JP6866647B2 - Resin composition and support with resin layer - Google Patents

Description

The present invention relates to a resin composition and a support with a resin layer.

The speed and capacity of signals used in mobile communication devices such as mobile phones, their base station devices, servers, network infrastructure devices such as routers, and electronic devices such as large computers are increasing year by year. Along with this, the printed wiring boards mounted on these electronic devices need to be compatible with high densities and high frequencies, and low relative permittivity and low dielectric loss tangent substrate materials that can reduce transmission loss are required. ing. In recent years, as applications that handle such high-frequency signals, in addition to the above-mentioned electronic devices, there are wiring boards used for probe cards in supercomputers and IC testers, and these wiring boards also reduce transmission loss and increase the frequency. The demand for response is increasing. Further, in addition to the above, practical application and practical planning of a new system handling high-frequency radio signals are in progress in the ITS field (automobiles, transportation system-related) and the indoor short-range communication field. In the future, it is expected that further low transmission loss substrate materials will be required for printed wiring boards mounted on these applications.

Further, due to concerns about environmental problems in recent years, mounting of electronic components by lead-free solder and materials containing no halogens are required. Therefore, the substrate material is required to have higher heat resistance than before.

A printed wiring board is usually manufactured by arranging copper foil on both sides of a prepreg so that a roughened surface is inside, press-molding, and then forming a circuit by etching. As a result, the formed circuit is secured not only by the chemical adhesive force but also by the anchor effect accompanying the increase in the surface area. However, when the circuit is formed by the above method, the shape of the circuit tends to be non-uniform, which causes deterioration of high frequency characteristics.

On the other hand, a multi-wire wiring board is known as a wiring board having excellent high frequency characteristics. A multi-wire wiring board is manufactured by providing an adhesive layer on a substrate, laying an insulating coated wire for forming a conductor circuit, fixing the wire by lamination or the like, and connecting the layers by through holes. Here, the cloth wire refers to a technique of fixing the wire by applying ultrasonic waves at the same time as the wire is laid on the adhesive layer. The multi-wire wiring board is also known as a wiring board capable of high-density wiring as well as being compatible with high frequencies. Fluorine-based resins or polyamide-imide-based resins are known as resins used for the adhesive layer of the multi-wire wiring board (see, for example, Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2014-241201 Japanese Unexamined Patent Publication No. 2011-1505045 JP-A-2010-245424

Since the multi-wire wiring board is manufactured by laying wires and fixing them on the adhesive layer as described above, the resin composition used for the adhesive layer of the multi-wire wiring board has a woven property (ultra-wire property). (Migration property by ultrasonic waves) is required to be ensured. Further, the resin composition used for the conventional multi-wire wiring board is difficult to secure the stability as a varnish and the film property and flexibility of the resin composition alone, and the wiring board is formed by using the resin composition. There is still room for improvement in terms of film handleability during production.

In view of the current situation, the present invention has excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent) and heat resistance, and also has high levels of wire flow, stability as a varnish, and film handleability. It is an object of the present invention to provide a resin composition to be provided and a support with a resin layer.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by a specific resin composition, and have completed the present invention.

That is, the present invention comprises (A) a compound having a maleimide group, a divalent group having at least two imide bonds, a saturated or unsaturated divalent hydrocarbon group, and (B) a compound having a maleimide group. A resin containing (C) a diaminosiloxane compound, wherein the component (B) is a compound other than the component (A), and the component (C) is a compound other than the components (A) and (B). A composition (hereinafter, referred to as “first resin composition” for convenience) is provided.

According to the first resin composition, it has excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent) and heat resistance, and also has high levels of wirelinability, stability as a varnish, and film handleability. A resin composition can be provided.

Further, the present invention comprises (A) a compound having a maleimide group, a divalent group having at least two imide bonds, a saturated or unsaturated divalent hydrocarbon group, and (B) a compound having a maleimide group. It contains (C) a siloxane-modified polyimide resin which is a reaction product of a diaminosiloxane compound, the component (B) is a compound other than the component (A), and the component (C) is the component (A) and (B). ) A resin composition (hereinafter, referred to as “second resin composition” for convenience) which is a compound other than the component is provided.

According to the second resin composition, it has excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent) and heat resistance, and also has high levels of wirelinability, stability as a varnish, and film handleability. A resin composition can be provided.

In the first and second resin compositions, it is preferable that the divalent group contains a group having two imide groups represented by the following formula (I). By including the component (A) having such a structure, the mechanical strength of the resin film or the like produced from the resin composition can be increased.

［式（Ｉ）中、Ｒ^１は４価の有機基を示す。］

[In formula (I), R ¹ represents a tetravalent organic group. ]

In the first and second resin compositions, the saturated or unsaturated divalent hydrocarbon group preferably contains a group represented by the following formula (II). By including the component (A) having such a structure, high frequency characteristics, heat resistance, linearity, stability as a varnish and film handleability can be more effectively enhanced.

［式（ＩＩ）中、Ｒ^２及びＲ^３は各々独立に炭素数４〜５０のアルキレン基を示し、Ｒ^４は炭素数４〜５０のアルキル基を示し、Ｒ^５は炭素数２〜５０のアルキル基を示す。］

[In formula (II), R ² and R ³ each independently represent an alkylene group having ^{4 to} 50 carbon atoms, R 4 represents an alkyl group having ^{4 to 50 carbon atoms, and R 5} has 2 to 50 carbon atoms. Indicates an alkyl group. ]

In the first and second resin compositions, the component (C) preferably contains a compound represented by the following formula (XV). By containing the component (C) having such a structure, a resin composition excellent in high frequency characteristics, low thermal expansion characteristics, adhesiveness to a conductor, heat resistance and low hygroscopicity can be obtained.

［式（ＸＶ）中、Ｒ^３１及びＲ^３２は各々独立にアルキル基又はアリール基を示し、同一分子中の複数のＲ^３１及びＲ^３２は同一でも異なっていてもよく、Ｒ^３３はアルキレン基を示し、同一分子中の複数のＲ^３３は同一でも異なっていてもよく、ｎは１〜１００の整数を示す。］

[In formula (XV), R ³¹ and R ³² each independently represent an alkyl group or an aryl group, and a plurality of R ³¹ and R ³² in the same molecule may be the same or different, and R ³³ has an alkylene group. As shown, a plurality of R ^33s in the same molecule may be the same or different, and n represents an integer of 1 to 100. ]

The first and second resin compositions preferably further contain (D) an elastomer. By further containing the elastomer, the high frequency characteristics and heat resistance of the resin composition can be further improved, and the mechanical strength, flexibility, and toughness of the resin film or the like produced from the resin composition can be enhanced. ..

The first and second resin compositions preferably further contain the catalyst (E). By further containing the catalyst, curing of the resin composition can be promoted, and high frequency characteristics and film handleability can be further improved.

The present invention provides a support with a resin layer, comprising a support base material and a resin layer containing the first or second resin composition provided on the support base material. Since the support with a resin layer according to the present invention is formed by using each of the resin compositions according to the present invention, the same effect as each resin composition according to the present invention can be obtained.

According to the present invention, a resin composition having excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent) and heat resistance, and also having high levels of wire flow, stability as a varnish, and film handleability. And a support with a resin layer can be provided.

It is a schematic cross-sectional view which shows the support with a resin layer which concerns on this embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, the high frequency region refers to a region of 0.3 GHz to 300 GHz, and particularly refers to a region of 3 GHz to 30 GHz.

[First resin composition]
The first resin composition according to the present embodiment comprises (A) a maleimide group, a compound having a divalent group having at least two imide bonds and a saturated or unsaturated divalent hydrocarbon group, and (B). It contains a compound having a maleimide group and a (C) diaminosiloxane compound.

<(A) Maleimide group, compound having a divalent group having at least two imide bonds and a saturated or unsaturated divalent hydrocarbon group>
The compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group according to the present embodiment may be referred to as "component (A)". The component (A) is, for example, a compound having a maleimide group and a divalent group bonded to the maleimide group, and the divalent group is a saturated or unsaturated divalent hydrocarbon group bonded to the maleimide group and It is a compound containing at least two imide groups other than the maleimide group. Of these, the maleimide group is referred to as "structure (a)", the divalent group bonded to the maleimide group is referred to as "structure (b)", and the saturated or unsaturated divalent hydrocarbon group bonded to the maleimide group is referred to as "structure (b)". At least two imide groups other than "b1)" and the maleimide group may be referred to as "structure (b2)". By using the component (A), a resin composition having high frequency characteristics, linearity and stability as a varnish can be obtained.

The structure (a) is not particularly limited, and is a general maleimide group. The structure (a) is bonded to the structure (b1) of the structure (b) described later, but the bonding position with the structure (b1) in the structure (a) is not limited. Examples of the bonding position with the structure (b1) in the structure (a) include the nitrogen atom of the maleimide group as represented by the following formula (XIV). In the following formula (XIV), (b1) represents the structure (b1).

The structure (b) includes a structure (b1) and a structure (b2). Of these, the structure (b1) is combined with the structure (a).

The saturated or unsaturated divalent hydrocarbon group in the structure (b1) is not particularly limited, and is a saturated or unsaturated divalent linear hydrocarbon group or a saturated or unsaturated divalent branched hydrocarbon. It may be either a group and a saturated or unsaturated divalent cyclic hydrocarbon group. Further, the unsaturated divalent cyclic hydrocarbon group may be an aromatic group. The saturated or unsaturated divalent hydrocarbon group may have 8 to 300, 8 to 250, 8 to 200 or 8 to 100 carbon atoms. The structure (b1) is preferably an alkylene group having branches of 8 to 300, 8 to 250, 8 to 200 or 8 to 100 carbon atoms, and has branches of 10 to 70 carbon atoms. It is more preferably an alkylene group which may be present, and further preferably an alkylene group which may have a branch having 15 to 50 carbon atoms. Since the component (A) has the structure (b1), the flexibility of the resin composition according to the present embodiment is improved, and the handleability (tackiness, cracking, powder removal, etc.) of the film produced from the resin composition is improved. ) And the strength can be increased. Further, the structure having the number of carbon atoms (b1) is preferable because the molecular structure can be easily made three-dimensional and the free volume of the polymer can be increased to reduce the density, that is, the dielectric constant.

The structure (b1) includes, for example, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group, a nonadesilene group, an icosilene group, a henicosilene group, a docosylene group, a tricosylene group, a tetracosylene group, and a penta. Alkylene groups such as cocilene group, hexacocilene group, heptacosylene group, octacosylene group, nonacoxylen group and triacontylene group; arylene group such as benzylene group, phenylene group and naphthylene group; phenylene methylene group, phenylene ethylene group, benzylpropylene group, An arylene alkylene group such as a naphthylene methylene group and a naphthylene ethylene group; an arylene alkylene group such as a phenylenedi methylene group and a phenylenedi ethylene group can be mentioned.

From the viewpoint of more effectively enhancing high frequency characteristics, heat resistance, linearity, stability as a varnish, and film handleability, a group represented by the following formula (II) as the structure (b1) is particularly preferable.

In formula (II), R ² and R ³ each independently represent an alkylene group having 4 to 50 carbon atoms. From the viewpoint of further improvement of flexibility and easiness of synthesis, R ² and R ³ are each independently preferably an alkylene group having 5 to 25 carbon atoms, and preferably an alkylene group having 6 to 10 carbon atoms. More preferably, it is an alkylene group having 7 to 10 carbon atoms.

In formula (II), R ⁴ represents an alkyl group having 4 to 50 carbon atoms. From the viewpoint of further improvement and ease of synthesis of flexibility, it is preferred that R ⁴ is an alkyl group having 5 to 25 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms, the carbon number 7 to It is more preferably 10 alkyl groups.

In formula (II), R ⁵ represents an alkyl group having 2 to 50 carbon atoms. From the viewpoint of further improvement and ease of synthesis of flexibility, it is preferable that R ⁵ is an alkyl group having 3 to 25 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, carbon atoms 5 It is more preferably an alkyl group of 8.

From the viewpoint of more effectively enhancing high frequency characteristics, linearity, stability as a varnish, and film handleability, it is preferable that a plurality of structures (b1) are present in the component (A). In that case, the structures (b1) may be the same or different. For example, it is preferable that 2 to 40 structures (b1) are present in the component (A), more preferably 2 to 20 structures (b1) are present, and 2 to 10 structures (b1) are present. Is even more preferable.

The structure (b2) is not particularly limited, and examples thereof include groups represented by the following formula (I).

In formula (I), R ¹ represents a tetravalent organic group. R ¹ is not particularly limited as long as it is a tetravalent organic group, but for example, from the viewpoint of handleability, it may be a hydrocarbon group having 1 to 100 carbon atoms, or a hydrocarbon group having 2 to 50 carbon atoms. It may be a hydrocarbon group having 4 to 30 carbon atoms.

R ¹ may be substituted and may contain a substituted or unsubstituted siloxane group. Examples of the siloxane group include groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like.

When R ¹ is substituted, the substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, an alkoxy group, a mercapto group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, a substituted heterocyclic group. , Aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, aryloxy group, substituted aryloxy group, halogen atom, haloalkyl group, cyano group, nitro group, nitroso group, amino group, amide group, -C ( O) H, -C (O)-, _{-S-, -S (O) 2-} , -OC (O) -O-, -C (O) -NR ^X , -NR ^X C (O) -N _{^{(R X) 2, -OC (}} O) -N (R X) 2, acyl group, oxyacyl group, a carboxyl group, a carbamate group, a sulfonyl group, a sulfonic amide and sulfuryl group. Here, ^RX represents a hydrogen atom or an alkyl group. One type or two or more types of these substituents can be selected according to the purpose, application and the like.

As R ¹ , for example, a tetravalent residue of an acid anhydride having two or more anhydride rings in one molecule, that is, an acid anhydride group (-CO (= O) OC (=) It is preferably a tetravalent group excluding two O)-). Examples of the acid anhydride include compounds as described below.

From the viewpoint of high frequency characteristics, R ¹ is preferably aromatic, and more preferably a residue obtained by removing two acid anhydride groups from pyromellitic anhydride. That is, the structure (b2) is more preferably a group represented by the following formula (III).

From the viewpoint of high frequency characteristics and compatibility with other resins, particularly high molecular weight thermoplastic elastomer resins, it is preferable that a plurality of structures (b2) are present in the component (A). In that case, the structures (b2) may be the same or different. The number of structures (b2) in the component (A) is preferably 2 to 40, more preferably 2 to 20, and even more preferably 2 to 10.

From the viewpoint of the dielectric property, the structure (b2) may be a group represented by the following formula (IV) or the following formula (V).

The component (A) may be, for example, a compound represented by the following formula (XIII).

In the formula (XIII), R represents a saturated or unsaturated divalent hydrocarbon group, and the saturated or unsaturated divalent hydrocarbon group having the same structure as the above structure (b1) can be used. R ¹ represents the same tetravalent organic group as ^{R 1} in formula (I), n represents an integer of 1 to 10.

As the component (A), a commercially available compound can also be used. Examples of commercially available compounds include products manufactured by Digigner Moleculars Incorporated (DMI), and specifically, BMI-1500, BMI-1700, BMI-3000, BMI-5000, and BMI. -9000 (both are product names) and the like. From the viewpoint of obtaining better high frequency characteristics, it is more preferable to use BMI-3000 as the component (A).

The content of the component (A) in the first resin composition is not particularly limited. The content of the component (A) may be 2% by mass or more, 5% by mass or more, or 10% by mass or more, based on the total mass of the resin composition, 98% by mass or less, 90% by mass or less, 50. It may be mass% or less or 30 mass% or less. From the viewpoint of heat resistance, flame retardancy and film handleability, the content of the component (A) is preferably 2 to 98% by mass, preferably 2 to 90% by mass, based on the total mass of the resin composition. Is more preferable, 5 to 50% by mass is further preferable, and 10 to 30% by mass is particularly preferable.

The molecular weight of the component (A) is not particularly limited. The Mw of the component (A) may be 1000 or more, 1500 or more, or 3000 or more, and may be 30,000 or less, 20000 or less, or 15000 or less. From the viewpoint of solvent solubility, compatibility and film handleability, the weight average molecular weight (Mw) of the component (A) is preferably 1000 to 30,000, more preferably 1500 to 20000, and 3000 to 15000. It is more preferable to have.

The Mw of the component (A) can be measured by a gel permeation chromatography (GPC) method.

The measurement conditions of GPC are as follows.
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolum HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [All manufactured by Tosoh Corporation, product name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Measurement temperature: 40 ° C

(A) The method for producing the component is not limited. The component (A) may be prepared, for example, by reacting an acid anhydride with a diamine to synthesize an amine-terminated compound, and then reacting the amine-terminated compound with the clause maleic anhydride.

Examples of the acid anhydride include polybutadiene-graft-maleic anhydride, polyethylene-graft-maleic anhydride, polyethylene-maleic anhydride alternating copolymer, polymaleic anhydride-1-octadecene alternating copolymer, polypropylene-graft. -Maleic anhydride, poly (styrene-co-maleic anhydride), pyromellitic anhydride, maleic anhydride, succinic anhydride, 1,2,3,4-cyclobutanetetracarboxylic hydride, 1,4,5 , 8-Naphthalenetetracarboxylic hydride, 3,4,9,10-Perylenetetracarboxylic hydride, Bicyclo [2.2.2] Oct-7-en-2,3,5,6-tetra Carboic acid dianhydride, diethylenetriaminepentaacetichydride, ethylenediaminetetraacetichydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetra Carboxyl dianhydride, 4,4'-oxydiphthalix anhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic hydride, 2,2'-bis (3,4-dicarboxy) Phenyl) Hexafluoropropane dianhydride, 4,4'-bisphenol A diphthalic anhydride, 5- (2,5-dioxytetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, ethylene Glycolbis (trimeritic acid anhydride), hydroquinone diphthalic acid anhydride, allylnadic acid anhydride, 2-octen-1-ylsuccinic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic acid Anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,8-naphthalic anhydride, glutaric anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride and tetradecenyl succinate Acid anhydride can be mentioned. One type of these acid anhydrides may be used alone or two or more types may be used in combination depending on the purpose, application and the like. ^{As described above, as R 1} of the above formula (I), a tetravalent organic group derived from the acid anhydride as described above can be used. From the viewpoint of better dielectric properties, the acid anhydride is preferably pyromellitic anhydride.

Examples of the amine include 1,10-diaminodecane, 1,12-diaminododecane, dimerdiamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1, 3-Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomentan, 1,8-diaminooctane, 1,9-diaminononan, 3,3' -Diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, 9,10-diaminophenantrene, 4,4'-diaminooctafluorobiphenyl, 3,5-diaminobenzoic acid, 3,7- Diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2 , 4-cumendiamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1, 4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis (amino-3-chlorophenyl) ethane, bis (4-amino-3,5-dimethylphenyl) ) Methan, bis (4-amino-3,5-diethylphenyl) methane, bis (4-amino-3-ethyldiaminofluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis (4-amino-) 3-Methylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, 4,4'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, 2,2-bis (4- (4-amino)) Phenoxy) phenyl) sulfone, 2,2-bis (4- (3-aminophenoxy) phenyl) sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenylsulfide, 3,4'-oxydianiline , 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (4-ami) Nophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4 , 4'-diamino-3,3'-dimethoxybiphenyl, bisaniline M, bisaniline P, 9,9-bis (4-aminophenyl) fluorene, o-trizine sulfone, methylenebis (anthranic acid), 1,3-bis ( 4-Aminophenoxy) -2,2-dimethylpropane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) Butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3', 5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis ( 4-Aminophenyl) Hexafluoropropane, polyoxyalkylenediamines, 1,3-cyclohexanebis (methylamine), m-xylylene diamine, p-xylylene diamine, bis (4-amino-3-methylcyclohexyl) methane , 1,2-bis (2-aminoethoxy) ethane and 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2,6 ] decane. These may be used alone or in combination of two or more, depending on the purpose, application and the like.

<(B) Compound having maleimide group>
The resin composition of the present embodiment contains (B) a compound having a maleimide group. The compound having a maleimide group (B) according to the present embodiment may be referred to as "component (B)". The compound that can correspond to both the component (A) and the component (B) is attributed to the component (A).

By using the component (A) and the component (B) in combination, the resin composition of the present embodiment can further improve heat resistance and linearity while maintaining good high frequency characteristics. The reason for this is that the cured product obtained from the resin composition containing the component (A) and the component (B) has a structural unit composed of the component (A) having high frequency characteristics and properties for further improving heat resistance and linearity. It is presumed that this is because it contains a polymer having a structural unit composed of the component (B).

The component (B) preferably has a lower coefficient of thermal expansion than the component (A). As the component (B) having a lower coefficient of thermal expansion than the component (A), for example, a compound having a molecular weight smaller than that of the component (A), a compound having more aromatic rings than the component (A), and a main chain (A). ) Compounds shorter than the component and the like can be mentioned.

Such a component (B) is not particularly limited, and may contain a compound having an aromatic group bonded to a maleimide group, an aliphatic group bonded to a maleimide group, or the like, in addition to the maleimide group. From the viewpoint of more effectively reducing the coefficient of thermal expansion, the component (B) preferably contains a maleimide group and a compound having an aromatic group bonded to the maleimide group. Since the aromatic group is rigid and has a low coefficient of thermal expansion, the coefficient of thermal expansion can be further reduced by using a maleimide group and a compound having an aromatic group bonded to the maleimide group. Further, the compound having a maleimide group is preferably a polymaleimide compound having two or more maleimide groups.

Specific examples of the compound having a maleimide group as the component (B) are not particularly limited, but for example, bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, and bis (4-maleimidephenyl) ether. , Bis (4-maleimidephenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide and 2, 2-Bis (4- (4-maleimidephenoxy) phenyl) propane can be mentioned. These may be used alone or in combination of two or more. Among these, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, 3,3-dimethyl-5,5-, from the viewpoint of high reactivity and improvement of high frequency characteristics and lineability. It is preferable to use at least one selected from the group consisting of diethyl-4,4-diphenylmethanebismaleimide and 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane. From the viewpoint of solubility in organic solvents, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, bis (4-maleimidephenyl) methane and 2,2-bis (4- (4) -It is preferable to use at least one selected from the group consisting of maleimide phenoxy) phenyl) propane. From the viewpoint of low cost, it is preferable to use bis (4-maleimidephenyl) methane. From the viewpoint of linearity, it is preferable to use 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane.

From the viewpoint of moldability, the component (B) preferably contains, for example, a polyaminobismaleimide compound represented by the following formula (VI).

In the formula (VI), A ⁴ represents a group represented by the following formula (VII), (VIII), (IX), or (X), and A ⁵ represents a group represented by the following formula (XI). ..

In formula (VII), R ¹⁰ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom.

In formula (VIII), R ¹¹ and R ¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group ^{having 1 to 5 carbon atoms or a halogen atom, and A 6} is an alkylene group or an alkylidene group having 1 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, ketone group, single bond or group represented by the following formula (VIII-1).

In formula (VIII-1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group ^{having 1 to 5 carbon atoms or a halogen atom, and A 7} is an alkylene group having 1 to 5 carbon atoms. Shows an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond.

In formula (IX), i represents an integer of 1-10.

In formula (X), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j represents an integer of 1 to 8.

In formula (XI), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, and A ⁸ is An alkylene group or alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a group represented by the following formula (XI-1) or a group represented by the following formula (XI-2). Indicates a group represented by.

In the formula (XI-1), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁹ is an alkylene group having 1 to 5 carbon atoms. , Isopropylidene group, m-phenylenediisopropylidene group, p-phenylenediisopropylidene group, ether group, sulfide group, sulfonyl group, ketone group or single bond.

In formula (XI-2), R ²¹ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ¹⁰ and A ¹¹ independently represent 1 to 5 carbon atoms, respectively. Shows an alkylene group, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond.

The polyaminobismaleimide compound represented by the above formula (VI) is, for example, a compound having two maleimide groups at the terminal and an aromatic diamine compound having two primary amino groups in the molecule in an organic solvent. Obtained by Michael addition reaction.

The aromatic diamine compound having two primary amino groups in the molecule is not particularly limited, and is, for example, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 2,2. '-Dimethyl-4,4'-diaminobiphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline , 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline and 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene. These may be used alone or in combination of two or more.

From the viewpoint of high solubility in organic solvents, high reaction rate during synthesis, and high heat resistance, 4,4'-diaminodiphenylmethane and 4,4'-diamino-3,3'-dimethyl-diphenylmethane Alternatively, 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene is preferable. These may be used alone or in combination of two or more, depending on the purpose, application and the like.

The organic solvent used in producing the polyaminobismaleimide compound is not particularly limited, and for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl. Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N, N-dimethylformamide, N, Examples thereof include nitrogen-containing compounds such as N-dimethylacetamide and N-methyl-2-pyrrolidone. One of these may be used alone, or two or more thereof may be mixed and used. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide and N, N-dimethylacetamide are preferable from the viewpoint of solubility.

The content of the component (B) in the resin composition is not particularly limited. The content of the component (B) may be 2% by mass or more, 5% by mass or more, or 10% by mass or more, based on the total mass of the resin composition, 98% by mass or less, 90% by mass or less, 50. It may be mass% or less or 30 mass% or less. From the viewpoint of heat resistance, flame retardancy and linearity, the content of the component (B) is preferably 2 to 98% by mass, preferably 2 to 90% by mass, based on the total mass of the resin composition. It is more preferably 5 to 50% by mass, and further preferably 10 to 30% by mass from the viewpoint of film handleability.

The blending ratio of the component (A) and the component (B) in the resin composition is not particularly limited. From the viewpoint of high frequency characteristics and coefficient of thermal expansion, the mass ratio (B) / (A) of the component (A) to the component (B) is preferably 0.1 to 10, and preferably 0.2 to 5. More preferably, it is more preferably 0.3 to 3, and particularly preferably 0.5 to 2.

<(C) Diaminosiloxane compound>
The resin composition of the present embodiment contains (C) a diaminosiloxane compound. The (C) diaminosiloxane compound according to the present embodiment may be referred to as “(C) component”. The compound that can correspond to both the component (A) and the component (C) is attributed to the component (A). In addition, the compound that can correspond to both the component (B) and the component (C) is attributed to the component (B).

The resin composition of the present embodiment has excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent) and heat resistance by further using the component (C) in combination with the component (A) and the component (B). It is possible to obtain a resin composition which is provided with high levels of lineability, stability as a varnish, and film handleability. From the viewpoint of improving the reactivity with the component (A) and the component (B), the component (C) is preferably a diaminosiloxane compound having an aliphatic skeleton.

The diaminosiloxane compound is, for example, a siloxane compound having a primary amino group at both ends. Examples of the siloxane compound having a primary amino group at both ends include a compound having a structure represented by the following formula (XV).

In formula (XV), R ³¹ and R ³² each independently represent an alkyl group or an aryl group, and a plurality of R ³¹ and R ³² in the same molecule may be the same or different. Examples of the alkyl group include a methyl group. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group and a cyano group. R ³³ represents an alkylene group, and a plurality of R ^33s in the same molecule may be the same or different. Examples of the alkylene group include an ethylene group, a propylene group and a butylene group. Although n indicates an integer of 1 to 100, it may be an integer of 1 to 20.

By using the component (C) having such a structure, excellent compatibility of the component (A), the component (B) and the component (D) described later can be ensured.

The component (C) may be, for example, a compound represented by the following formula (XVI).

In formula (XVI), n represents an integer from 1 to 100.

As the component (C), a commercially available compound can also be used. Examples of commercially available compounds include PAM-E (amino group equivalent: 130 g / mol), KF-8010 (amino group equivalent: 430 g / mol), and X-22-161A (amino group equivalent: 800 g / mol). , X-22-161B (amino group equivalent: 1500 g / mol), KF-8012 (amino group equivalent: 2200 g / mol), KF-8008 (amino group equivalent: 5700 g / mol), X-22-9409 (amino group) Equivalent: 700 g / mol, side chain phenyl type), X-22-1660B-3 (amino group equivalent: 2200 g / mol, side chain phenyl type) (above, manufactured by Shinetsu Chemical Co., Ltd., trade name), BY-16- 853U (amino group equivalent: 460 g / mol), BY-16-853 (amino group equivalent: 650 g / mol) and BY-16-853B (amino group equivalent: 2200 g / mol) (all manufactured by Toray Dow Corning Co., Ltd.) Product name). These may be used alone or in combination of two or more. Among these, selected from the group consisting of PAM-E, KF-8010, X-22-161A, X-22-161B, BY-16-853U and BY-16-853 from the viewpoint of reactivity with the maleimide group. It is preferable to use at least one of the above, and from the viewpoint of obtaining even better high frequency characteristics, the group consisting of PAM-E, KF-8010, X-22-161A, BY-16-853U and BY-16-853. It is more preferable to use at least one selected more. On the other hand, from the viewpoint of varnish compatibility, it is preferable to use at least one selected from the group consisting of KF-8010, X-22-161A and BY-16-853.

The content of the component (C) in the resin composition is not particularly limited. The content of the component (C) may be 5% by mass or more, 10% by mass or more, or 20% by mass or more, based on the total mass of the resin composition, and may be 50% by mass or less, 40% by mass or less, or 30% by mass. It may be mass% or less. From the viewpoint of compatibility, heat resistance, adhesiveness and material cost of the resin composition of the present embodiment, the content of the component (C) may be 5 to 50% by mass based on the total mass of the resin composition. It is preferably 10 to 40% by mass, more preferably 20 to 30% by mass.

<(D) Elastomer>
The resin composition of the present embodiment may further contain (D) an elastomer from the viewpoint of obtaining better high frequency characteristics. From the viewpoint of film formability and moisture absorption resistance, the elastomer is preferably a thermoplastic elastomer. The thermoplastic elastomer is composed of a hard segment component and a soft segment component, and generally, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Examples of the thermoplastic elastomer include a saturated thermoplastic elastomer. Examples of the saturated thermoplastic elastomer include chemically modified saturated thermoplastic elastomers and non-modified saturated thermoplastic elastomers. Examples of the elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and derivatives thereof. These may be used alone or in combination of two or more.

As the elastomer, for example, from the viewpoint of obtaining better heat resistance and insulation reliability, it is preferable to use at least one selected from the group consisting of styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, and silicone-based elastomers. From the viewpoint of obtaining even better high-frequency characteristics, it is more preferable to use at least one selected from the group consisting of styrene-based elastomers and olefin-based elastomers.

These elastomers may have a reactive functional group at the end of the molecule or in the chain. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryloyl group, a methacryloyl group, a vinyl group and a maleic anhydride group. Among these reactive functional groups, at least one selected from the group consisting of an epoxy group, an amino group, an acryloyl group, a methacryloyl group, a vinyl group and a maleic anhydride group from the viewpoint of compatibility and linearity of the varnish is selected. It is preferable to have at least one selected from the group consisting of an epoxy group, an amino group and maleic anhydride.

As the elastomer, a commercially available product can be used. Examples of commercially available chemically modified saturated thermoplastic elastomers include Toughtech M1911, M1913 and M1943 (all manufactured by Asahi Kasei Corporation, trade name). On the other hand, examples of the non-denatured saturated thermoplastic elastomer include Tough Tech H1041, H1051, H1043 and H1053 (all manufactured by Asahi Kasei Corporation, trade name).

The content of (D) elastomer in the resin composition is not particularly limited. The content of the component (D) may be 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total mass of the resin composition, and may be 70% by mass or less, 60% by mass or less, or 50% by mass. It may be mass% or less. The content of the component (D) is preferably 10 to 70% by mass based on the total mass of the resin composition, and is 20 to 60% by mass from the viewpoint of obtaining better high frequency characteristics and compatibility with the varnish. It is more preferably%, and further preferably 30 to 50% by mass from the viewpoint of obtaining better linearity.

<(E) catalyst>
The resin composition of the present embodiment may further contain (E) a catalyst, if necessary, in order to accelerate the curing of the components (A) and (B). Examples of the catalyst include peroxides, imidazole compounds, organophosphorus compounds, secondary amines, tertiary amines and quaternary ammonium salts. These may be used alone or in combination of two or more. From the viewpoint of reactivity, it is preferable to use at least one selected from the group consisting of peroxides, imidazole compounds and organophosphorus compounds, and particularly from the viewpoint of good self-polymerization of maleimide groups, peroxidation is performed. It is more preferable to use a substance.

Examples of the peroxide include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di. Examples thereof include (tert-butylperoxy) hexane, 1,4-bis (tert-butylperoxyisopropyl) benzene and tert-butylhydroperoxide.

The content of the catalyst (E) in the resin composition can be appropriately adjusted depending on the type of catalyst or resin, or the application to which the resin composition according to the present embodiment is applied. The content of the component (E) may be 0.1% by mass or more, 0.5% by mass or more, or 0.75% by mass or more, based on the total mass of the resin composition, and is 10% by mass or less. It may be 5% by mass or less or 3% by mass or less. In the case of peroxide, for example, the content of the component (E) is 0.1 to 10% by mass based on the total mass of the resin composition from the viewpoint of obtaining better high frequency characteristics and film handleability. Is more preferable, 0.5 to 5% by mass is more preferable, and 0.75 to 3% by mass is further preferable.

In addition, the first resin composition may further contain any component as shown below, for example.

(Inorganic filler)
The resin composition of the present embodiment may further contain an inorganic filler. By optionally containing an appropriate inorganic filler, the heat resistance, flame retardancy, high elastic modulus and the like of the resin composition can be more effectively improved. The inorganic filler is not particularly limited, but silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, Examples thereof include glass powder such as barium sulfate, aluminum borate, potassium titanate, E glass, T glass, and D glass, or hollow glass beads. These may be used alone or in combination of two or more.

As the inorganic filler, it is preferable to use silica from the viewpoint of more effectively improving high frequency characteristics and heat resistance. Examples of silica include precipitated silica having a high water content produced by a wet method and dry silica produced by a dry method and containing almost no bound water or the like. Examples of the dry silica include crushed silica, fumed silica, molten spherical silica, and the like, depending on the manufacturing method. Among these, it is preferable to use fused spherical silica from the viewpoint of low thermal expansion and high fluidity when filled in a resin.

When an inorganic filler is used, its average particle size is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm. By setting the average particle size to 0.1 μm or more, good fluidity can be maintained when the resin is highly filled, and by setting the average particle size to 10 μm or less, the probability of mixing coarse particles is reduced, which is caused by the coarse particles. The occurrence of defects can be suppressed. Here, the average particle size is the particle size of a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles as 100%. The average particle size can be measured with a particle size distribution measuring device or the like using a laser diffraction / scattering method.

When an inorganic filler is used, the amount used is not particularly limited, but for example, it is preferably 20 to 300 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the solid content in the resin composition. preferable. When the content of the inorganic filler in the resin composition is within the above range, good heat resistance and moldability can be easily obtained.

When an inorganic filler is used, a coupling agent can be used in combination as needed for the purpose of improving the dispersibility of the inorganic filler and the adhesion with the organic component. Such a coupling agent is not particularly limited, and for example, a titanate coupling agent and various silane coupling agents can be used. These may be used alone or in combination of two or more. The amount of the coupling agent used is also not particularly limited, and may be 0.1 to 5 parts by mass or 0.5 to 3 parts by mass with respect to 100 parts by mass of the inorganic filler used. Within this range, there is little deterioration of various properties, and it becomes easy to effectively exhibit the features of the use of the inorganic filler.

When a coupling agent is used, a so-called integral blend treatment method may be used in which the inorganic filler is mixed in the resin composition and then the coupling agent is added. However, the coupling agent is added to the inorganic filler in advance. A method using a dry or wet surface-treated inorganic filler is preferable. By using this method, the features of the above-mentioned inorganic filler can be exhibited more effectively. When the coupling agent is added by the integral blend treatment method, the coupling agent to be used shall be a coupling agent other than the above component (C), and the surface of the coupling agent may be treated with the coupling agent in advance. When a filler is used, a coupling agent corresponding to the above component (C) can also be used.

(Organic filler)
The resin composition of the present embodiment may further contain an organic filler. Examples of the organic filler include a resin filler having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin and the like, an acrylic acid ester resin, a methacrylic acid ester resin, and a conjugated diene resin. A resin filler having a core-shell structure having a rubber-like core layer made of, etc., and a glass-like shell layer made of acrylic acid ester-based resin, methacrylic acid ester-based resin, aromatic vinyl-based resin, vinyl cyanide-based resin, etc. Can be mentioned. In addition, polyethylene, polypropylene, polystyrene, polyphenylene ether resin and silicone resin can also be used as a thermoplastic resin.

(Flame retardants)
The resin composition of the present embodiment may further contain a flame retardant. The flame retardant is not particularly limited, but includes halogen-containing flame retardants such as brominated flame retardants and chlorine flame retardants, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, red phosphorus and the like. Examples include phosphorus-based flame retardants, nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide. .. One type of these flame retardants may be used alone, or two or more types may be used in combination.

(UV absorber)
The resin composition of the present embodiment may further contain an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and examples thereof include a benzotriazole-based ultraviolet absorber.

(Antioxidant)
The resin composition according to this embodiment may further contain an antioxidant. The antioxidant is not particularly limited, and examples thereof include a hindered phenol-based antioxidant and a hindered amine-based antioxidant.

(Photopolymerization initiator)
The resin composition according to the present embodiment may further contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and examples thereof include a benzophenone-based photopolymerization initiator, a benzylketal-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator.

(Optical brightener)
The resin composition according to the present embodiment may further contain a fluorescent whitening agent. The fluorescent whitening agent is not particularly limited, and examples thereof include a stilbene derivative.

In the resin composition according to the present embodiment, each of the above components is dissolved or uniformly dispersed in an organic solvent from the viewpoint of facilitating handling by diluting and facilitating the production of a support with a resin layer described later. It is preferably in the state of a varnish. The means for preparing the varnish, the conditions and the like are not particularly limited. For example, after sufficiently uniformly stirring and mixing each main component in a predetermined blending amount with a mixer or the like, kneading is performed using a mixing roll, an extruder, a kneader, a roll, an extruder or the like, and the obtained kneaded product is further cooled. And a method of crushing. The kneading format is also not particularly limited.

The organic solvent used for producing the varnish is not particularly limited, and for example, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, an alcohol solvent such as methyl cellosolve, an ether solvent such as tetrahydrofuran and toluene, Examples thereof include aromatic solvents such as xylene and mesitylen. One of these may be used alone, or two or more thereof may be used in combination. From the viewpoint of solubility of the resin composition, ketone solvents such as methyl isobutyl ketone and cyclohexanone and aromatic solvents such as toluene and mesitylene are preferable, and since they are easily volatilized during coating, residual dissolution is unlikely to remain and they are highly versatile. In that respect, methyl isobutyl ketone and toluene are particularly preferred.

The amount of the organic solvent used is preferably, for example, such that the solid content of the resin composition in the varnish is 30 to 90% by mass, and from the viewpoint of maintaining good handleability and coatability of the varnish. , 40 to 50% by mass, more preferably used.

[Second resin composition]
The second resin composition according to the present embodiment includes (A) a maleimide group, a compound having a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group, and (B). It contains a siloxane-modified polyimide resin which is a reaction product of a compound having a maleimide group and a (C) diaminosiloxane compound.

That is, in the second resin composition, the above-mentioned components (A), (B) and (C) are reacted in advance to prepare a siloxane-modified polyimide resin, and the obtained reaction product, the siloxane-modified polyimide resin, is produced. It is obtained by preparing a resin composition using the resin composition. By using the siloxane-modified polyimide resin obtained by reacting the components (A), (B) and (C) in advance in this way, the molecular weight of the siloxane-modified polyimide resin can be adjusted to a desired value. , The compatibility of varnish (stability as varnish) can be further improved.

The components (A), (B) and (C) in the second resin composition are the same as the respective components in the first resin composition, and redundant description will be omitted here.

The method for producing the siloxane-modified polyimide resin by reacting the component (A), the component (B) and the component (C) in advance is not particularly limited, but can be optionally carried out in the presence of a reaction catalyst. .. Examples of the reaction catalyst include amine compounds such as triethylamine, pyridine and tributylamine, imidazole compounds such as methylimidazole and phenylimidazole, phosphorus compounds such as triphenylphosphine and alkalis such as lithium amide, sodium amide and potassium amide. Metal amides can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.

The amount of the component (A), the component (B) and the component (C) charged in producing the siloxane-modified polyimide resin is not particularly limited. For example, the total number of moles of the component (A) and the component (B) with respect to the number of moles of the component (C) in the resin composition is preferably 0.5 to 10 in terms of molar ratio, and is 1.5 to 6 It is more preferably 0.0, and even more preferably 2.5 to 5.0.

The molecular weight of the obtained siloxane-modified polyimide resin can be appropriately adjusted depending on the type of resin or the application to which the resin composition according to this embodiment is applied. For example, from the viewpoint of heat resistance and compatibility with varnish, the weight average molecular weight (Mw) of the siloxane-modified polyimide resin is preferably 5000 to 100,000, more preferably 7500 to 50000, and preferably 1000 to 30000. Is more preferable, and 1500 to 25000 is particularly preferable.

The Mw of the siloxane-modified polyimide resin can be confirmed by a gel permeation chromatography (GPC) method by sampling at regular intervals after the start of the reaction.

The content of the siloxane-modified polyimide resin in the second resin composition is not particularly limited, but is 10 to 99% by mass, 20 to 90% by mass, 30 to 70% by mass, or 40 based on the total mass of the resin composition. It may be ~ 50% by mass.

In addition to the above-mentioned siloxane-modified polyimide resin, the second resin composition includes (D) elastomer, (E) catalyst, inorganic filler, organic filler, flame retardant, ultraviolet absorber, and antioxidant, if necessary. , Photopolymerization initiator, fluorescent whitening agent and the like can be further contained. These arbitrary components are the same as each component in the first resin composition, and redundant description will be omitted here.

Further, in the second resin composition, each of the above components is dissolved or uniformly dispersed in the organic solvent from the viewpoint of facilitating handling by diluting and facilitating the production of a support with a resin layer described later. It is preferably in the state of a varnish. The means for preparing the varnish, the conditions, the organic solvent used for producing the varnish, and the like are the same as those in the first resin composition, and redundant description will be omitted.

The relative permittivity (Dk) of the cured product of the first and second resin compositions of the present embodiment is not particularly limited, but the Dk at 10 GHz is 3.6 or less from the viewpoint of being preferably used in the high frequency band. Is preferable, 3.1 or less is more preferable, and 3.0 or less is further preferable. The lower limit of Dk is not particularly limited, but may be, for example, about 1.0. Further, from the viewpoint of suitable use in the high frequency band, the dielectric loss tangent (Df) of the cured products of the first and second resin compositions of the present embodiment is preferably 0.004 or less, preferably 0.003 or less. More preferably. The lower limit of Df is not particularly limited and may be, for example, about 0.0001. Dk and Df can be measured by the method shown in Examples described later.

The coefficient of thermal expansion (CTE) of the first and second resin compositions of the present embodiment is not particularly limited, but is preferably, for example, 150 ppm / ° C. or lower, more preferably 130 ppm / ° C. or lower, and 110 ppm. It is more preferably / ° C. or lower, and particularly preferably 90 ppm / ° C. or lower. The lower limit of CTE is not particularly limited, but may be, for example, 10 ppm / ° C. or higher. CTE can be measured according to IPC-TM-650 2.4.24.

The glass transition temperature (Tg) of the first and second resin compositions of the present embodiment is not particularly limited, but is preferably 120 ° C. or higher, more preferably 170 ° C. or higher, and 250 ° C. or higher, for example. Is more preferable. The upper limit of Tg is not particularly limited, but may be, for example, 300 ° C. or lower. Tg can be measured by the method shown in Examples described later.

[Support with resin layer]
The support with a resin layer according to the present embodiment includes a support base material and a resin layer containing the first and / or second resin compositions provided on the support base material. FIG. 1 is a schematic cross-sectional view showing a support with a resin layer according to the present embodiment. As shown in FIG. 1, the support 10 with a resin layer comprises a support base material 1 and a resin layer 2 containing the first and / or second resin composition provided on the support base material 1. Be prepared. The resin layer refers to a film-like, uncured or semi-cured (B-staged) resin composition, and is also referred to as a resin film.

The method for producing the support with the resin layer is not limited, and for example, it can be obtained by applying the resin composition on the support base material and drying the formed resin layer. Specifically, the resin composition or a varnish containing the resin composition is applied onto a supporting base material using a coating machine such as a kiss coater, a roll coater, a comma coater, a die coater, or a bar coater, and then a heating and drying furnace. The organic solvent may be volatilized by heating and drying at a medium level. This makes it possible to obtain a support with a resin layer in a state where the resin layer is semi-cured. The coating machine can be appropriately selected depending on the desired thickness of the resin layer.

The semi-cured state is preferably a state in which the adhesive force between the resin composition and the circuit pattern substrate or the like is ensured when the resin composition is cured. Further, in the multi-wire wiring board, it is preferable that good migration is ensured by ultrasonic waves between the wire and the resin layer.

The drying conditions can be, for example, a condition in which the content of the organic solvent in the resin layer after drying is 10% by mass or less, preferably 5% by mass or less. The drying conditions vary depending on the amount of the organic solvent in the varnish, the boiling point of the organic solvent, etc., but for example, by drying the varnish containing 20 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 20 minutes. A resin layer can be formed. Further, as the drying conditions, it is preferable to appropriately set suitable conditions by a simple experiment in advance.

The thickness of the resin layer in the support with the resin layer varies depending on the application, but for example, for a wiring board, it is usually preferable that the thickness of the conductor layer and the diameter of the wire of the circuit board or more are equal to or larger. The thickness of the conductor layer is, for example, 3 to 70 μm, and is preferably 5 to 50 μm, more preferably 5 to 30 μm, from the viewpoint of lightness, thinness, shortness, and miniaturization of the multilayer printed wiring board. Therefore, the thickness of the resin layer can be, for example, 5 μm or more, and for example, the thickness of the conductor layer or more is set in the range of 80 μm or less, preferably 60 μm or less, more preferably 40 μm or less. You can choose.

On the other hand, regarding the multi-wire wiring board, for example, when the wire diameter used is 65 to 100 μm, the thickness of the resin layer can be 50 μm or more, and from the viewpoint of ensuring wire embedding property, the resin layer The thickness is preferably 70 to 120 μm.

In the support with a resin layer according to the present embodiment, for example, two supports with a resin layer having the same or different thickness are bonded to each other by using a method such as hot roll laminating to form one resin. It can also be a layered support.

The supporting base material is not particularly limited, but for example, polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyvinyl chloride; polycarbonate; polyimide; mold release paper; metals such as copper foil and aluminum foil. Foil is mentioned. These supporting base materials and the protective film described later may be subjected to a matte treatment, a corona treatment, a mold release treatment, or the like.

The thickness of the supporting base material is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm, for example.

In the support with a resin layer, a protective film similar to the support base material can be further provided on the surface of the resin layer opposite to the support base material. By providing the protective film, it is possible to prevent foreign matter from entering the resin layer. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. The support with a resin layer can be wound and stored in a roll shape, for example.

The semi-cured resin layer is further heated in a heating furnace at a temperature of, for example, 170 to 250 ° C., preferably 185 to 230 ° C. for 60 to 150 minutes to thermally cure the resin layer and cure the resin. Layers can be obtained.

According to the resin composition and the support with a resin layer according to the present embodiment, it has excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent) and heat resistance, and also has wirelinability, stability as a varnish, and a film. It can be provided with a high level of handleability.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.

[Siloxane-modified polyimide resin]
The siloxane-modified polyimide resin was synthesized according to the following procedure. In a flask, 50 parts by mass of BMI-3000 [Mw: about 3000, Mn: about 4500, manufactured by Digigner Moleculars Incorporated (DMI), trade name] as a component (A), and BMI- as a component (B). 4000 [2,2-bis (4- (4-maleimidephenoxy) phenyl) propane by 50 parts by mass, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name], and (C) component KF-8010 [primary amino at both ends] A siloxane compound having a group, manufactured by Shinetsu Silicone Co., Ltd., trade name] was added in an amount of 2.5 parts by mass and toluene to prepare a toluene solution having a solid content of 30% by mass. The obtained toluene solution was heated in an oil bath at 130 ° C., and the time at which reflux started (the time when the internal temperature was around 113 ° C.) was defined as the reaction start time. After the start of the reaction, sampling was performed every hour, the Mw of the sampled reaction product was confirmed by GPC, and the reaction was terminated when the Mw did not increase.

The measurement conditions of GPC are as follows.
Pump: 880-PV [Manufactured by JASCO Corporation, trade name]
Degassa: DG-1110 [manufactured by Uniflows Co., Ltd., product name]
Autosampler: AS-8020 [manufactured by Tosoh Corporation, product name]
Constant temperature bath: 860-CO [manufactured by JASCO Corporation, product name]
UV detector: 870-UV [manufactured by JASCO Corporation, trade name]
Eluent: tetrahydrofuran Flow rate: 0.5 μL / min Pressure: 40 kg / cm ²
Measurement temperature: 40 ° C
Standard material for calibration curve: TSK standard polystyrene [Product name, manufactured by Tosoh Corporation]

The presumed structure of the BMI-3000 is as shown in the following formula (XII-3). In formula (XII-3), n represents an integer of 1-10.

[Diamine-modified polyimide resin]
The diamine-modified polyimide resin was synthesized according to the following procedure. In a flask, 50 parts by mass of BMI-3000 as the component (A), 50 parts by mass of BMI-1000 [bis (4-maleimidephenyl) methane, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name] as the component (B), trimethyl. Add 2.5 parts by mass of hexamethylenediamine (mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine) and toluene to make a toluene solution with a solid content of 30% by mass. Prepared. The obtained toluene solution was heated in an oil bath at 130 ° C., and the time at which reflux started (the time when the internal temperature was around 113 ° C.) was defined as the reaction start time. After the start of the reaction, sampling was performed every hour, the Mw of the sampled reaction product was confirmed by GPC, and the reaction was terminated when the Mw did not increase. The Mw of the obtained diamine-modified polyimide resin was 3000.

[Resin composition (varnish)]
Various resin compositions were prepared according to the following procedure. The amounts of the raw materials used for preparing the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5 are collectively shown in Tables 1 and 2. Each numerical value shown in Table 1 and Table 2 indicates a mass part.

Each component shown in Table 1 or Table 2 was mixed at 25 ° C. for 30 minutes or more, and then filtered through a # 200 nylon mesh (opening 75 μm) to obtain a resin composition (varnish).

Elastomers include Toughtec M1911 [Chemically modified saturated thermoplastic elastomer, manufactured by Asahi Kasei Co., Ltd., trade name], Toughtech M1943 [Chemically modified saturated thermoplastic elastomer, manufactured by Asahi Kasei Co., Ltd., trade name] or Toughtech H1041 [Non-modified saturated] Mold thermoplastic elastomer, manufactured by Asahi Kasei Co., Ltd., trade name] was used. As the inorganic filler, SC-2050KNK [spherical fused silica, surface treatment: phenylaminosilane coupling agent (1% by mass / total solid content in slurry), dispersion medium: methyl isobutyl ketone (MIBK), solid content concentration: 70 Mass%, average particle size: 0.5 μm, density: 2.2 g / cm ³ , manufactured by Admatex Co., Ltd., trade name] was used. As the catalyst, perhexine 25B [2,5-dimethyl-2,5-di (t-butylperoxy) hexane, manufactured by NOF CORPORATION, trade name] was used.

<Characteristic evaluation of resin composition (varnish)>
(Varnish compatibility)
With respect to the varnishes obtained in Examples and Comparative Examples, the separation and / or precipitation of the resin was visually confirmed. The compatibility of the varnish was evaluated based on the following criteria.
A: No separation / precipitation was observed for 7 days or more from the preparation of the varnish.
B: Resin precipitation was observed 4 days after the preparation of the varnish.
C: Resin precipitation was observed 2 days after the preparation of the varnish.
D: Resin precipitation was observed on the day of preparation of the varnish.

[Support with resin layer]
The resin compositions (crocodile) obtained in Examples and Comparative Examples were released as a supporting base material using a desktop coater (automatic coating device PI-1210, manufactured by Tester Sangyo Co., Ltd., trade name). Apply on a PET film (thickness: 38 μm, NR-1, manufactured by Teijin DuPont Film Co., Ltd., trade name) at a coating speed of 50 mm / sec, dry at 130 ° C. for 10 minutes, and half on the PET film. A support with a resin layer having a cured resin layer was produced. The coating thickness is adjusted using an applicator (YBA type baker applicator, manufactured by Yoshimitsu Seiki Co., Ltd., trade name) so that the thickness of the resin layer of the support with the resin layer after drying is 50 ± 5 μm. did.

<Characteristic evaluation of support with resin layer>
(Flexibility)
The flexibility of the support with the resin layer produced above was evaluated based on the following criteria. If the evaluation result is "A", it is judged that the flexibility is good.
A: It was confirmed that there was no crack or peeling even when bent, and the original state was restored.
B: Cracks or peeling were observed when bent.

(Independent film property)
When the resin layer in the support with the resin layer produced above was peeled off from the PET film as the supporting base material, it was visually evaluated whether or not the resin layer alone had film properties. The film property of the film alone was evaluated based on the following criteria. If the evaluation result is "A", it is judged that the film property by itself is good.
A: No cracking or tearing of the film was observed when peeled from the supporting base material.
B: When peeled from the supporting base material, cracking or tearing of the film was observed.

(Linearity)
The sample for linearity evaluation was prepared as follows.
After preparing two supports with the above resin layers and stacking them so that the resin layers are in contact with each other, the resin layers are pasted together using a clean room hot roll laminator (ML-600D, manufactured by MCK Co., Ltd., trade name). I matched it. Next, on a base material (I-671, manufactured by Hitachi Kasei Co., Ltd., trade name) that has been previously dried in a dryer (clean oven CSO-H005, manufactured by Kusumoto Kasei Co., Ltd., product name) at 130 ° C. for 30 minutes. A support with a resin layer from which one of the PET films was peeled off was laminated so that the peeled surface of the PET film was in contact with the base material, and hot roll laminating was performed again to obtain a sample for evaluation of fabricity. The thickness of the resin layer in the sample was 100 μm. The laminating conditions were all performed at a temperature of 110 ± 5 ° C., a pressure of 3.0 ± 0.5 kg / cm ² , and a speed of 0.3 m / min.

Subsequently, the PET film was peeled off from the obtained sample for evaluating the wire property, and a wire (φ100 μm) was laid on the exposed resin layer surface while performing ultrasonic output (frequency: 25 kHz) using a cloth machine. And formed a wire pattern. In this wire, an insulating layer (fluororesin) and an adhesive layer (epoxy adhesive) are coated on the outer peripheral side surface of a copper core wire in this order.

The wire lineability was evaluated by observing each of the 30 wire patterns using an optical microscope (digital microscope VHX-1000, manufactured by KEYENCE CORPORATION, trade name) and measuring the number of wire peelings.

(Dielectric characteristics: relative permittivity Dk and dielectric loss tangent Df)
Low profile copper foil with a thickness of 18 μm (F3-WS, M surface Rz: 3 μm, Furukawa Electric Co., Ltd.) having a roughened surface (M surface) and a non-roughened surface (shiny surface) opposite to the M surface. Made, product name) was prepared. Subsequently, the PET film was peeled off from the above-mentioned support with a resin layer, two obtained semi-cured resin films were laminated, and then the above-mentioned copper foil was arranged so that its non-roughened surface was in contact with each other at 180 ° C./. A double-sided metal-clad cured resin film (thickness: 0.3 mm) was produced by heat-press molding under press conditions of 2.0 MPa / 120 minutes. Press molding is a 105t high temperature vacuum press manufactured by Meiki Co., Ltd. (main body: MHPCV-610-610-3S-105, manufactured by Meiki Co., Ltd., product name, heat medium heating and cooling device: MH-66ES, Maeda Co., Ltd.) This was done using the ironworks, trade name).

The dielectric properties were measured by the cavity resonator perturbation method using the obtained outer layer copper foil of the double-sided metal-clad cured resin film as a test piece, which was cut into a length of 60 mm, a width of 2 mm, and a thickness of 0.3 mm. A vector network analyzer E8364B manufactured by Agilent Technologies was used as the measuring instrument, CP531 (10 GHz band resonator) manufactured by Kanto Denshi Applied Development Co., Ltd. was used as the cavity resonator, and CPMA-V2 was used as the measurement program. The conditions were a frequency of 10 GHz and a measurement temperature of 25 ° C.

(Heat-resistant)
The coefficient of thermal expansion (CTE) is determined by the thermomechanical analyzer TMA (manufactured by TA Instruments), which uses a test piece obtained by etching the copper foil on both sides of the double-sided metal-clad cured resin film produced above and cutting it into 5 mm squares. , Q400), and the measurement was performed in accordance with the IPC standard (IPC-TM-650 2.4.24). Measurements ^are carried out in the temperature range of twenty to two hundred and sixty ° C. The 1 st the run at a heating rate of 10 ° C. / ^min, at a temperature range of twenty to three hundred and two ° C. The 2 nd the run increased at a rate of temperature increase of 10 ° C. / min It was.

Further, for the test piece for CTE measurement, a dynamic viscoelasticity measuring device DVE (manufactured by UBM Co., Ltd., trade name) is used under the conditions of a chuck distance of 20 mm, a basic frequency of 10 Hz, and a temperature rise rate of 5 ° C./min. The dynamic viscoelasticity from 40 to 360 ° C. was measured, and the value of the peak temperature of tan δ in the obtained viscoelasticity curve was defined as the glass transition temperature (Tg).

The results of each of the above characteristic evaluations are shown in Tables 3 and 4.

＊１：ワイヤ剥がれが多数確認された。

* 1: Many wire peelings were confirmed.

As is clear from the results shown in Table 3, it was confirmed that the resin compositions of Examples 1 to 9 were excellent in compatibility with the varnish and excellent in stability as the varnish. Further, the support with a resin layer produced by using the resin compositions of Examples 1 to 9 is excellent in film properties (flexibility, film property by itself, wire property), and further, Example 1 It was confirmed that the cured products of the resin compositions of ~ 9 were excellent in both dielectric properties (relative permittivity, dielectric loss tangent) and heat resistance (thermal expansion coefficient, glass transition temperature).

On the other hand, as is clear from the results shown in Table 4, the support with a resin layer and the cured product produced by using the resin composition of Comparative Example 1 have the same film properties and dielectric properties as those of Examples. It was inferior to the resin composition. Further, the resin compositions of Comparative Examples 2 to 5 have poor stability as a varnish, and the support with a resin layer and the cured product produced by using the resin composition have both film characteristics and cured product characteristics. Was also inferior to the resin composition of Examples.

1 ... Support base material, 2 ... Resin layer, 10 ... Support with resin layer.

Claims (6)

(A) A compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group,
(B) A compound having a maleimide group and
(C) Containing a siloxane-modified polyimide resin which is a reaction product of a diaminosiloxane compound,
The component (B), wherein (A) is a compound other than the component, the component (C), component (A) and compound der other than the component (B) is,
A resin composition in which the component (C) contains a compound represented by the following formula (XV).

[In formula (XV), R ³¹ and R ³² each independently represent an alkyl group or an aryl group, and a plurality of R ³¹ and R ³² in the same molecule may be the same or different, and R ³³ has an alkylene group. As shown, a plurality of R ^33s in the same molecule may be the same or different, and n represents an integer of 1 to 100. ] The resin composition according to claim 1 , wherein the divalent group contains a group having two imide groups represented by the following formula (I).

[In formula (I), R ¹ represents a tetravalent organic group. ] The resin composition according to claim 1 or 2 , wherein the saturated or unsaturated divalent hydrocarbon group contains a group represented by the following formula (II).

[In formula (II), R ² and R ³ each independently represent an alkylene group having ^{4 to} 50 carbon atoms, R 4 represents an alkyl group having ^{4 to 50 carbon atoms, and R 5} has 2 to 50 carbon atoms. Indicates an alkyl group. ] (D) The resin composition according to any one of claims 1 to 3 , further containing an elastomer. (E) The resin composition according to any one of claims 1 to 4 , further containing a catalyst. A support with a resin layer comprising a support base material and a resin layer containing the resin composition according to any one of claims 1 to 5 provided on the support base material.

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