JP7286569B2 - Thermosetting resin composition, thermosetting adhesive, thermosetting resin film, and laminate, prepreg, and circuit board using the thermosetting resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition, a thermosetting adhesive, a thermosetting resin film, and a laminate, prepreg, and circuit board using the thermosetting resin composition.

2. Description of the Related Art In recent years, as electronic devices have become smaller and have higher performance, miniaturization and higher density of wiring are required in multilayer printed wiring boards. In the next generation, materials for high-frequency bands will be required, and transmission loss reduction will be essential as a noise countermeasure. ing.

Epoxy resin compositions containing epoxy resins, specific phenolic curing agents, phenoxy resins, rubber particles, polyvinyl acetal resins, etc. disclosed in Patent Documents 1 and 2 are known as insulating materials for multilayer printed wiring boards. However, it has been found that these materials cannot satisfy the high-frequency band applications typified by the keyword 5G. On the other hand, Patent Document 3 reports that an epoxy resin composition containing an epoxy resin, an active ester compound, and a triazine-containing cresol novolac resin is effective in reducing the dielectric loss tangent, but this material is also suitable for high frequency applications. A lower dielectric is required.

On the other hand, Patent Document 4 reports that a resin film composed of a resin composition containing a bismaleimide resin having a long-chain alkyl group as a non-epoxy material and a curing agent is excellent in low dielectric properties. It is a combination of a bismaleimide resin having a substantially long-chain alkyl group and a hard low-molecular-weight aromatic maleimide, and there are problems with compatibility, and uneven properties and curing tend to occur. It is very difficult to achieve a high glass transition temperature (Tg) of

From this point of view, Patent Documents 5 and 6, which use polyphenylene ether, look suitable, but Patent Document 5 uses non-reactive polyphenylene ether, and is easier to handle than thermosetting resins. is also difficult, and there is a high possibility that the adhesiveness will be inferior. Moreover, Patent Document 6 contains a thermoplastic elastomer and is used as a soft adhesive, which is not preferable as a substrate material.
Patent Document 7 exemplifies a resin composition composed of a modified polyphenylene ether containing an unsaturated group at the polymer terminal and an acrylate compound, a methacrylate compound, and a maleimide compound as a crosslinkable curing agent, but the structure of the maleimide compound is unknown. and there is no description of its effect.

JP 2007-254709 A JP 2007-254710 A JP 2011-132507 A Republished publication 2016/114287 JP 2017-002124 A Republished publication 2016/117554 WO2019/065941

Accordingly, an object of the present invention is to provide a thermosetting resin composition having excellent adhesion to metal foils, a high glass transition temperature and low dielectric properties, and adhesives, films, laminates, prepregs and circuit boards using the same. is to provide

In order to solve the above problems, in the present invention,
A thermosetting resin composition,
(A) polyphenylene ether resin having a reactive double bond at the molecular chain end: 100 parts by mass,
(B) (meth) acrylic acid ester compound: 10 to 50 parts by mass,
(C) A cyclic imide compound containing at least two cyclic imide groups in one molecule, which has at least one dimer acid skeleton or at least one linear alkylene group having 6 or more carbon atoms in one molecule or a cyclic imide compound having at least one linear alkenylene group having 6 or more carbon atoms: 30 to 100 parts by mass,
(D) reaction initiator: 0.3 to 10 parts by mass,
(E) Adhesion aid containing an epoxy resin having two or more epoxy groups per molecule: 0.3 to 10 parts by mass.

Such a composition has excellent adhesion to metal foils, has a high glass transition temperature and low dielectric properties, and has excellent compatibility of each component, so there is little unevenness in curing and variation in properties during curing. A curable resin composition can be obtained.

Moreover, in the present invention, the component (D) can contain an organic peroxide.

Such a composition can further improve the effects of the present invention.

（前記式中、Ｒ^１は独立して水素原子、又は炭素数１～６の脂肪族炭化水素基、Ｘは炭素数６～２４の２価の芳香族炭化水素基、ｘは０～２０、ｙは０～２０であり、ｘとｙは両方が同時に０になることはない。） In the present invention, the polyphenylene ether resin of component (A) may have a structure represented by the following general formula (1) and a weight average molecular weight of 500 to 5,000.

(In the above formula, R ¹ is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, X is a divalent aromatic hydrocarbon group having 6 to 24 carbon atoms, x is 0 to 20, y ranges from 0 to 20, and both x and y cannot be 0 at the same time.)

With such a composition, the heat resistance, dielectric properties, and rigidity of the cured product of the resin composition can be enhanced.

（前記式中、Ｒ^１は前記と同様であり、Ｙは単結合、又は炭素数１～１０の直鎖状、炭素数３～１０の分岐鎖状又は環状の２価の脂肪族炭化水素基である。） Moreover, in the present invention, X in the above formula (1) can be selected from divalent aromatic hydrocarbon groups represented by the following formula (2).

(In the above formula, R ¹ is the same as above, Y is a single bond, or a linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. is.)

With such a composition, the heat resistance, dielectric properties, and rigidity of the cured product of the resin composition can be further enhanced.

（式中、ｘ’は０～２０、ｙ’は０～２０であり、両方が同時に０にならない。） Further, in the present invention, the component (A) may be a polyphenylene ether resin represented by the following formula (3).

(In the formula, x' is 0 to 20, y' is 0 to 20, and both are not 0 at the same time.)

With such a composition, the heat resistance, dielectric properties, and rigidity of the cured product of the resin composition can be further enhanced.

In the present invention, the component (B) may have two or more (meth)acrylic groups per molecule, and the (meth)acrylic acid ester compound may have eight or more carbon atoms.

With such a composition, it is possible to obtain effects such as an improvement in the adhesive strength of the resin composition, and it is also possible to improve the flexibility of the uncured resin composition.

（前記式中、Ａは独立して芳香族環又は脂肪族環を含む４価の有機基を示す。Ｂは２価のヘテロ原子を含んでもよい脂肪族環を有する炭素数６～１８のアルキレン基である。Ｑは独立して炭素数６以上の直鎖アルキレン基又は直鎖アルケニレン基を示す。Ｒは独立して炭素数６以上の直鎖又は分岐鎖のアルキル基を示す。ｎは１～１０の数を表す。ｍは０～１０の数を表す。） Further, in the present invention, the cyclic imide compound as the component (C) may have a structure represented by the following general formula (4).

(In the above formula, A independently represents a tetravalent organic group containing an aromatic ring or an aliphatic ring. B is an alkylene having 6 to 18 carbon atoms and an aliphatic ring which may contain a divalent heteroatom. Q is independently a linear alkylene group or alkenylene group having 6 or more carbon atoms, R is independently a linear or branched alkyl group having 6 or more carbon atoms, n is 1 Represents a number of ~10. m represents a number of 0 to 10.)

Such a composition not only has excellent dielectric properties, but can also improve tracking resistance.

（なお、上記構造式中の置換基が結合していない結合手は、前記式（４）において環状イミド構造を形成するカルボニル炭素と結合するものである。） Further, in the present invention, A in the formula (4) can be any one of the following structures.

(Note that the bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon forming the cyclic imide structure in the above formula (4).)

Such a composition not only has better dielectric properties, but can also improve tracking resistance.

Further, in the present invention, in the component (C), the proportion of components having a weight average molecular weight of 1,000 or less can be 5% by mass or more in the component (C).

Such a composition can improve compatibility with components (A) and (B).

Further, in the present invention, a 60% by mass anisole solution of the composition comprising components (A) to (E) can be transparent at 25°C.

With such a composition, unevenness of the cured product is less likely to occur during curing, and the uniformity of product physical properties can be improved.

Moreover, in this invention, an inorganic filler can be further included as (F) component.

With such a composition, the coefficient of thermal expansion of the cured product can be kept small.

Further, in the present invention, the inorganic filler of the component (F) may be treated with a silane coupling agent having an organic group capable of reacting with the component (C).

With such a composition, an effect of adhesion to a substrate and an effect of improving dielectric properties can be obtained.

Also, in the present invention, when cured at 150° C. for 1 hour and further at 180° C. for 2 hours, the glass transition temperature measured by DMA (Dynamic Mechanical Analysis) may be 150° C. or higher.

Such a composition can further improve the effects of the present invention.

Further, in the present invention, an adhesive or a film comprising the thermosetting resin composition, a laminate containing the thermosetting resin composition, a prepreg containing a semi-cured product of the thermosetting resin composition, the thermosetting A circuit board containing a cured product of the flexible resin composition can be obtained.

Such adhesives, films, laminates, prepregs, and circuit boards are thermosetting resin compositions that have excellent adhesion to metal foils, high Tg and low dielectric properties, and excellent compatibility of each component. is used, there is little curing unevenness and characteristic variation during curing.

The thermosetting resin composition of the present invention has excellent adhesion to metal foil, high Tg and low dielectric properties, and excellent compatibility of each component, so that there is no curing unevenness and characteristic variation during curing. few. Therefore, the thermosetting resin composition of the present invention is useful as adhesives, films, laminates, prepregs and circuit boards.

As described above, there has been a demand for the development of a thermosetting resin composition that exhibits excellent adhesion to metal foils, a high Tg, and low dielectric properties.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the following thermosetting resin composition can achieve the above objects, and completed the present invention.

That is, the present invention is a thermosetting resin composition,
(A) polyphenylene ether resin having a reactive double bond at the molecular chain end: 100 parts by mass,
(B) (meth) acrylic acid ester compound: 10 to 50 parts by mass,
(C) A cyclic imide compound containing at least two cyclic imide groups in one molecule, which has at least one dimer acid skeleton or at least one linear alkylene group having 6 or more carbon atoms in one molecule or a cyclic imide compound having at least one linear alkenylene group having 6 or more carbon atoms: 30 to 100 parts by mass,
(D) reaction initiator: 0.3 to 10 parts by mass,
(E) A thermosetting resin composition characterized by containing 0.3 to 10 parts by mass of an adhesion promoter containing an epoxy resin having two or more epoxy groups in one molecule.

Although the present invention will be described in detail below, the present invention is not limited thereto.

(A) Polyphenylene ether resin having a reactive double bond at the molecular chain end Component (A) is a polyphenylene ether resin having a reactive double bond at the molecular chain end. Component (A) is a base resin for the present resin composition, and is used to enhance heat resistance, dielectric properties, and rigidity of the cured product of the resin composition.

（前記式中、Ｒ^１は独立して水素原子、又は炭素数１～６の脂肪族炭化水素基、Ｘは炭素数６～２４の２価の芳香族炭化水素基、ｘは０～２０、ｙは０～２０であり、ｘとｙは両方が同時に０になることはない。） Component (A) preferably has a structure represented by the following general formula (1).

(In the above formula, R ¹ is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, X is a divalent aromatic hydrocarbon group having 6 to 24 carbon atoms, x is 0 to 20, y ranges from 0 to 20, and both x and y cannot be 0 at the same time.)

R ¹ in the above formula (1) is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, but a hydrogen atom and a methyl group are preferred in terms of availability of raw materials.

（前記式中、Ｒ^１は前記と同様であり、Ｙは単結合、又は炭素数１～１０の直鎖状、炭素数３～１０の分岐鎖状又は環状の２価の脂肪族炭化水素基である。） X in the above formula (1) is a divalent aromatic hydrocarbon group having 6 to 24 carbon atoms, preferably a divalent aromatic hydrocarbon group represented by the following formula (2).

(In the above formula, R ¹ is the same as above, Y is a single bond, or a linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. is.)

Y in the formula (2) is a single bond or a linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, branched chain or cyclic hydrocarbon group having 1 to 10 carbon atoms, A single bond, a linear or branched divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms and 3 to 5 carbon atoms is preferred from the viewpoint of ease of bonding and heat resistance.
Specific examples include divalent aromatic hydrocarbon groups having the following structures.

（式中、ｘ’は０～２０、ｙ’は０～２０であり、両方が同時に０にならない。） From the above, it is more preferable that the component (A) is a polyphenylene ether resin represented by the following formula (3).

(In the formula, x' is 0 to 20, y' is 0 to 20, and both are not 0 at the same time.)

The weight average molecular weight (Mw) of the polyphenylene ether resin, which is the component (A), is measured by gel permeation chromatography (GPC) with a polystyrene standard from the viewpoint of handling properties such as stickiness and compatibility with organic solvents and other components. It is preferably 500 to 5,000, more preferably 800 to 3,000, in terms of weight average molecular weight.
The weight-average molecular weight (Mw) referred to in the present invention refers to the weight-average molecular weight measured by GPC under the following conditions using polystyrene as a standard material.
[Measurement condition]
Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min
Detector: RI (differential refractive index detector)
Column: TSK-GEL H type (manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 5 μL

(B) (Meth)acrylic acid ester compound The component (B) of the present invention is a (meth)acrylic acid ester compound, which imparts flexibility to the resin composition before curing, and can be applied to a substrate such as a metal foil. It is a compound that improves the adhesive strength of The (meth)acrylic acid ester compound to be used is not particularly limited, but the number of (meth)acrylic groups in one molecule is preferably 2 or more, more preferably 2 to 4, from the viewpoint of curability and rigidity of the cured product. preferable. (Meth)acrylic acid ester compounds having 8 or more carbon atoms are preferred, and those having 12 to 30 carbon atoms are more preferred. If the number of carbon atoms is 8 or more, effects such as improvement in adhesive strength of the resin composition can be obtained, and the flexibility of the uncured resin composition can also be improved.

As the (meth)acrylic acid ester compound, one that is liquid at room temperature is preferred, and one that does not have an aromatic skeleton is preferably used. Examples of the (meth)acrylic acid ester compounds include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, tricyclodecanedimethanol diacrylate, 9,9-bis[4- (2-hydroxyethoxy)phenyl]fluorene diacrylate, bisphenol A type diacrylate, trimethylolpropane triacrylate, tris(2-acryloxymethyl)isocyanurate, ditrimethylolpropane tetraacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol methacrylate, dipropylene glycol methacrylate, tricyclodecanedimethanol methacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene methacrylate, bisphenol A type dimethacrylate, trimethylolpropane trimethacrylate, tris ( 2-methacryloxymethyl)isocyanurate, ditrimethylolpropane tetramethacrylate and the like.

Component (B) is added in an amount of 10 to 50 parts by mass, preferably 12 to 30 parts by mass, more preferably 15 to 25 parts by mass, per 100 parts by mass of component (A). If the amount is less than 10 parts by mass, it is difficult to produce a cured film, and if it exceeds 50 parts by mass, the dielectric properties deteriorate.

(C) Cyclic imide compound Component (C) is a cyclic imide compound having at least two cyclic imide groups in one molecule and at least one dimer acid skeleton in one molecule, or at least one carbon It is a cyclic imide compound having a linear alkylene group with 6 or more carbon atoms or at least one linear alkenylene group with 6 or more carbon atoms. The straight-chain alkylene group and the straight-chain alkenylene group may have either one or both of them. Since the cyclic imide compound (C) has a straight-chain alkylene group or straight-chain alkenylene group having 6 or more carbon atoms, the cured product of the composition containing this not only has excellent dielectric properties, but also has a phenyl group. The content ratio is lowered, and the tracking resistance is improved. In addition, since the cyclic imide compound of component (C) has a straight-chain alkylene group or a straight-chain alkenylene group, the uncured product and cured product of the composition containing this can be made low in elasticity, and the resin before and after curing Flexibility of the composition can be imparted. Flexibility-imparting agents for resin compositions generally have poor heat resistance, but component (C) has a cyclic imide skeleton with excellent heat resistance, and is therefore effective in solving this problem.
When having a linear alkenylene group, the number of carbon-carbon double bonds in one molecule is preferably 2 to 12, more preferably 2 to 6, and 2 to 4. is more preferred. The number of carbon-carbon double bonds refers to only the double bonds of the linear alkylene group, and does not include the number of double bonds of cyclic imide groups and aromatic rings. When the number of carbon-carbon double bonds is within this range, when the composition of the present invention is made into a thermosetting resin film, the film has excellent flexibility and high strength.

The cyclic imide structure in component (C) may be located anywhere in the molecule, but preferably at the molecular terminal, more preferably both at the molecular terminal and intramolecularly (in the molecular chain). Moreover, the cyclic imide structure may have a carbon-carbon double bond therein, and preferably has a carbon-carbon double bond in the cyclic imide structure at the terminal of the molecule.

式（４）中、Ａは独立して芳香族環又は脂肪族環を含む４価の有機基を示す。Ｂは２価のヘテロ原子を含んでもよい脂肪族環を有する炭素数６から１８のアルキレン基である。Ｑは独立して炭素数６以上の直鎖アルキレン基又は直鎖アルケニレン基を示す。Ｒは独立して炭素数６以上の直鎖又は分岐鎖のアルキル基を示す。ｎは１～１０の数を表す。ｍは０～１０の数を表す。 The cyclic imide compound (C) is preferably a maleimide compound, more preferably a bismaleimide compound represented by the following formula (4).

In formula (4), A independently represents a tetravalent organic group containing an aromatic ring or an aliphatic ring. B is an alkylene group having 6 to 18 carbon atoms and having an aliphatic ring which may contain a divalent heteroatom. Q independently represents a straight-chain alkylene group or straight-chain alkenylene group having 6 or more carbon atoms. Each R independently represents a linear or branched alkyl group having 6 or more carbon atoms. n represents a number from 1 to 10; m represents a number from 0 to 10;

Q in formula (4) is a straight-chain alkylene group or straight-chain alkenylene group, which has 6 or more carbon atoms, preferably 6 or more and 20 or less, more preferably 7 or more and 15 or less. .

Further, R in formula (4) is an alkyl group, which may be a straight-chain alkyl group or a branched alkyl group, and has 6 or more carbon atoms, preferably 6 or more and 12 or less.

（上記構造式中の置換基が結合していない結合手は、式（４）において環状イミド構造を形成するカルボニル炭素と結合するものである。） A in formula (4) represents a tetravalent organic group containing an aromatic ring or an aliphatic ring, and is preferably any of the tetravalent organic groups represented by the following structural formulas.

(The bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in formula (4).)

（上記構造式中の置換基が結合していない結合手は、式（４）において環状イミド構造を形成する窒素原子と結合するものである。） Further, B in formula (4) is an alkylene group having 6 to 18 carbon atoms having an aliphatic ring which may contain a divalent heteroatom, and the alkylene group preferably has 8 to 15 carbon atoms. is. B in formula (4) is preferably any of the alkylene groups having an aliphatic ring represented by the following structural formula.

(The bond to which no substituent is bonded in the above structural formula is bonded to the nitrogen atom forming the cyclic imide structure in formula (4).)

n in formula (4) is a number of 1-10, preferably a number of 2-7. m in formula (4) is a number from 0 to 10, preferably a number from 0 to 7.

The weight-average molecular weight (Mw) of the cyclic imide compound of component (C) is not particularly limited, including the properties at room temperature, but the weight-average molecular weight converted to polystyrene standards by gel permeation chromatography (GPC) measurement is 500. 50,000 is more preferable, and 800 to 40,000 is particularly preferable. If the molecular weight is 500 or more, the resulting composition containing the cyclic imide compound is likely to form a film, and if the molecular weight is 50,000 or less, the resulting composition will have too high a viscosity and flowability will decrease. There is no fear, and moldability such as laminate molding is improved.
In component (C), the proportion of components having a weight average molecular weight of 1,000 or less is preferably 5% by mass or more, more preferably 5 to 20% by mass, in component (C). More preferably, it is up to 6% by mass. It is preferable that component (C) contains 5% by mass or more of a component having a weight average molecular weight of 1,000 or less because compatibility with components (A) and (B) is improved.

As the (C) component cyclic imide compound, one obtained by reacting a corresponding acid anhydride and a diamine by a conventional method may be used, or a commercially available product may be used. Examples of commercially available products include BMI-689, BMI-1500, BMI-2500, BMI-3000, BMI-3000gel, BMI-3000J, and BMI-5000 (manufactured by Designer Molecules Inc.). Further, the cyclic imide compound may be used singly or in combination of multiple kinds.
Component (C) is added in an amount of 30 to 100 parts by mass, preferably 35 to 70 parts by mass, more preferably 40 to 60 parts by mass, per 100 parts by mass of component (A). If the amount is less than 30 parts by mass, it is difficult to produce a cured film, and if it exceeds 100 parts by mass, the glass transition temperature (Tg) is lowered.

(D) Reaction initiator The reaction initiator, component (D), is added to promote the cross-linking reaction of the thermosetting resins, components (A), (B) and (C). The component (D) is not particularly limited as long as it promotes the cross-linking reaction, and examples thereof include radical initiators such as organic peroxides. Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2 ,5-di(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane , n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy Oxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like can be mentioned.

The amount of the reaction initiator to be used is 0.3 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of (A). If it is out of the above range, the cured product of the resin composition of the present invention may be unbalanced in terms of heat resistance, moisture resistance, etc., or may cure very slowly or rapidly during molding.

(E) Adhesion aid The adhesion aid, which is component (E), is added to improve the adhesion of the thermosetting resin composition containing components (A), (B) and (C) to metals and the like. It is something to do. Component (E) is not particularly limited as long as it is an epoxy resin having at least two epoxy groups. , naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, xylylene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin , phosphorus atom-containing epoxy resins, glycidylamine type epoxy resins, isocyanuric skeleton type epoxy resins, and the like.
Any one type of epoxy resin may be used alone, or two or more types may be used in combination.

The blending amount of component (E) is 0.3 to 10 parts by mass, preferably 0.5 to 8 parts by mass, more preferably 1 to 5 parts by mass based on 100 parts by mass of component (A). be. If the amount is less than 0.3 parts by mass, the effect of improving adhesion to metals is not sufficiently obtained, and if it exceeds 10 parts by mass, moisture resistance and dielectric properties are deteriorated.

A 60% by weight anisole solution of the composition comprising components (A) to (E) above is preferably transparent at 25°C. If the anisole solution is transparent, it is clear that the components are uniformly dispersed, and unevenness of the cured product is less likely to occur during curing, improving the uniformity of product physical properties.

In the present invention, "transparent" means that even if there is coloring, there is no undissolved residue or turbidity visually, and the anisole solution of the resin composition is put in a quartz cell, and the direct light transmittance at 740 nm with an optical path length of 1 mm. shall be 50% or more when measured.

In the present invention, in addition to the above components, the following optional components can be blended.

(F) Inorganic filler The inorganic filler, which is the component (F), is added to increase the strength and rigidity of the cured product of the thermosetting resin composition of the present invention and to adjust the coefficient of thermal expansion. can be done. As the inorganic filler of the component (F), those that are usually blended in epoxy resin compositions and silicone resin compositions can be used. For example, silicas such as spherical silica, fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, barium sulfate, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass fiber and glass particles and the like. Furthermore, fluororesin-containing and/or coating fillers and hollow particles are also included for improving dielectric properties.

The average particle size and shape of the component (F) inorganic filler are not particularly limited, but spherical silica having an average particle size of 0.5 to 5 μm is preferably used when forming into a film. The average particle diameter is a value obtained as a mass average value _D50 (or median diameter) in particle size distribution measurement by laser light diffraction method.

Further, the inorganic filler of component (F) is preferably treated with a silane coupling agent having an organic group capable of reacting with the cyclic imide group of component (C). Such silane coupling agents include epoxy group-containing alkoxysilanes, amino group-containing alkoxysilanes, (meth)acrylic group-containing alkoxysilanes, and unsaturated alkyl group-containing alkoxysilanes.

From the viewpoint of reducing the viscosity and thixotropy of the resin composition before curing, improving the mechanical strength and dielectric properties of the cured product, and improving the adhesion to metals such as copper, (meth) acrylic groups are used. and/or an amino group-containing alkoxysilane is preferably used as the silane coupling agent. Specific examples of silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and the like.

The amount of the inorganic filler as component (F) is preferably 30 to 400 parts by mass, particularly preferably 60 to 350 parts by mass, per 100 parts by mass of (A). If it is 30 parts by mass or more, the coefficient of thermal expansion (CTE) of the cured product can be kept small, and sufficient strength can be obtained, which is preferable. Moreover, if it is 400 parts by mass or less, the flexibility as a film is excellent, and appearance defects do not occur.

(G) Silane Coupling Agent Apart from the silane coupling agent used as the surface treatment agent for the inorganic filler as component (F), a silane coupling agent can also be added as component (G). The purpose of this component (G) is to improve the adhesion and dielectric properties of the thermosetting resin composition of the present invention. The type of silane coupling agent used here is not particularly limited, but (meth)acrylic group-containing alkoxysilanes are particularly preferred from the viewpoint of improving adhesion.

The content of component (G) is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 4.0% by mass, based on 100 parts by mass of (A). If the content is 0.1% by mass or more, the effect of adhesion to the substrate and the effect of improving dielectric properties can be sufficiently obtained. Voids and pinholes do not occur when the resin is removed, and bleeding does not occur from the resin surface.

Other Additives The thermosetting resin composition of the present invention may further contain various additives as required. Examples of such additives include epoxy resins, organopolysiloxanes having reactive functional groups such as amino groups and epoxy groups, silicone oils having no functional groups such as dimethylsilicone oil, cyanate resins, etc., in order to improve resin properties. Thermosetting resins, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, light stabilizers, pigments, dyes, etc. may be blended to improve wettability with fillers and adhesion to substrates. , coupling agents other than silane coupling agents such as organotitanium compounds, ion trapping agents to improve electrical properties, and non-halogen compounds such as phosphorus compounds and metal hydrates to impart flame retardancy. A flame retardant or the like may be added. Furthermore, a fluorine-containing material or the like may be blended in order to improve dielectric properties.

Method for Producing Resin Composition Solution (Varnish) The resin composition of the present invention can be dissolved in an organic solvent to form a varnish, which can be applied to a substrate or formed into a film. Here, a method for producing a resin composition solution will be described. The resin composition solution (varnish) of the present invention is prepared by dissolving each component such as components (A), (B), (C), (D) and (E), which are raw materials of the present invention, in an organic solvent. It can be obtained, and may be easily melted by applying heat during melting. Each component of the resin composition may be individually dissolved in an organic solvent and then mixed with a predetermined amount of each solution, or a predetermined amount of each component, which is the raw material of the resin composition, may be mixed in advance. of organic solvent may be added to dissolve. Examples of the dissolution method include a method of mixing each component and an organic solvent in a container equipped with a stirring device and stirring the mixture.

The organic solvent to be used is not particularly limited as long as each component is soluble. Cycloaliphatic ketones can be preferably used. The above solvents may be used alone or in combination of two or more.

Adhesives/Films/Laminates The thermosetting resin composition of the present invention can be used as an adhesive. At this time, the resin composition can be applied, dried and cured, but it can also be used as a film. In the case of forming a film and using it as an adhesive film (bonding film), for example, by laminating it on a substrate to obtain an adhesive film with a substrate, the varnish of the resin composition of the present invention is applied to the substrate and dried. Alternatively, an adhesive film may be prepared in advance on a release film or release paper, and this may be adhered to the base material.
Examples of substrates include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate; various plastic films such as polycarbonate films and polyimide films; Metal foil such as aluminum foil and the like are included. At this time, a laminate obtained by laminating a film on a metal foil is called a metal-clad laminate. The substrate and a protective film (separator) described later may be subjected to surface treatment such as mud treatment and corona treatment. In addition, a mold release treatment may be performed with a mold release agent such as a silicone resin mold release agent, an alkyd resin mold release agent, or a fluororesin mold release agent.
Another method of producing an adhesive film is a method of producing it using an extruder equipped with a T-die. In this manufacturing method, a thermosetting resin composition prepared by melting and mixing each component is used instead of varnish.

Examples of methods for applying the varnish of the resin composition include ordinary coating methods and printing methods. Specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calender coating, dam coating, dip coating , coating such as die coating, intaglio printing such as gravure printing, and printing such as stencil printing such as screen printing can be used.

Although the drying conditions for drying the organic solvent are not particularly limited, it is desirable to adjust the temperature within the range of 60 to 150° C. according to the organic solvent and reaction accelerator used. When the temperature is 60° C. or higher, the solvent is less likely to remain in the adhesive or film, and the applied resin component does not phase-separate or precipitate due to volatilization of the solvent, which is preferable. When the temperature is 150° C. or lower, curing of the resin composition does not proceed and the coating film does not become rough due to a sudden temperature rise, which is preferable. There is no particular limitation on the drying time, but treatment for 1 to 30 minutes is preferable in consideration of practicality. The thickness of the film can be adjusted by adjusting the concentration and coating thickness of the varnish, but the thickness of the resin composition layer of the adhesive film is preferably in the range of 10 to 120 μm. In particular, when the adhesive film is used for a circuit board, which will be described later, the thickness of the resin composition layer of the adhesive film is preferably equal to or greater than the thickness of the conductor layer of the circuit board. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably in the range of 10 to 100 μm. More preferably it is in the range of 80 μm.

A release film or release paper can be laminated as a protective film on the dried adhesive film. Examples of the release film or release paper include those obtained by applying a release agent to the various plastic films that can be used as the base material, pyrene-coated paper, silicone release paper, and the like. The thickness of the separator is preferably 10 to 100 μm in the case of a release film using a plastic film as a base material, and 50 to 200 μm in the case of a release paper using paper as a base material. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. The adhesive film can be wound into a roll and stored.

Prepreg Prepreg includes a semi-cured product of the thermosetting resin composition of the present invention. It can be produced by drying and semi-curing the resin composition.

As the reinforcing substrate, for example, glass cloth, quartz glass, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc., which are commonly used as prepreg substrates, can be used. A cloth can be preferably used.

A method of coating or impregnation includes a hot melt method or a solvent method.
The hot-melt method is a method in which the thermosetting resin composition of the present invention in a molten state is directly applied to a reinforcing substrate using a die coater, or a film-like laminate material prepared by the method described above is laminated on the reinforcing substrate. The method.
The solvent method is a method in which the reinforcing substrate is immersed in the varnish produced by the method described above and then dried.
Further, the prepreg may be prepared by continuously thermally laminating the adhesive films produced by the above-described method from both sides of the reinforcing substrate under heating and pressure conditions. The support and protective film may be the same as those described above for the adhesive film.

The thermosetting resin composition is dried by heating the reinforcing substrate impregnated or coated with the thermosetting resin composition of the present invention, for example, at 60 to 150 ° C. under the conditions of 5 to 60 minutes. , becomes a semi-cured state.

The prepreg of the present invention preferably contains 25 to 75% by mass of the thermosetting resin composition of the present invention with respect to the reinforcing substrate.

Circuit Board/Multilayer Printed Wiring Board The circuit board of the present invention comprises a cured product of the thermosetting resin composition of the present invention. The cured product forms, for example, an insulating layer. Substrates used for circuit boards include, for example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, the circuit board refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. Alternatively, a multilayer printed wiring board having patterned conductor layers (circuits) formed on both sides is also included. The surface of the conductor layer may be previously subjected to roughening treatment such as blackening treatment or copper etching.

As a method of forming an insulating layer on a circuit board, there is a method of applying the varnish prepared by the method described above to the circuit board, drying it, and curing it by heating. Specifically, it is applied using a dispenser and dried at 60 to 150° C. for 0.5 to 2 hours.

Another method of forming an insulating layer on a circuit board includes a method of laminating the film-like laminate material produced by the method described above on one or both sides of the circuit board using a vacuum laminator. When the film-like laminate material has a protective film, after removing the protective film, the film-like laminate material and the circuit board are preheated as necessary, and the film-like laminate material is pressurized and heated. Laminate on circuit board. After lamination, it is preferable to smoothen the laminated film-like laminate material by, for example, hot-pressing the film-like laminate material under normal pressure. The conditions for the smoothing treatment may be the same as the conditions for the thermocompression bonding of the laminate. Smoothing treatment can be performed with a commercially available laminator. The laminating treatment and the smoothing treatment may be performed continuously using the above-mentioned commercially available vacuum laminator.

After the film-like laminate material is laminated on the circuit board, the insulating layer can be formed by cooling to around room temperature, peeling off the support if necessary, and heating and curing the resin composition. The order of peeling off can be appropriately changed. Thereby, an insulating layer can be formed on the circuit board.

Still another method of forming an insulating layer on a circuit board includes a method of laminating the film-like laminate material produced by the above-described method on one side or both sides of the circuit board using a vacuum press. In this method, a general vacuum hot press is used to apply heat and pressure under reduced pressure to heat and cure the resin composition on the circuit board to form an insulating layer.

Moreover, the method of manufacturing a circuit board (multilayer printed wiring board) using the prepreg manufactured by the method mentioned above is also mentioned. It can be produced by laminating one or more prepregs of the present invention on an interior circuit board, sandwiching a metal plate with a release film interposed therebetween, and press-laminating under pressure and heating conditions.

After manufacturing the circuit board, the insulating layer formed on the circuit board is drilled to form via holes and through holes, the surface of the insulating layer is roughened, and plating is formed on the insulating layer. and a conductor layer can be produced. These steps can be performed according to a general method for manufacturing a circuit board or a multilayer printed wiring board.

Thus, the thermosetting resin composition of the present invention is suitably used for rigid type circuit boards (printed wiring boards, etc.).

The conditions for heat-curing these compositions may be appropriately selected according to the type and content of the resin component in the resin composition, preferably 150° C. to 220° C. for 20 to 300 minutes, more preferably It is selected in the range of 160° C. to 210° C. for 30 to 120 minutes. The glass transition temperature (Tg) of this cured product is preferably 150°C or higher, more preferably 160 to 200°C, from the viewpoint of heat resistance. This Tg is based on measurement data by DMA (Dynamic Mechanical Analysis) of a cured product after curing at 150° C. for 1 hour and further at 180° C. for 2 hours.

In addition , the thermosetting resin composition of the present invention can be applied to many things such as semiconductor devices, coverlay films, and electromagnetic wave shielding members.

EXAMPLES The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples.

(A) Polyphenylene ether resin having a reactive double bond at the molecular chain end (A-1): terminal styrene-modified polyphenylene ether resin (OPE-2st-1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 1,200 )

(B) (Meth) acrylic acid ester compound (B-1): bifunctional dicyclopentadiene acrylate (KAYARAD R684, manufactured by Nippon Kayaku Co., Ltd.)

(C) Cyclic imide compound (C-1): Linear alkylene group-containing maleimide compound-1 represented by the following formula (BMI-3000gel, manufactured by Designer Molecules Inc., component with a weight average content of 1,000 or less: about 12% )

(C-2): Linear alkylene group-containing maleimide compound-2 represented by the following formula (BMI-1500, manufactured by Designer Molecules Inc., components having a weight average molecular weight of 1,000 or less: about 20%)

(C-3): Linear alkylene group-containing maleimide compound-3 represented by the following formula (BMI-3000J, manufactured by Designer Molecules Inc., components with a weight average molecular weight of 1,000 or less: about 1%)

(C-4) 4,4'-diphenylmethanebismaleimide (BMI-1000: manufactured by Daiwa Kasei Co., Ltd., for comparative example)

(D) Reaction initiator (D-1) dicumyl peroxide "Percumyl D" (manufactured by NOF Corporation)

(E) Adhesion aid (E-1) BisA type epoxy resin "JER-828" (manufactured by Mitsubishi Chemical Corporation)
(E-2) Dicyclopentadiene type epoxy resin "HP-7200" (manufactured by DIC Corporation)
(E-3) Isocyanuric skeleton type epoxy resin "TEPIC-S" (manufactured by Nissan Chemical Industries, Ltd.)
(E-4) Glycidylamine type epoxy resin "JER-630" (manufactured by Mitsubishi Chemical Corporation)

(F) Inorganic filler (F-1) Methacryl-modified silane coupling agent (KBM-503, Shin-Etsu Chemical Co., Ltd. ( Co., Ltd.) treated product

[Examples 1 to 9, Comparative Examples 1 to 4]
Each component was dissolved and dispersed in anisole according to the formulation (parts by mass) shown in Tables 1 and 2, and the non-volatile content was adjusted to 60% by mass to obtain a varnish of a resin composition. A varnish of the resin composition was applied onto a PET film having a thickness of 38 μm with a roller coater so that the thickness after drying was 50 μm, and dried at 80° C. for 15 minutes to obtain an uncured resin film.

<Varnish Transparency>
Regarding the varnish before film formation, regarding the resin composition that does not contain the inorganic filler of the component (F), there is no undissolved residue or turbidity visually, and a 60% by mass anisole solution of the resin composition is placed in a quartz cell. When the direct light transmittance with an optical path length of 1 mm and 740 nm is measured at 25 ° C. with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Science Co., Ltd.), ○ is 50% or more, and x is not. and Examples 6, 7, 9 and Comparative Example 2, in which component (F) was blended, were not evaluated for this item, so they are indicated as "-" in Tables 1 and 2.

<Film properties>
When the uncured resin film was bent 90 degrees at 25° C., it was visually confirmed whether the film was cracked or broken. A case where no cracks or breakage was observed was evaluated as ◯, and a case where even a small amount of cracks or breakage was observed was evaluated as x.

<Moisture absorption characteristics>
The uncured resin film was cured by step curing at 150° C. for 1 hour and further at 180° C. for 2 hours. Thereafter, the weight change was measured after being stored at 85° C. and 85% RH for one week. Less than 1% was rated as ◯, and 1% or more was rated as x.

<Relative permittivity, dielectric loss tangent>
The uncured resin film was cured by step curing at 150° C. for 1 hour and further at 180° C. for 2 hours. After that, a network analyzer (E5063-2D5 manufactured by Keysight Co., Ltd.) and a stripline (manufactured by Keycom Co., Ltd.) were connected to measure the dielectric constant and dielectric loss tangent of the film at a frequency of 10 GHz.

<Glass transition temperature>
The uncured resin film was cured by step curing at 150° C. for 1 hour and further at 180° C. for 2 hours. After the cured film was sufficiently cooled, it was measured using DMA-800 (manufactured by TA Instruments) to measure Tg.

<Adhesion>
The thermosetting resin composition of the present application is applied to a copper foil of 10 × 10 mm, and after drying, a 2 × 2 mm silicon chip is placed on it, and the resin composition is cured under the above curing conditions. A test piece for adhesion was produced. Using a bond tester DAGE-SERIES-4000PXY (manufactured by DAGE), the test piece was measured for shear adhesive strength at room temperature (25° C.).

The measurement results are shown in Tables 1 and 2 below.

※１：フィルム状硬化物の作製が不可能であったか、又はフィルム状硬化物が出来たとしてもハンドリング上測定が困難であった。

*1: It was impossible to prepare a film-like cured product, or even if a film-like cured product was made, it was difficult to measure due to handling.

From the above results, the thermosetting resin composition of the present invention has excellent adhesion to metal foil, has both a high glass transition temperature and low dielectric properties, and has excellent compatibility of each component. It has an excellent feature that there is little unevenness and characteristic variation.
On the other hand, in Comparative Examples 1 and 2, the adhesion to the metal foil was poor, and in Comparative Examples 3 and 4, it was impossible to prepare a film-like cured product, or even if a film-like cured product was produced, it was difficult to measure due to handling. there were.
From the above results, the usefulness of the thermosetting resin composition of the present invention was confirmed.

In addition, this invention is not limited to the said embodiment. The above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of

Claims (17)

A thermosetting resin composition,
(A) polyphenylene ether resin having a reactive double bond at the molecular chain end: 100 parts by mass,
(B) (meth) acrylic acid ester compound: 10 to 50 parts by mass,
(C) A cyclic imide compound containing at least two cyclic imide groups in one molecule, which has at least one dimer acid skeleton or at least one linear alkylene group having 6 or more carbon atoms in one molecule or a cyclic imide compound having at least one linear alkenylene group having 6 or more carbon atoms: 30 to 100 parts by mass,
(D) reaction initiator: 0.3 to 10 parts by mass,
(E) Adhesion promoter containing an epoxy resin having two or more epoxy groups in one molecule: 0.3 to 10 parts by mass , wherein the (meth)acrylic group of the component (B) is in one molecule 2 or more, and the (meth)acrylic acid ester compound has 8 or more carbon atoms . 2. The thermosetting resin composition according to claim 1, wherein the component (D) contains an organic peroxide. The heat according to claim 1 or claim 2, wherein the polyphenylene ether resin of component (A) has a structure represented by the following general formula (1) and has a weight average molecular weight of 500 to 5,000. A curable resin composition.

(In the above formula, R ¹ is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, X is a divalent aromatic hydrocarbon group having 6 to 24 carbon atoms, x is 0 to 20, y ranges from 0 to 20, and both x and y cannot be 0 at the same time.) 4. The thermosetting resin composition according to claim 3, wherein X in formula (1) is selected from divalent aromatic hydrocarbon groups represented by formula (2) below.

(In the above formula, R ¹ is the same as above, Y is a single bond, or a linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. is.) 5. The thermosetting resin composition according to any one of claims 1 to 4, wherein the component (A) is a polyphenylene ether resin represented by the following formula (3).

(In the formula, x' is 0 to 20, y' is 0 to 20, and both are not 0 at the same time.) 6. The thermosetting resin composition according to any one of claims 1 to 5 , wherein the cyclic imide compound as component (C) has a structure represented by the following general formula (4). .

(In the above formula, A independently represents a tetravalent organic group containing an aromatic ring or an aliphatic ring. B is an alkylene having 6 to 18 carbon atoms and an aliphatic ring which may contain a divalent heteroatom. Q is independently a linear alkylene group or alkenylene group having 6 or more carbon atoms, R is independently a linear or branched alkyl group having 6 or more carbon atoms, n is 1 Represents a number of ~10. m represents a number of 0 to 10.) 7. The thermosetting resin composition according to claim 6 , wherein A in formula (4) is any one of the following structures.

(Note that the bond to which no substituent is bonded in the above structural formula is bonded to the carbonyl carbon forming the cyclic imide structure in the above formula (4).) 8. The component (C) according to any one of claims 1 to 7 , wherein the proportion of components having a weight average molecular weight of 1,000 or less is 5% by mass or more in the component (C). The thermosetting resin composition according to . 9. The thermosetting resin according to any one of claims 1 to 8 , wherein a 60 mass% anisole solution of the composition comprising components (A) to (E) is transparent at 25°C. Composition. 10. The thermosetting resin composition according to any one of claims 1 to 9 , further comprising an inorganic filler as component (F). 11. The thermosetting resin composition according to claim 10 , wherein the inorganic filler of component (F) is treated with a silane coupling agent having an organic group capable of reacting with component (C). thing. 12. The glass transition temperature measured by DMA is 150° C. or higher when cured at 150° C. for 1 hour and further at 180° C. for 2 hours. A thermosetting resin composition. An adhesive comprising the thermosetting resin composition according to any one of claims 1 to 12 . A film comprising the thermosetting resin composition according to any one of claims 1 to 12 . A laminate comprising the thermosetting resin composition according to any one of claims 1 to 12 . A prepreg comprising a semi-cured product of the thermosetting resin composition according to any one of claims 1 to 12 . A circuit board comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 12 .