherein the component (C) has one or more functional groups selected from the group consisting of an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group.   The resin composition according to claim 1 or 2, wherein the component (A) is a bifunctional or higher functional naphthalene skeleton epoxy resin.   The resin composition according to claim 1, further comprising a curing agent.   The resin composition of any one of Claims 1-4 which is a resin composition for components embedding.   The resin composition according to any one of claims 1 to 5, wherein the inorganic filler has an average particle size of 10 µm or less, and particles of 20 µm or more are removed by classification.   Hardened | cured material which hardened the resin composition of any one of Claims 1-6.   The hardened | cured material of Claim 7 whose glass transition temperature is 170 degreeC or more.   The hardened | cured material of Claim 7 or 8 whose product (alpha) xE of a linear thermal expansion coefficient ((alpha)) and an elasticity modulus (E: GPa) is 150 or less.   The cured body according to claim 7 or 8, wherein the linear thermal expansion coefficient (α) is 25 ppm or less, and the product α × E of the linear thermal expansion coefficient (α) and the elastic modulus (E: GPa) is 150 or less. .   The component built-in board | substrate formed using the hardening body of any one of Claims 7-10.