WO2018097010A1

WO2018097010A1 - Resin composition, thermosetting film using same, resin cured product, laminate, printed wiring board and semiconductor device

Info

Publication number: WO2018097010A1
Application number: PCT/JP2017/041129
Authority: WO
Inventors: 佐藤　淳也; 津与志黒川; 吉田　真樹
Original assignee: ナミックス株式会社
Priority date: 2016-11-24
Filing date: 2017-11-15
Publication date: 2018-05-31
Also published as: JP6917636B2; JPWO2018097010A1; TW201823350A; CN109923176A; KR20190080887A; KR102399159B1; CN109923176B; TWI743251B

Abstract

Provided are: a thermosetting film which has excellent bonding strength to a metal foil contained in wiring lines of a printed wiring board and a substrate material such as a polyimide, while exhibiting dielectric characteristics in a high frequency region, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1-100 GHz; and a resin composition which is used for the production of this thermosetting film. A resin composition which contains (A) an epoxy resin, (B) a resin that has a dielectric loss tangent (tan δ) of less than 0.005 in a frequency region of 1-100 GHz and (C) an imidazole compound wherein a side chain having an alkyl group with 5 or more carbon atoms is present at the 1-position of a heterocyclic ring.

Description

Resin composition, thermosetting film, cured resin, laminate, printed wiring board, and semiconductor device using the same

The present disclosure relates to a resin composition, and a thermosetting film, a resin cured product, a laminated board, a printed wiring board, and a semiconductor device using the resin composition.

In recent years, electrical and electronic devices have been reduced in size, weight, and performance. Along with this, printed wiring boards used in these devices, especially multilayer printed wiring boards, are required to have higher multi-layers, higher density, thinner, lighter weight, higher reliability, and moldability. ing. In addition, with the recent demand for higher speed transmission signals in printed wiring boards, the frequency of transmission signals has increased significantly. Thereby, it is required that the material used for the printed wiring board can reduce electric signal loss in a high frequency region, specifically, in a region having a frequency of 1 GHz or more.

Dielectric properties (low dielectric constant (ε), excellent dielectric properties in the high-frequency region) are also used for interlayer adhesives used in multilayer printed wiring boards or adhesive films used as surface protective films (ie, coverlay films) of printed wiring boards. In addition, it is required to show a low dielectric loss tangent (tan δ). Specifically, the dielectric constant in the frequency range of 1 to 10 GHz is required to be 3.5 or less, and the dielectric loss tangent (tan δ) in the frequency range of 1 to 10 GHz is required to be 0.010 or less. . In the present disclosure, “˜” in a numerical range means that numerical values described before and after the numerical value are included in the region. That is, the numerical range “X to Y” means X or more and Y or less. An adhesive film that satisfies the above conditions of dielectric constant and dielectric loss tangent has been proposed in Patent Document 1, for example.

However, there is a demand for further improvement in adhesion strength to polyimide contained in the substrate of the printed wiring board. Therefore, the adhesive strength of the adhesive film described in Patent Document 1 may not always be sufficient.

JP 2011-068713 A

In order to solve the above-described problems in the prior art, an object of the present disclosure is to provide the following resin composition, a thermosetting film using the same, a cured resin, a laminated board, a printed wiring board, and a semiconductor device. There is. This thermosetting film has an excellent adhesive strength after curing to a metal foil contained in the wiring of the printed wiring board and a substrate material such as polyimide. The thermosetting film exhibits dielectric properties in a high frequency region, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1 to 100 GHz. Said resin composition can be used for preparation of this thermosetting film.

In order to achieve the above object, one aspect (first aspect) of the present disclosure includes
(A) epoxy resin,
(B) a resin having a dielectric loss tangent (tan δ) of less than 0.005 in the frequency range of 1 to 100 GHz;
and,
(C) an imidazole compound in which a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring;
The resin composition containing this is provided.

The (C) imidazole compound contained in the resin composition of the first aspect is preferably a compound represented by the following formula (I).

(In Formula (I), R ¹ , R ² , and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M is 0 or 1. R ⁴ Is an alkylene group having 1 to 3 carbon atoms or —CH ₂ CH ₂ COO—, and R ⁵ is an alkyl group having 5 to 10 carbon atoms.)

The resin (B) contained in the resin composition of the first aspect is preferably at least selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. One resin.

The second aspect of the present disclosure provides a thermosetting film formed from the resin composition.

Also, a third aspect of the present disclosure provides a cured resin product that is the cured resin composition or the thermosetting film.

Moreover, the 4th aspect in this indication provides the laminated board containing the said resin hardened | cured material.

Further, the fifth aspect of the present disclosure provides a printed wiring board including the above resin cured product.

Also, a sixth aspect of the present disclosure provides a semiconductor device including the resin cured product.

The thermosetting film formed from the resin composition of the first aspect described above has excellent adhesion to a metal foil contained in the wiring of the printed wiring board and a substrate material such as polyimide after curing. It has strength and exhibits dielectric characteristics in a high frequency region, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1 to 100 GHz.

Hereinafter, an embodiment of the present disclosure will be described in detail.
The resin composition of this embodiment includes (A) an epoxy resin, (B) a resin having a dielectric loss tangent (tan δ) of less than 0.005 in the frequency range of 1 to 100 GHz, and (C) the first position of the heterocyclic ring. In addition, an imidazole compound having a side chain containing an alkyl group having 5 or more carbon atoms is included. Each component of the resin composition of this embodiment is described below.

(A) Epoxy resin Examples of the epoxy resin of component (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, siloxane type epoxy resin, biphenyl type epoxy resin. Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, epoxy resin having naphthalene skeleton, and epoxy resin having anthracene skeleton. In the resin composition of the present embodiment, the compounds exemplified here may be used alone, or two or more compounds may be mixed and used.

Also, from the viewpoint of improving dielectric properties, the epoxy resin of component (A) preferably contains any of a biphenyl type epoxy resin, an epoxy resin having a naphthalene skeleton, and an epoxy resin having an anthracene skeleton. Examples of commercially available biphenyl type epoxy resins include NC-3000H manufactured by Nippon Kayaku Co., Ltd., examples of commercially available epoxy resins having a naphthalene skeleton include HP4032D manufactured by DIC Corporation, and a commercially available anthracene skeleton. As an example of the epoxy resin, JERIX8800 manufactured by Mitsubishi Chemical Corporation can be given.

From the viewpoint of improving dielectric properties and peel strength with respect to copper foil, the epoxy resin of component (A) is preferably a naphthalene type epoxy resin.

The content of the epoxy resin as the component (A) is preferably 2 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 100 parts by mass in total of the components (A) and (B). 2 to 10 parts by mass. When there are too few (A) components, the adhesiveness of the thermosetting film formed from the resin composition of this embodiment will deteriorate. When the amount of the component (A) is too large, the amount of the component (B) is relatively decreased, so that the dielectric properties in the high frequency region of the thermosetting film are deteriorated.

(B) Component resin has a dielectric loss tangent (tan δ) of less than 0.005 in the frequency range of 1 to 100 GHz. This is because the thermosetting film formed from the resin composition of the present disclosure has excellent dielectric properties in a high frequency region, that is, a low dielectric constant (ε) in a frequency region of 1 GHz or more and a low dielectric loss tangent. Contributes to (tan δ).

The resin of component (B) is preferably at least one resin selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene thermoplastic elastomer, and a polyimide resin. Only one of these resins may be used, or two or more resins may be used in combination.

As the component (B), when a modified PPE resin is used, a compound represented by the following general formula (1) is preferably used.

In the formula (1), — (O—X—O) — is represented by the following general formula (2) or (3).

In formula (2), R ₁ , R ₂ , R ₃ , R ₇ , and R ₈ are alkyl groups or phenyl groups having 6 or less carbon atoms, and may be the same or different from each other. R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other.

Wherein _{_{_{(3), R 9, R}}} 10, R 11, R 12, R 13, R 14, R 15 and _{R 16,} is a hydrogen atom, an alkyl group or a phenyl group, the 6 or less carbon atoms, They may be the same or different from each other. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In the formula (1), — (YO) — is represented by the general formula (4). In the formula (1), one type of structure or two or more types of structures represented by the formula (4) are randomly arranged.

In the formula (4), R ₁₇ and R ₁₈ are an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other. R ₁₉ and R ₂₀ are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other.

In the formula (1), a and b represent integers of 0 to 100. However, at least one of a and b is not 0.

Examples of -A- in formula (3) include methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1- And divalent organic groups such as methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene. However, this divalent organic group is not limited to these groups.

Among the compounds represented by the formula (1), R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ , and R ₁₈ are preferably an alkyl group having 3 or less carbon atoms, and R ₄ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ , and R ₂₀ are a hydrogen atom or an alkyl group having 3 or less carbon atoms is there. Particularly preferably, — (O—X—O) — represented by the general formula (2) or the general formula (3) is the general formula (5), the general formula (6), or the general formula (7). More preferably, — (YO) — represented by the general formula (4) is the formula (8) or the formula (9).

The method for producing the compound represented by the formula (1) is not particularly limited. For example, it can be produced by vinylbenzyl etherifying a terminal phenolic hydroxyl group of a bifunctional phenylene ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound.

The number average molecular weight of the compound represented by the formula (1) is preferably in the range of 500 to 3,000, more preferably in the range of 1000 to 2500 in terms of polystyrene by the GPC method. When the number average molecular weight is 500 or more, there is little stickiness when the resin composition of this embodiment is formed into a coating film. Moreover, if a number average molecular weight is 3000 or less, the fall of the solubility to a solvent can be suppressed.

The styrene-based thermoplastic elastomer as the component (B) refers to a thermoplastic elastomer containing styrene, a homologue thereof, or an analogue thereof. Examples of the styrenic thermoplastic elastomer as the component (B) include polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS), styrene- Examples include butadiene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and polybutadiene (PB). One of the elastomers exemplified here may be used alone, or two or more elastomers may be mixed and used. From the viewpoint of improving the dielectric properties with respect to the metal foil contained in the wiring of the printed wiring board and the substrate material such as polyimide, SEEPS is preferable.

When a polyimide resin is used as the component (B), a solvent-soluble polyimide resin is preferably used. In the present embodiment, the term “solvent soluble” means that 20% by weight or more is dissolved in at least one solvent selected from the solvents shown below at 23 ° C. These solvents include hydrocarbon solvents such as toluene, xylene, ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ether solvents 1,4-dioxane, tetrahydrofuran, diglyme, glycol ether solvents. Methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, ester solvents such as ethyl acetate, butyl acetate, ethyl lactate, gamma butyrolactone, benzyl alcohol, N- Methyl pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

The solvent-soluble polyimide of the present embodiment can be obtained by reacting a diamine and a tetracarboxylic acid component at a temperature of 130 ° C. or higher to cause an imidization reaction. Preferably, the solvent-soluble polyimide is a polyimide resin having excellent flexibility, toughness, and heat resistance. The polyimide resin is obtained by reacting a tetracarboxylic acid component with dimer diamine. In this reaction that produces a solvent-soluble polyimide, a portion of dimer diamine may be replaced by silicone diamine.

Examples of the tetracarboxylic acid component used here include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone. Tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1, 2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxy) Enoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and 4,4 Examples include '-(4,4'-isopropylidenediphenoxy) diphthalic dianhydride.

Examples of dimeramine include Versamine 551 (trade name, manufactured by BASF Japan Ltd .; 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)) cyclohexene) and Versamine 552 (trade name, manufactured by Cognics Japan, Inc .; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (both are trade names, manufactured by Croda Japan Co., Ltd.).

The solvent-soluble polyimide resin has a polyimide molecular structure generated by a reaction between a tetracarboxylic acid component and dimer diamine. An acid anhydride group or an amino group is present at the end of the molecular structure. Dimer acid, which is a raw material of dimeramine, can be obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms (a mixture of oleic acid, linoleic acid, linolenic acid, and the like). By the dimerization reaction, a mixture containing a reaction product having a linear chain, an alicyclic ring, an alicyclic ring having a double bond, or an aromatic ring in an amount corresponding to the reaction probability is obtained. Dimerized amine is obtained by amination of this reaction mixture as it is. Therefore, the solvent-soluble polyimide resin obtained by polymerization of tetracarboxylic acid and dimer diamine has a complicated molecular structure that is generated as a result of irregular binding of each molecule of dimer acid contained in the reaction mixture. This complex molecular structure cannot be clearly identified. However, examples of molecular structures that can be inferred include molecular structures represented by the following chemical structural formulas. The solvent-soluble polyimide resin used in this embodiment is considered to be a mixture of polyimide resins having these molecular structures. (These structural formulas are merely examples. The molecular structure of the solvent-soluble polyimide resin used in the present embodiment is not limited to these.)

In the above chemical formula, n is an integer. R ¹⁰ , R ²⁰ , R ³⁰ , and R ⁴⁰ are organic groups. For example, R ¹⁰ and R ²⁰ are — (CH ₂ ) _n1 — (CH═CH) _n2 — (CH ₂ ) _n3 —CH ₃ and may be the same or different from each other. R ³⁰ and R ⁴⁰ are — (CH ₂ ) _n1 — (CH═CH) _n2 — (CH ₂ ) _n3 —, and may be the same or different from each other. n1 and n3 are integers from 0 to 18. n2 is an integer of 0, 1, or 2. The total number of carbon atoms in the dimer diamine component is 36.

The resin content of the component (B) is preferably 70 to 98 parts by weight, more preferably 80 to 98 parts by weight, and still more preferably 90 to 98 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). 98 parts by mass.
When there is too little resin of (B) component, it will become difficult to obtain the dielectric characteristic in the desired high frequency area | region of the thermosetting film formed from the resin composition of this embodiment. When there is too much resin of (B) component, the quantity of (A) component will reduce relatively. Therefore, the adhesiveness and sclerosis | hardenability of the thermosetting film formed from the resin composition of this embodiment deteriorate.

The action of the (C) component imidazole compound varies depending on the resin used as the (B) component. When the resin used as the component (B) is a resin that causes a curing reaction with the epoxy resin of the component (A), such as a polyimide resin, the imidazole compound of the component (C) acts as a curing catalyst. . On the other hand, when the resin used as component (B) is a resin that does not react with the epoxy resin of component (A), such as a modified PPE resin or a styrene thermoplastic elastomer, the imidazole compound of component (C) is ( A) It acts as a curing catalyst for the epoxy resin itself.

Imidazole compounds are conventionally used as curing agents or curing catalysts for epoxy resins. In the resin composition of this embodiment, an imidazole compound having a specific structure in which a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring as the component (C). . Thereby, the thermosetting film formed from the resin composition has excellent adhesive strength with respect to the substrate material such as metal foil and polyimide contained in the wiring of the printed wiring board, and has a high frequency range. In particular, the dielectric characteristics of the low dielectric constant (ε) and the low dielectric loss tangent (tan δ) are shown in the frequency range of 1 to 100 GHz. The reason for this will be described in detail below.

When the imidazole compound acts as a curing agent or a curing catalyst for the epoxy resin, the unshared electron pair of the nitrogen atom at the 3-position of the heterocyclic ring contributes to the curing reaction. On the other hand, a long hydrocarbon chain such as an alkyl group having 5 or more carbon atoms at the 1-position of the heterocyclic ring improves the dielectric characteristics in the high frequency region, that is, has a low dielectric constant in the frequency region of 1 to 100 GHz. (Ε) and low dielectric loss tangent (tan δ). An imidazole compound in which a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring has a frequency of 1 to 100 GHz without impairing the reactivity when acting as a curing agent curing catalyst for an epoxy resin. A low dielectric constant (ε) and a low dielectric loss tangent (tan δ) can be achieved. This point is also apparent from the results of Examples described later. The imidazole compound used in Comparative Example 3 described later has a long hydrocarbon chain as a side chain of the heterocyclic ring. However, the side chain is at the 2-position of the heterocycle. Therefore, the reactivity is impaired when acting as a curing agent or curing catalyst for an epoxy resin due to steric hindrance. Further, when the imidazole compound used in the examples is thermally decomposed, 2-ethyl-4-methylimidazole and 2-ethylhexyl are generated. However, even if these are used, it becomes clear from Comparative Examples 3 and 5 described later that the reactivity when acting as a curing agent or a curing catalyst for the epoxy resin is insufficient.

The (C) component imidazole compound is not particularly limited as long as a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring. For example, an imidazole compound represented by the following formula (I) can be used.

In formula (I), R ¹ , R ² , and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m is 0 or 1. R ⁴ is an alkylene group having 1 to 3 carbon atoms or —CH ₂ CH ₂ COO—. R ⁵ is an alkyl group having 5 to 10 carbon atoms.

Preferable examples of the imidazole compound as component (C) include the following formulas (I1) to (I4). Only one of these examples of imidazole compounds may be used, or two or more imidazole compounds may be used in combination. Among these, the following formulas (I3) and (I4) are preferable from the viewpoint of a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a 100 GHz region. From the viewpoint of controlling the reactivity, the following formula (I4) is more preferable.

The content of the imidazole compound as the component (C) is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass in total of the epoxy resin as the component (A) and the resin as the component (B). The amount is preferably 0.5 to 3.0 parts by mass. When there is too little content of (C) component, the sclerosis | hardenability of the thermosetting film formed from the resin composition of this embodiment will deteriorate, Furthermore, the adhesiveness of the thermosetting film, toughness, and heat resistance May decrease. On the other hand, when there is too much content of (C) component, there exists a possibility that the shelf life of the thermosetting film formed from the resin composition of this embodiment may deteriorate. Moreover, as a result of the impaired physical properties of the cured product of the thermosetting film, there is a risk that the adhesiveness, toughness, and heat resistance of the cured product may be reduced.

The resin composition of the present embodiment can be obtained by dissolving or dispersing a raw material containing the above components (A) to (C) and other components added as necessary in an organic solvent. . There is no restriction | limiting in particular in another component. Examples of other components include inorganic fillers such as silica filler, flame retardants, coupling agents, leveling agents, dispersants, and antifoaming agents. There are no particular limitations on the apparatus for dissolving or dispersing these raw materials. As a stirrer provided with a heating device, a dissolver, a planetary mixer, a lyric machine, a three-roll mill, a ball mill, a bead mill, or the like can be used. These devices may be used in combination as appropriate.

The resin composition of the present embodiment has suitable characteristics shown below. First, as for the resin composition of this embodiment, the cured resin has sufficient adhesive strength. Specifically, the peel strength (180 degree peel) of the cured resin with respect to the polyimide film measured in accordance with JIS C6481 is preferably 6.5 N / cm or more, more preferably 7.0 N / cm or more, and still more preferably. Is 7.5 N / cm or more. Further, the cured resin has a peel strength (180 degree peel) with respect to the glossy copper foil surface measured according to JIS C6481, preferably 6.5 N / cm or more, more preferably 7.0 N / cm or more, and still more preferably. 7.5 N / cm or more.

The cured product of the resin composition of the present embodiment preferably has excellent dielectric properties in a high frequency region. Specifically, the dielectric constant (ε) of the cured product in the frequency region of 1 to 100 GHz is preferably 3.5 or less, more preferably 3.0 or less. The dielectric loss tangent (tan δ) in the frequency region of 1 to 100 GHz is preferably 0.010 or less, more preferably 0.0095 or less.

The thermosetting film of the present embodiment is formed from the above resin composition. Specifically, the thermosetting film is obtained by drying a resin composition applied on at least one surface of a desired support. As a support body, the support body which has a desired form according to the manufacturing method of a thermosetting film is selected suitably. A specific support is not particularly limited. Examples of the support that can be used include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene. When the thermosetting film of the present embodiment is provided in the form of a film peeled from the support, the support is preferably subjected to a release treatment with a release agent such as a silicone compound.

The method for applying the resin composition to the support is not particularly limited. A preferable method is a micro gravure method, a slot die method, or a doctor blade method from the viewpoint of thinning and controlling the film thickness. A film having a thickness of, for example, 5 to 500 μm５ can be obtained by the slot die method.

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

The film obtained by the above procedure can be thermally cured at a temperature of 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 electric or electronic applications, the resin composition is preferably press-cured under the above-mentioned curing conditions.

The thickness of the film obtained by the above procedure is preferably 5 μm or more and 200 μm or less. When the thickness of the film is less than 5 μm, required film characteristics such as insulation may not be obtained. The thickness of the film is more preferably 15 μm to 150 μm, and still more preferably 20 μm to 100 μm.

The thermosetting film of the present embodiment in which the cured resin has the characteristics described above is suitable for an adhesive film, an interlayer adhesive film, and a coverlay film for electrical or electronic use.

In the semiconductor device of this embodiment, the resin composition of the present disclosure is used for interlayer adhesion of the constituent elements. Specifically, for example, the resin composition of the present disclosure is used for interlayer adhesion between an electronic component and a substrate. Or the thermosetting film formed from the resin composition of this embodiment is used in the semiconductor device containing an electronic component.

Hereinafter, the present embodiment will be described in detail by way of examples. However, this embodiment is not limited to these examples.

(Examples 1 to 11, Comparative Examples 1 to 4)
A predetermined amount of each resin (A-1, A-2, A-3, B-1, B-2, B-3, B-4, and B-5) and a predetermined amount in the composition shown in the following table Of toluene was weighed into a container. Subsequently, the mixture of resin and toluene was heated and dissolved using a heating stirrer, and then cooled to room temperature. Subsequently, a predetermined amount of imidazole compound or the like (C-1, C′-1, C′-2, C′-3, and C′-4) was added to the mixture. Then, the mixture of the obtained component (A), component (B), and component (C) or (C ′) is rotated or revolved (Mazerustar (trade name), manufactured by Kurashiki Boseki Co., Ltd.). ), The resin composition was prepared by stirring and mixing for 3 minutes. In Example 11, however, a fused spherical silica filler (MP-15EF manufactured by Tatsumori Co., Ltd., average particle size 1.5 μm) was added to the resin composition as an inorganic filler, and then a bead mill was used. Silica filler was dispersed in the resin composition. A coating liquid containing the resin composition was prepared by adjusting the viscosity of the resin composition thus obtained with toluene.

The components used when creating the resin composition are as follows.
Component (A): Epoxy resin (A-1):
Epoxy resin having naphthalene skeleton, HP4032D (trade name), manufactured by DIC Corporation, epoxy equivalents 136 to 148 (A-2);
An epoxy resin having an anthracene skeleton, JERYX8800 (trade name), manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 (A-3); and
Epoxy resin having biphenyl skeleton, NC-3000H (trade name), manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288

Component (B): Resin having a tan δ of less than 0.005 in the frequency range of 1 to 100 GHz (B-1): Solvent-soluble polyimide resin synthesized by the following procedure: Stirrer, water separator, thermometer, and nitrogen In a reaction vessel equipped with a gas introduction tube, 210.0 g of commercially available aromatic tetracarboxylic dianhydride (BTDT-UP (trade name), manufactured by Evonik Japan Co., Ltd.), 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane. Was charged. The solution in the reaction vessel was heated to 60 ° C. Next, 341.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, manufactured by Croda Japan Co., Ltd.) was dropped into the reaction solution. Then, imidation reaction was performed at 140 degreeC for 10 hours. Thereafter, the solvent was distilled off under reduced pressure and toluene substitution was performed to obtain a solvent-soluble polyimide resin (A-2) solution (nonvolatile content: 30.1%). The number average molecular weight (Mn) by GPC measurement was 15000. The dielectric loss tangent (tan δ) measured by the procedure described later was 0.0029.
(B-2): Solvent-soluble polyimide resin synthesized by the following procedure: In the same reaction vessel as (B-1), commercially available aromatic tetracarboxylic dianhydride (BTDA-PF (trade name), Evonik Japan Co., Ltd.) 190.0 g, cyclohexanone 912.0 g, and methylcyclohexane 182.4 g were charged. The solution in the reaction vessel was heated to 60 ° C. Next, 288.1 g of a commercially available dimer diamine (PRIAMINE 1075 (trade name), manufactured by Croda Japan Co., Ltd.) and 24.7 g of a commercially available silicone diamine (KF-8010 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) Added dropwise to the solution. Then, imidation reaction was performed at 140 degreeC for 10 hours. As a result, a polyimide resin solution (non-volatile content: 30.8%) was obtained. The number average molecular weight (Mn) by GPC measurement was 14000. The dielectric loss tangent (tan δ) measured by the procedure described later was 0.0036.
(B-3): Solvent-soluble polyimide resin synthesized by the following procedure (B-1) In the same reaction vessel, commercially available aromatic tetracarboxylic dianhydride (BisDA1000 (trade name), manufactured by SABIC Japan Co., Ltd.) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged. The solution in the reaction vessel was heated to 60 ° C. Next, 43.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, manufactured by Croda Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane were added dropwise to the reaction solution. Then, imidation reaction was performed at 140 degreeC for 10 hours. As a result, a solvent-soluble polyimide resin (B-1) solution (nonvolatile content: 29.5%) was obtained. The number average molecular weight (Mn) by GPC measurement was 15000. The dielectric loss tangent (tan δ) measured by the procedure described later was 0.0019.
(B-4): Dielectric loss tangent (tan δ) measured by the same procedure as the modified PPE resin represented by the above general formula (1), OPE-2St (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co., Inc. (B-1) ) Was 0.0040.
(B-5): The dielectric loss tangent (tan δ) measured by the same procedure as that of thermoplastic elastomer (SEEPS), Septon 4044 (trade name), manufactured by Kuraray Co., Ltd. (B-1) was 0.0008.

Component (C): Imidazole compound (C-1): Imidazole compound having a structure represented by the following formula, EH-2021 (trade name), manufactured by ADEKA Corporation

(C′-1): 1-benzyl-2-phenylimidazole, 1B2PZ (trade name), manufactured by Shikoku Chemicals Co., Ltd. (C′-2): 2-ethyl-4-methylimidazole, 2E4MZ (trade name), Shikoku Kasei Kogyo Co., Ltd. (C'-3): 1-cyanoethyl-2-undecylimidazole, C11ZCN (trade name), Shikoku Kasei Kogyo Co., Ltd. (C'-4): 2-ethylhexyl acrylate, Nacalai Made by Tesque Corporation

The following evaluation was performed using the coating liquid prepared by the above procedure.
1. PI peel strength The coating liquid was applied on the surface of a 50 μm-thick PET film coated with a release agent using an applicator so that the dried coating film had a thickness of 25 ± 5 μm. The substrate coated with the coating solution was dried at 80 ° C. for 15 minutes. The base material was peeled from the uncured film thus produced. Thereafter, the laminated film obtained by sandwiching the uncured film between two polyimide films (Upilex (registered trademark) 12.5CA, manufactured by Ube Industries, Ltd.) is press-cured with a vacuum press (200 ° C. × 1 MPa for 60 minutes). A test piece was obtained by cutting the obtained laminated film containing a cured film into a width of 10 mm. The peel strength of the cured film was measured by peeling each of the two polyimide films of the test piece from the cured film in the opposite direction to each other by autograph. The average value of the values obtained by the five measurements was calculated as the peak intensity measurement value.
2. Dielectric constant (ε), dissipation factor (tan δ)
1. After the uncured film obtained in the above was cured on the substrate surface for 200 ° C. for 60 minutes, the substrate was peeled from the cured film. Ε and tan δ of the cured film cut to 130 × 70 mm were measured by the SPDR method at a dielectric resonance frequency of 2 GHz. The results are shown in the table below.

In each of Examples 1 to 11, a PI peel strength of 7.0 N / cm or more, a dielectric constant (ε) of 3.0 or less, and a dielectric loss tangent (tan δ) of 0.010 or less were shown. In addition, Example 2 and 3 and Example 1 differ in the mixture ratio of the imidazole compound of (C) component. Examples 4 and 5 are different from Example 1 in the type of component (A) epoxy resin. Examples 6 to 9 and Example 1 differ in the type of resin as component (B). Examples 10 to 11 and Example 1 differ in the blending ratio of component (B) to component (A). Among these, in Example 11, the silica filler is further used. In Comparative Example 1, an imidazole compound having a benzyl group at the 1-position of the heterocyclic ring is used in place of the imidazole compound as the component (C). In Comparative Example 2, there is no alkyl group having 5 or more carbon atoms at the 1-position of the heterocyclic ring of the imidazole compound. In Comparative Example 3, an imidazole compound having a side chain having an alkyl group having 5 or more carbon atoms at the 2-position of the heterocyclic ring is used in place of the imidazole compound of component (C). In Comparative Example 4, a compound corresponding to the thermal decomposition product of the imidazole compound (C-1) used in the examples is blended. Comparative Examples 1 to 4 all showed a PI peel strength of less than 7.0 N / cm and a dielectric loss tangent (tan δ) that exceeded 0.010.
The resin composition according to the embodiment of the present disclosure may be the following first to third resin compositions.
The first resin composition comprises (A) an epoxy resin, (B) a resin having a dielectric loss tangent (tan δ) of less than 0.005 in the region of a frequency of 1 to 100 GHz, and (C) the first position of the heterocyclic ring. Including imidazole compounds in which a side chain having a C5 or higher alkyl group is present.
The second resin composition is the first resin composition in which the (C) imidazole compound is represented by the following formula (I).

(In the formula (I), R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is 0 or 1, and R ⁴ is An alkylene group having 1 to 3 carbon atoms or a group: —CH ₂ CH ₂ COO—, and R ⁵ represents an alkyl group having 5 to 10 carbon atoms.
In the third resin composition, the (B) resin is at least one selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. 1 or 2 resin composition.
The thermosetting film according to the embodiment of the present disclosure may be formed of any one of the first to third resin compositions.
The cured resin according to the embodiment of the present disclosure may be any one of the first to third resin compositions or a cured resin obtained by curing the thermosetting film.
The laminated board which concerns on embodiment of this indication may be a laminated board containing the said resin hardened | cured material.
The printed wiring board according to the embodiment of the present disclosure may be a printed wiring board including the resin cured product.
The semiconductor device according to the embodiment of the present disclosure may be a semiconductor device including the cured resin.

Claims

(A) an epoxy resin;
(B) a resin having a dielectric loss tangent (tan δ) of less than 0.005 in a frequency range of 1 to 100 GHz;
and,
(C) A resin composition comprising an imidazole compound having a side chain having an alkyl group having 5 or more carbon atoms at the 1-position of a heterocyclic ring.
The resin composition of Claim 1 containing the said (C) imidazole compound represented by following formula (I).

(In Formula (I), R 1 , R 2 , and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M is 0 or 1. R 4 Is an alkylene group having 1 to 3 carbon atoms or —CH 2 CH 2 COO—, and R 5 is an alkyl group having 5 to 10 carbon atoms.)
The resin composition according to claim 1 or 2, wherein the (B) resin is at least one selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. .
A thermosetting film formed from the resin composition according to any one of claims 1 to 3.
A cured resin, which is a cured resin composition according to any one of claims 1 to 3 or a thermosetting film according to claim 4.
A laminate comprising the cured resin product according to claim 5.
A printed wiring board containing the cured resin according to claim 5.
A semiconductor device comprising the cured resin product according to claim 5.