JP6854505B2 - Resin composition, thermosetting film using it - Google Patents

Description

The present invention relates to a resin composition and a thermosetting film using the same.
The present invention also relates to the resin composition, a laminated board using the thermosetting film, and a semiconductor device.

The adhesive layer formed between the IC chip and the substrate, or between the laminated boards, has a coefficient of thermal expansion (CTE) from the viewpoint of reliability against temperature changes (no peeling, cracking, warpage, etc.). It is desired to be low.

The temperature rise due to heat generated from the IC chip, etc., the temperature change due to the temperature drop after use, or the change in the environmental temperature for the in-vehicle parts, etc. are relatively gradual from room temperature (25 ° C) to medium temperature (about 100 ° C). Therefore, reliability against temperature change (no peeling, cracking, warpage, etc.) is rarely a problem, but in the high temperature range of 100 ° C or higher, the temperature tends to change in a short time, so that it is resistant to temperature change. Reliability (no peeling, cracking, warping, etc.) tends to be a problem.

When lowering the CTE of the adhesive layer, a method of highly filling the filler adhesive layer is usually adopted.
However, the more the adhesive layer is filled with the filler, the lower the adhesive strength is.

An object of the present invention is to provide a thermosetting film having both low CTE and high adhesive strength after curing, and a resin composition used for producing the same, in order to solve the above-mentioned problems in the prior art. To do.

In order to achieve the above object, the present invention
(A) Solvent-soluble polyimide resin,
(B) Epoxy resin having an anthracene skeleton,
(C) Curing catalyst and
(D) A resin composition comprising an inorganic filler is provided.

In the resin composition of the present invention, the solvent-soluble polyimide resin (A) is preferably a polyimide resin obtained by reacting a tetracarboxylic acid component with a dimer diamine.

In the resin composition of the present invention, it is preferable that the inorganic filler (D) contains hollow silica.

The resin composition of the present invention may further contain (E) a silane coupling agent.

The present invention also provides a thermosetting film formed by the resin composition of the present invention.

The present invention also provides a resin composition of the present invention or a cured resin product obtained by curing a thermosetting film of the present invention.

The present invention also provides a laminated board containing the cured resin product of the present invention.

The present invention also provides a semiconductor device containing the cured resin product of the present invention.

In the resin composition of the present invention, by using (A) a solvent-soluble polyimide resin and (B) an epoxy resin having an anthracene skeleton in combination, a thermosetting film produced using the resin composition is used after curing. Since the CTE can be made lower, even if the amount of the inorganic filler added is reduced as compared with the conventional thermosetting film, the CTE equivalent to that of the conventional thermosetting film can be obtained after curing, and the conventional heat can be obtained. Adhesive strength can be improved as compared with a curable film.
Further, when the amount of the inorganic filler added is the same as that of the conventional thermosetting film, the adhesive strength equivalent to that of the conventional thermosetting film can be obtained, and the adhesive strength after curing is higher than that of the conventional thermosetting film. CTE can be lowered.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains (A) a solvent-soluble polyimide resin, (B) an epoxy resin having an anthracene skeleton, (C) a curing catalyst, and (D) an inorganic filler. Each component of the resin composition of the present invention is described below.

(A) Solvent-soluble polyimide resin The solvent-soluble polyimide of the component (A) may be soluble in a solvent, and its structure and the like are not particularly limited. Soluble means that it dissolves in at least one of the following solvents at 23 ° C. in an amount of 20% by weight or more. Hydrocarbon-based solvent toluene, xylene, ketone-based solvent acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ether-based solvent 1,4-dioxane, tetrahydrofuran, diglime, glycol ether-based solvent methyl cellosolve, ethyl Cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, as ester solvents, ethyl acetate, butyl acetate, ethyl lactate, gamma butyrolactone, others, benzyl alcohol, N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

The solvent-soluble polyimide of the component (A) can be obtained by reacting a diamine and a tetracarboxylic acid component at a temperature of 130 ° C. or higher to carry out an imidization reaction. As the solvent-soluble polyimide of the component (A), a polyimide resin obtained by reacting a tetracarboxylic acid component with a dimer diamine is preferable because it is excellent in adhesiveness, flexibility, toughness, and heat resistance. Further, in the solvent-soluble polyimide of the component (A), a part of the diamine diamine may be replaced with a silicone diamine.

Examples of the tetracarboxylic acid component used here include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone. Tetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Ethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1, 2,3,4-Flantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) Diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) Diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridenediphthalic acid dianhydride, 3, 3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphinoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (tri) Phenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 4,4'-( 4,4'-isopropyridenediphenoxy) Diphthalic acid dianhydride and the like can be mentioned.

Diamine diamines include, for example, Versamine 551 (trade name, manufactured by BASF Japan Co., Ltd .; 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)) cyclohexene), Versamine 552 ( Product names, manufactured by Cognix Japan Co., Ltd .; hydrogenated with Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (all trade names, manufactured by Crowder Japan Co., Ltd.) and the like.

上記の化学式中、ｎは、整数を示し、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は有機基を示し、例として、Ｒ₁、Ｒ₂は、−（ＣＨ₂）_n1−（ＣＨ＝Ｃ_n2−（ＣＨ₂）_n3−ＣＨ₃を示し、同じ場合も異なる場合もある。Ｒ₃、Ｒ₄は、（ＣＨ₂）_n1−（ＣＨ＝ＣＨ）_n2−（ＣＨ₂）_n3−を示し、同じ場合も異なる場合もある。ｎ₁、ｎ₃は、０〜１８の整数であり、ｎ₂は０または１または２の整数である。またダイマージアミン成分における炭素数の合計は３６である。 The solvent-soluble polyimide resin of the component (A) has a structure in which the tetracarboxylic acid component reacts with dimerdiamine and is polymerized by an imide bond. Dimer acid, which is a raw material of dimer diamine, is a dimerized unsaturated fatty acid having 18 carbon atoms (a mixture of oleic acid, linoleic acid, linolenic acid, etc.). , An alicyclic, an alicyclic having a double bond, an alicyclic ring, and the like are produced to form a mixture thereof, and an amine of this as it is is a dimer diamine. Therefore, the molecular structure of the solvent-soluble polyimide resin of the component (A) obtained by polymerizing the tetracarboxylic acid component and the dimer diamine is complicated because each molecule of the dimer acid, which is a mixture, is irregularly bonded. ,It can not be identified. Examples of the molecular structure that can be inferred include those shown in the following chemical structural formulas, which are considered to be a mixture of these. (These structural formulas are merely examples and are not limited to these.)

In the above chemical formula, n indicates an integer, R ₁ , R ₂ , R ₃ , and R ₄ indicate an organic group, and as an example, R ₁ , R ₂ are − (CH ₂ ) _n1 − (CH = C). _n2 − (CH ₂ ) _{n3 − CH 3} and may be the same or different. R ₃ and R ₄ indicate (CH ₂ ) _n1 − (CH = CH) _n2 − (CH ₂ ) _n3 −. It may be the same or different. N ₁ and n ₃ are integers from 0 to 18, n ₂ is an integer of 0 or 1 or 2, and the total number of carbon atoms in the dimerdiamine component is 36.

また、市販品としては、ｊＥＲ ＹＸ８８００（商品名、三菱化学（株）製）が挙げられる。 (B) Epoxy resin having an anthracene skeleton The epoxy resin of the component (B) is not particularly limited as long as it is an epoxy resin having an anthracene skeleton. Further, as a specific example of the epoxy resin having an anthracene skeleton, those shown in the following formulas are exemplified.

Examples of commercially available products include jER YX8800 (trade name, manufactured by Mitsubishi Chemical Corporation).

The resin composition of the present invention is thermosetting using a resin composition by using a solvent-soluble polyimide as a component (A) and an epoxy resin having an anthracene skeleton as a component (B) as essential components. The CTE after curing of the film is low, and the film exhibits specific behavior. Normally, a CTE such as an epoxy resin has a large CTE (α2) at a high temperature above the glass point (Tg), but in the resin composition of the present invention, the solvent-soluble polyimide of the component (A) and the component (B) are used. By using an epoxy resin having an anthracene skeleton as an essential component, the CTE in a high temperature range of 100 ° C. or higher after curing of a thermosetting film produced by using the resin composition is lowered. That is, the CTE is low in a high temperature range of 100 ° C. or higher where the temperature is likely to change in a short time. As a result, the cured product of the thermosetting film produced by using the resin composition of the present invention has a small dimensional change even over the entire temperature range changing from a low temperature to a high temperature, and cracks due to a temperature change such as a heat cycle. Defects such as peeling and peeling are unlikely to occur.
The solvent-soluble polyimide is disclosed in Japanese Patent Application Laid-Open No. 2012-162658 and the like, and it is described that it may be combined with various epoxy resins, but these documents do not describe CTE.

The epoxy resin having the anthracene skeleton of the component (B) preferably has an epoxy equivalent of 160 to 220. If it is less than 160, it tends to be hard and brittle, and if it is more than 220, it may not be possible to reduce the CTE of the thermosetting film produced by using the resin composition. The epoxy resin of the component (B) preferably has an epoxy equivalent of 170 to 190.

In the resin composition of the present invention, the blending ratio (mass ratio) ((A): (B)) of the solvent-soluble polyimide resin of the component (A) and the epoxy resin having the anthracene skeleton of the component (B) is determined. It is preferably 95: 5 to 70:30. When the amount of the solvent-soluble polyimide resin of the component (A) is larger than that of 95: 5, there is a possibility that a low CTE cannot be obtained due to the effect of the component B. On the other hand, when the amount of the epoxy resin having the anthracene skeleton of the component (B) is larger than 70:30, the cured product becomes hard and brittle, and the adhesiveness, flexibility and toughness may be impaired.
The blending ratio of both ((A): (B)) is more preferably 90: 10 to 80:20.

(C) Curing catalyst The curing catalyst of the component (C) is a curing of a thermosetting film formed by using the resin composition of the present invention, more specifically, a solvent-soluble polyimide resin of the component (A) and ( It is a catalyst that promotes the curing reaction with the epoxy resin having the anthracene skeleton of the component B) and the curing reaction of the epoxy resin having the anthracene skeleton of the component (B).
As the curing catalyst of the component (C), an amine-based curing catalyst and an imidazole-based curing catalyst are preferable because they have good curability. An imidazole-based curing catalyst is more preferable because it has relatively good storage stability.
Examples of amine-based curing catalysts include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, and ethylenediamine. , Hexamethylenediamine, diethylenetriamine, triethylenetetramine and other aliphatic amines, and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and the like.
Examples of the imidazole-based curing catalyst include 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and the like. Examples of commercially available products include EH-2021, EH-5010S (trade name, manufactured by ADEKA Corporation), EMI24, BMI12, IBMI12 (trade name, manufactured by Mitsubishi Chemical Corporation) and the like.

The content of the component (C) is appropriately selected according to the type of curing catalyst used as the component (C). When an imidazole-based curing catalyst is used as the component (C), 0.1 part by mass with respect to 100 parts by mass in total of the solvent-soluble polyimide resin of the component (A) and the epoxy resin having the anthracene skeleton of the component (B). It is preferably 5.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 3.0 parts by mass or less.
If the content of the component (C) is too small, the curability of the thermosetting film produced by using the resin composition of the present invention may deteriorate, and the adhesiveness, toughness, and heat resistance may decrease. On the other hand, if the content of the component (C) is too large, the shelf life of the thermosetting film produced by using the resin composition of the present invention may be deteriorated, and the original physical properties of the resin may be impaired in the cured product. Adhesiveness, toughness, and heat resistance may decrease.

(D) Inorganic filler Examples of the inorganic filler of the component (D) include silica, barium sulfate, calcium carbonate, talc, kaolin, clay, boron nitride, silicon nitride, aluminum nitride, silicon carbide, magnesium oxide, magnesium hydroxide, and magnesium carbonate. , Aluminum hydroxide, and at least one selected from alumina is preferable, and silica is more preferable from the viewpoint of low CTE. Further, the heat-curable film produced by using the resin composition of the present invention has electrical characteristics in a high frequency region, specifically, low dielectric constant (ε) in a frequency region of 1 to 100 GHz and low dielectric loss tangent. When (tan δ) is required, silica and hollow silica are preferable, and hollow silica is more preferable.

The inorganic filler of the component (D) preferably has an average particle size of 20 μm or less because the required film thickness can be reduced to 30 μm, and more preferably 15 μm or less.
Here, the shape of the filler is not particularly limited and may be any of spherical, amorphous, flaky and the like, but spherical is desirable from the viewpoint of dispersibility and appropriate coating.
In the present specification, the average particle size is the particle size at an integrated value of 50% in the particle size distribution on a volume basis, which is measured by a laser diffraction / scattering method. The average particle size can be measured by, for example, a laser scattering diffraction method particle size distribution measuring device: LS13320 (manufactured by Beckman Coulter, wet).

As the inorganic filler of the component (D), one which has been surface-treated with a silane coupling agent or the like may be used. When a surface-treated inorganic filler is used, the effect of improving the toughness of the cured product is expected by improving the dispersibility of the inorganic filler, the wettability with the resin component, and the bondability.

In the resin composition of the present invention, the content of the inorganic filler of the component (D) is preferably 45% by volume or more and 70% by volume or less, preferably 45% by volume, of all the components of the resin composition of the present invention excluding the solvent. It is more preferably% or more and 65% by volume or less, and most preferably 47% by volume or more and 55% by volume or less.
As described above, the resin composition of the present invention is prepared by using the resin composition by using the solvent-soluble polyimide of the component (A) and the epoxy resin having the anthracene skeleton of the component (B) as essential components. Since the CTE of the thermosetting film after curing can be made lower, even if the amount of the inorganic filler added is reduced as compared with the conventional thermosetting film, the same CTE as that of the conventional thermosetting film can be obtained. And, the adhesive strength can be improved as compared with the conventional thermosetting film.
Further, when the amount of the inorganic filler added is the same as that of the conventional thermosetting film, the adhesive strength equivalent to that of the conventional thermosetting film can be obtained, and the CTE is lower than that of the conventional thermosetting film. Can be made to.

The resin composition of the present invention may further contain the following components as optional components.

(E) Silane Coupling Agent The resin composition of the present invention contains a silane coupling agent as the component (E) in order to improve the peel strength of the thermosetting film produced using the resin composition after curing. You may.
The resin composition may contain at least one selected from a mercapto-based silane coupling agent, an amino-based silane coupling agent, and a glycidyl-based silane coupling agent as the silane coupling agent of the component (E). It is preferable to improve the peel strength of the produced thermosetting film.

Specific examples of the mercapto-based silane coupling agent include 3-mercaptopropyltrimethoxysilane (trade name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (trade name KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.). ).
Specific examples of the amino-based silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), N-2- (aminoethyl). ) -3-Aminopropyltrimethoxysilane (trade name KBM-603, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-Aminopropyltrimethoxysilane (trade name KBM-903, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-Aminopropyl Triethoxysilane (trade name KBE-903, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (trade name KBE-9103, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ), N-Phenyl-3-aminopropyltrimethoxysilane (trade name: KBM573, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
Specific examples of the glycidyl-based silane coupling agent include 3-glycidoxypropylmethyldimethoxysilane (trade name: KBM-402, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 3-glycidoxypropyltrimethoxysilane (trade name: KBM-). 403, manufactured by Shin-Etsu Chemical Industry Co., Ltd., 3-glycidoxypropylmethyldiethoxysilane (trade name KBE-402, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-glycidoxypropyltriethoxysilane (trade name KBE-403) , Made by Shin-Etsu Chemical Industry Co., Ltd.).

When a silane coupling agent is contained as the component (E), the resin component (component (A) and component (B)) according to the present invention and the component (F) (when the component (F) described later is contained) With respect to a total of 100 parts by mass, it is preferably 0.1 part by mass or more and 5.0 parts by mass or less, more preferably 0.3 parts by mass or more and 3.0 parts by mass or less, and 0.5 parts by mass or more. Most preferably, it is 3.0 parts by mass or less.

(F) Flame Retardant The resin composition of the present invention may contain a flame retardant as the component (F) in order to improve the flame retardancy of the thermosetting film produced using the resin composition after curing. Good.
Examples of the flame retardant of the component (F) include a phosphorus-based flame retardant, for example, an aromatic condensed phosphoric acid ester such as resorcinolbis-dixylenyl phosphate (trade name: PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.), and diethyl. Known phosphinic acid metal salts such as aluminum phosphinate (trade name Exolit OP935, manufactured by Clariant Japan Co., Ltd.) and melamine-based flame retardants such as melamine cyanurate (trade name XS-MC-15, manufactured by Ozeki Co., Ltd.) Flame retardants can be used.
When the flame retardant is contained, when the total of the components (A) and (B) is 100 parts by mass, it is preferably 30 parts by mass or more and 150 parts by mass or less, and 50 parts by mass or more and 120 parts by mass or less. Is more preferable.

The resin composition of the present invention dissolves the above-mentioned components (A) to (D), and the raw materials containing the components (E) and (F) added as necessary, and other components in an organic solvent. Alternatively, it can be obtained by dispersing or the like. The device for dissolving or dispersing these raw materials is not particularly limited, but a stirrer, a resolver, a planetary mixer, a raikai machine, a three-roll mill, a ball mill, a bead mill, or the like equipped with a heating device shall be used. Can be done. Moreover, you may use these devices in combination as appropriate.

The resin composition of the present invention has the following suitable properties.
In the resin composition of the present invention, the cured resin product has sufficient adhesive strength. Specifically, the cured resin product preferably has a peel strength (180 degree peel) of 3.5 N / cm or more, more preferably 4.5 N / cm, with respect to the roughened surface of the copper foil measured in accordance with JIS C6471. It is cm or more, more preferably 7 N / cm or more.

The resin composition of the present invention has a low coefficient of linear expansion (CTE) of the cured resin product. Specifically, the CTE measured by the procedure described in Examples described later is preferably 20 ppm or less, more preferably 15 ppm or less.

It is preferable that the cured resin composition of the resin composition of the present invention has excellent dielectric properties at high frequencies. Specifically, the dielectric constant (ε) in the frequency range of 1 to 100 GHz is preferably 3.5 or less, and more preferably 3.0 or less. Further, the dielectric loss tangent (tan δ) in the frequency region of 1 to 100 GHz is more preferably 0.0050 or less, and more preferably 0.0040 or less.

In the resin composition of the present invention to which a flame retardant is added as an optional component, the cured resin is excellent in flame retardancy. Specifically, the flame retardancy based on UL94 satisfies VTM-0.

The thermosetting film of the present invention is formed by the above-mentioned resin composition. Specifically, it is obtained by applying the resin composition to at least one surface of a desired support and then drying it.
The support is appropriately selected depending on the desired form in the method for producing a thermosetting film, and is not particularly limited, and examples thereof include a metal foil such as copper and aluminum, and a carrier film made of a resin such as polyester and polyethylene. When the thermosetting film of the present invention is provided in the form of a film peeled from the support, the support is preferably released from a mold release agent such as a silicone compound.

The method of applying the resin composition to the support is not particularly limited, but the microgravure method, the slot die method, and the doctor blade method are preferable from the viewpoint of thinning and film thickness control. By the slot die method, a film having a thickness of, for example, 5 to 500 μm can be obtained.

The drying conditions can be appropriately set according to the type and amount of the organic solvent used in the resin composition, the thickness of the coating, and the like, and are, for example, about 1 to 30 minutes at 50 to 120 ° C. Can be done. The film can be peeled off from the support at a desired timing.

The film obtained by the above procedure can be thermoset at, for example, 130 ° C. or higher and 250 ° C. or lower, preferably 150 ° C. or higher and 200 ° C. or lower for 30 to 180 minutes. When the film obtained by the above procedure is used as an adhesive film or an interlayer adhesive film for electrical and electronic applications, it is preferably press-cured under the above-mentioned curing conditions.

The thickness of the film obtained by the above procedure is preferably 10 μm or more and 200 μm or less. If the thickness of the film is less than 10 μm, the particle size of the filler used may be larger than the thickness of the film, and the required film characteristics such as insulation may not be obtained. The thickness of the film is more preferably 15 μm or more and 150 μm or less, and further preferably 20 μm or more and 100 μm or less.

The thermosetting film of the present invention, in which the cured resin has the above-mentioned characteristics, is an adhesive film for electrical and electronic applications, an interlayer adhesive film, and in particular, an adhesive used in applications where the usage environment may be as high as 100 ° C. Suitable for films and interlayer adhesive films. However, the thermosetting film of the present invention can also be used for applications other than the above, for example, a coverlay film for a printed wiring board.

The semiconductor device of the present invention uses the resin composition of the present invention for interlayer adhesion of components of the semiconductor device. Specifically, for example, a resin composition of the present invention is used for interlayer adhesion between an electronic component and a substrate, or a thermosetting formed by the resin composition of the present invention in an apparatus including the electronic component. A sex film is used.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

(Examples 1 to 12, Comparative Examples 1 to 7)
With the formulations shown in the table below, each resin (A-1, A-2, A-3, B-1, B'-1, B'-2), elastomer (A'), and soluble flame retardant (F) -1) and a predetermined amount of toluene are weighed in a container, melted by heating using a heating stirrer, cooled to room temperature, and then insoluble flame retardant (F-2) and curing catalyst (C-1). ), Fillers (D-1, D-2), and silane coupling agents (E-1, E-2, E-3) are weighed in, and a rotating / revolving stirrer (Mazelstar (trade name), After stirring and mixing for 3 minutes with (Kurashiki Spinning Co., Ltd.)), dispersion was performed using a bead mill, and the viscosity was adjusted with toluene to prepare a coating liquid containing a resin composition.

（Ｂ´）成分：アントラセン骨格を持たないエポキシ樹脂
（Ｂ´−１）：ビフェニル骨格を有するエポキシ樹脂、ＮＣ−３０００Ｈ（商品名）、日本化薬株式会社製、エポキシ当量２８８
（Ｂ´−２）：ナフタレン骨格を有するエポキシ樹脂、ＨＰ−６０００（商品名）、ＤＩＣ株式会社製、エポキシ当量２５０
（Ｃ）成分：硬化触媒
（Ｃ−１）：イミダゾール系触媒、ＥＨ−２０２１（商品名）、株式会社ＡＤＥＫＡ製
（Ｄ）成分：無機フィラー
（Ｄ−１）：中空シリカ、ＢＡ−１（商品名）、日揮触媒化成株式会社製
（Ｄ−２）：溶融シリカ、ＭＰ−１５ＥＦ（商品名）、株式会社龍森製
（Ｅ）成分：シランカップリング剤
（Ｅ−１）：３−メルカプトメチルジメトキシシラン、ＫＢＭ−８０２（商品名）、信越化学工業株式会社製
（Ｅ−２）：Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、ＫＢＭ−５７３（商品名）、信越化学工業株式会社製
（Ｅ−３）：３−グリシドキシプロピルトリメトキシシラン、ＫＢＭ−４０３（商品名）、信越化学工業株式会社製
（Ｆ）成分：難燃剤
（Ｆ−１）：レゾルシノールビス−ジキシレニルホスフェート、ＰＸ−２００（商品名）、大八化学工業株式会社製
（Ｆ−２）：メラミンシアヌレート、ＸＳ−ＭＣ−１５（商品名）、株式会社尾関製
（Ｆ−３）：ジエチルホスフィン酸アルミニウム、ＯＰ−９３５（商品名、クラリアントジャパン製） The components used when preparing the resin composition are as follows.
(A) Component: Solvent-soluble polyimide resin (A-1): Solvent-soluble polyimide resin synthesized by the following procedure A commercially available aromatic tetra in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. 65.0 g of carboxylic acid dianhydride (BisDA1000 (trade name), manufactured by SABIC Japan Co., Ltd.), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 43.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, manufactured by Claude Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane were added dropwise, and then the imide was added at 140 ° C. over 10 hours. By the chemical reaction, a solution of the solvent-soluble polyimide resin (A-1) (nonvolatile content 29.5%) was obtained. When GPC measurement was performed, the number average molecular weight (Mn) was 15,000.
(A-2): A commercially available aromatic tetracarboxylic dianhydride (BTDT-UP (trade name), Ebony Japan Co., Ltd.) is placed in the same reaction vessel as the solvent-soluble polyimide resin (A-1) synthesized by the following procedure. (Manufactured) 210.0 g, cyclohexanone 1008.0 g, and methylcyclohexane 201.6 g were charged, and the solution was heated to 60 ° C. Next, 341.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, manufactured by Claude Japan Co., Ltd.) was added dropwise, and then an imidization reaction was carried out at 140 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure. By performing toluene substitution, a solution (nonvolatile content 30.1%) of a solvent-soluble polyimide resin (A-2) was obtained. When GPC measurement was performed, the number average molecular weight (Mn) was 15,000.
(A-3): Commercially available aromatic tetracarboxylic dianhydride (BTDA-PF (trade name), Ebony Japan Co., Ltd.) is placed in the same reaction vessel as the solvent-soluble polyimide resin (A-1) synthesized by the following procedure. (Manufactured by) 190.0 g, 912.0 g of cyclohexanone, and 182.4 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Then, 288.1 g of a commercially available diamine diamine (PRIAMINE 1075 (trade name), manufactured by Claude Japan Co., Ltd.) and 24.7 g of a commercially available silicone diamine (KF-8010 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise. Then, the imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of a polyimide resin (nonvolatile content: 30.8%). When GPC measurement was performed, the number average molecular weight (Mn) was 14,000.
A': Elastomer (SEEPS), Septon 4044 (trade name), manufactured by Kuraray Co., Ltd. (B) Ingredients: epoxy resin having an anthracene skeleton (B-1): JER YX8800 (trade name), manufactured by Mitsubishi Chemical Corporation (below) Structure shown in the formula), epoxy equivalent 180

(B') Ingredient: Epoxy resin without anthracene skeleton (B'-1): Epoxy resin with biphenyl skeleton, NC-3000H (trade name), manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288
(B'-2): Epoxy resin having a naphthalene skeleton, HP-6000 (trade name), manufactured by DIC Corporation, epoxy equivalent 250
Component (C): Curing catalyst (C-1): Imidazole-based catalyst, EH-2021 (trade name), manufactured by ADEKA Co., Ltd. (D) Component: Inorganic filler (D-1): Hollow silica, BA-1 (commodity) Name), manufactured by Nikki Catalyst Kasei Co., Ltd. (D-2): fused silica, MP-15EF (trade name), manufactured by Ryumori Co., Ltd. (E) Ingredients: silane coupling agent (E-1): 3-mercaptomethyl Dimethoxysilane, KBM-802 (trade name), manufactured by Shin-Etsu Chemical Industry Co., Ltd. (E-2): N-phenyl-3-aminopropyltrimethoxysilane, KBM-573 (trade name), manufactured by Shin-Etsu Chemical Industry Co., Ltd. ( E-3): 3-glycidoxypropyltrimethoxysilane, KBM-403 (trade name), manufactured by Shin-Etsu Chemical Industry Co., Ltd. (F) Ingredients: flame retardant (F-1): resorcinolbis-dixylenyl phosphate, PX-200 (trade name), manufactured by Daihachi Chemical Industry Co., Ltd. (F-2): melamine silanelate, XS-MC-15 (trade name), manufactured by Ozeki Co., Ltd. (F-3): aluminum diethylphosphinate, OP-935 (Product name, manufactured by Clariant Japan)

The following evaluation was carried out on the coating liquid prepared by the above procedure.
1. 1. Peel strength The obtained coating liquid was applied onto a 50 μm-thick PET film to which a mold release agent was applied as a base material using a coating machine so that the dry coating film had a film thickness of 25 ± 5 μm. It was dried at 80 ° C. for 15 minutes to prepare an uncured film. The base material of this film is peeled off, copper foils are attached to both sides of the film, press-cured with a vacuum press (200 ° C x 60 minutes, 1 MPa), cut into 10 mm widths to make test pieces, and copper is used by autograph. The foil was peeled off in the 180 ° direction, and the peel strength was measured. The average value of each N = 5 was taken as the measured value.
2. Linear expansion coefficient 1. The base material of the uncured film obtained in (1) was peeled off, laminated to a thickness of about 300 μm, press-cured with a vacuum press (200 ° C. × 60 min, 1 MPa), and then cut into 20 × 5 mm for testing. The linear expansion coefficient was calculated by measuring the displacement with respect to the temperature change in the tension mode with TMA. The measurement temperature range was 25 ° C. to 250 ° C., and the coefficient of linear expansion within the temperature range of 110 to 140 ° C. was calculated.
3. 3. Permittivity (ε), Dissipation factor (tanδ)
1. 1. After curing the uncured film obtained in (1) for 200 ° C. × 60 min, the substrate was peeled off, cut into 130 × 70 mm, and ε and tan δ were measured at a dielectric resonance frequency of 2 GHz by the SPDR method.
The results are shown in the table below.

実施例１〜１２はいずれも銅箔１８０°ピール強度が３．０Ｎ／ｃｍ以上であり、線膨張係数が２０ｐｐｍ以下であった。なお、実施例２は、実施例１に対し、（Ｅ）成分のシランカップリング剤を変えた実施例である。実施例３は、実施例１に対し、（Ａ）成分の溶剤可溶性ポリイミドの配合割合を変えた実施例である。実施例４は、（Ａ）成分の溶剤可溶性ポリイミドを１種のみ添加した実施例であり、実施例６は（Ａ）成分の溶剤可溶性ポリイミドを実施例４とは別の１種のみ添加した実施例である。実施例５は、実施例４に対し、（Ｅ）成分のシランカップリング剤を添加しなかった実施例である。実施例７，８は、実施例４に対し（Ｂ）成分のアントラセン骨格を有するエポキシ樹脂の配合割合を変えた実施例である。実施例９は、実施例４に対し（Ｄ）成分の無機フィラーの種類を変えた実施例である。実施例１０は、実施例９に対し（Ｆ）成分の難燃剤を添加しなかった実施例である。実施例１１は、実施例１に対し（Ａ）成分の溶剤可溶性ポリイミドについて（Ａ−２）を（Ａ−３）に変えた実施例である。実施例１２は、実施例１の（Ｆ）成分の難燃剤を（Ｆ−３）の１種のみ添加し、かつその添加量を減量した実施例であり、このことにより銅箔１８０°ピール強度が向上し、難燃性の低下はなく実施例１と同等であり、ＶＴＭ−０相当であった。（Ｆ）成分の難燃剤として（Ｆ−３）を使用すると、他の難燃剤より添加量を減らしても難燃効果があるので、相対的に樹脂量を増やせ、接着強度の向上、あるいは（Ｄ）成分の無機フィラーを増やせるので更なる低ＣＴＥにつながる。
比較例１，２は、実施例６に対し（Ｂ）成分のアントラセン骨格を有するエポキシ樹脂の代わりに、ビフェニル骨格を有するエポキシ樹脂（Ｂ´−１）、ナフタレン骨格を有するエポキシ樹脂（Ｂ´−２）を使用した比較例であり、線膨張係数を調節する目的で（Ｄ）成分の無機フィラーの配合割合を増やしたところ、銅箔１８０°ピール強度が低下した。比較例３は、実施例６に対し（Ｂ）成分のアントラセン骨格を有するエポキシ樹脂の代わりに、ビフェニル骨格を有するエポキシ樹脂（Ｂ´−１）、を使用した比較例であり、（Ｄ）成分の無機フィラーの配合割合を実施例６と同じにしたところ、線膨張係数が上昇した。比較例４は、実施例５に対し（Ｂ）成分のアントラセン骨格を有するエポキシ樹脂の代わりに、ビフェニル骨格を有するエポキシ樹脂（Ｂ´−１）、を使用した比較例であり、（Ｄ）成分の無機フィラーの配合割合を５４ｖｏｌ％まで増量したところ、実施例５に対して、ＣＴＥは同等となったが、銅箔１８０°ピール強度が低下した。比較例５は、実施例６に対し（Ｂ）成分のアントラセン骨格を有するエポキシ樹脂の代わりに、ナフタレン骨格を有するエポキシ樹脂（Ｂ´−２）、を使用した比較例であり、（Ｄ）成分の無機フィラーの配合割合を実施例６と同じにしたところ、線膨張係数が上昇した。比較例６は、実施例１に対し（Ａ）成分の溶剤可溶性ポリイミド樹脂の代わりにエラストマー（ＳＥＥＰＳ）を添加した比較例であり、銅箔１８０°ピール強度が０Ｎ／ｃｍであり、線膨張係数も上昇した。比較例７は、実施例１０に対し（Ｂ）成分のアントラセン骨格を有するエポキシ樹脂の代わりに、ビフェニル骨格を有するエポキシ樹脂（Ｂ´−１）、を使用した比較例であり、線膨張係数が上昇した。

In each of Examples 1 to 12, the copper foil 180 ° peel strength was 3.0 N / cm or more, and the coefficient of linear expansion was 20 ppm or less. In addition, Example 2 is an Example in which the silane coupling agent of the component (E) was changed with respect to Example 1. Example 3 is an example in which the mixing ratio of the solvent-soluble polyimide of the component (A) is changed with respect to Example 1. Example 4 is an example in which only one type of solvent-soluble polyimide of component (A) is added, and Example 6 is an example in which only one type of solvent-soluble polyimide of component (A) is added, which is different from Example 4. This is an example. Example 5 is an example in which the silane coupling agent of the component (E) was not added to Example 4. Examples 7 and 8 are examples in which the blending ratio of the epoxy resin having the anthracene skeleton of the component (B) is changed from that of Example 4. Example 9 is an example in which the type of the inorganic filler of the component (D) is changed from that of Example 4. Example 10 is an example in which the flame retardant of the component (F) was not added to Example 9. Example 11 is an example in which (A-2) is changed to (A-3) for the solvent-soluble polyimide of the component (A) with respect to Example 1. Example 12 is an example in which only one of the flame retardants of the component (F) of Example 1 is added and the amount of the flame retardant added is reduced, whereby the copper foil 180 ° peel strength is increased. Was improved, and there was no decrease in flame retardancy, which was equivalent to that of Example 1 and was equivalent to VTM-0. When (F-3) is used as the flame retardant of the component (F), it has a flame retardant effect even if the amount added is smaller than that of other flame retardants. D) Since the amount of the inorganic filler of the component can be increased, it leads to further low CTE.
In Comparative Examples 1 and 2, the epoxy resin having a biphenyl skeleton (B'-1) and the epoxy resin having a naphthalene skeleton (B'-) were used instead of the epoxy resin having the anthracene skeleton of the component (B) as compared with Example 6. In the comparative example using 2), when the compounding ratio of the inorganic filler of the component (D) was increased for the purpose of adjusting the linear expansion coefficient, the copper foil 180 ° peel strength decreased. Comparative Example 3 is a comparative example in which an epoxy resin having a biphenyl skeleton (B'-1) is used instead of the epoxy resin having an anthracene skeleton of the component (B) with respect to Example 6, and the component (D) is used. When the blending ratio of the inorganic filler in No. 6 was the same as in Example 6, the coefficient of linear expansion increased. Comparative Example 4 is a comparative example in which an epoxy resin having a biphenyl skeleton (B'-1) is used instead of the epoxy resin having an anthracene skeleton of the component (B) as compared with Example 5, and the component (D) is used. When the blending ratio of the inorganic filler in No. 5 was increased to 54 vol%, the CTE was equivalent to that in Example 5, but the copper foil 180 ° peel strength was lowered. Comparative Example 5 is a comparative example in which an epoxy resin having a naphthalene skeleton (B'-2) is used instead of the epoxy resin having the anthracene skeleton of the component (B) as compared with Example 6, and the component (D) is used. When the blending ratio of the inorganic filler in No. 6 was the same as in Example 6, the coefficient of linear expansion increased. Comparative Example 6 is a comparative example in which an elastomer (SEEPS) was added instead of the solvent-soluble polyimide resin of the component (A) to Example 1, the copper foil 180 ° peel strength was 0 N / cm, and the coefficient of linear expansion. Also rose. Comparative Example 7 is a comparative example in which an epoxy resin having a biphenyl skeleton (B'-1) is used instead of the epoxy resin having the anthracene skeleton of the component (B) as compared with Example 10, and the coefficient of linear expansion is high. Rose.

Claims (7)

(A) Solvent-soluble polyimide resin,
(B) Epoxy resin having an anthracene skeleton,
(C) Curing catalyst and
(D) an inorganic filler seen including,
The solvent-soluble polyimide resin (A) is a polyimide resin obtained by reacting a tetracarboxylic acid component with a dimer diamine.
The blending ratio (mass ratio) ((A): (B)) of the solvent-soluble polyimide resin of the component (A) and the epoxy resin having an anthracene skeleton of the component (B) is 95: 5 to 70 :. A resin composition of 30. The resin composition according to claim 1 , wherein the inorganic filler (D) contains hollow silica. The resin composition according to claim 1 or 2 , further containing (E) a silane coupling agent. A thermosetting film formed by the resin composition according to any one of claims 1 to 3. The resin composition according to any one of claims 1 to 3 or the cured resin product obtained by curing the thermosetting film according to claim 4. A laminated board containing the cured resin product according to claim 5. A semiconductor device containing the cured resin product according to claim 5.