JP2002105308A - Curable polyphenylene ether-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition suitable for forming an insulating layer of a printed wiring board having sufficient adhesion to a copper plated film forming a conductor circuit after curing without deteriorating excellent dielectric characteristics and mechanical characteristics of a polyphenylene ether-based resin. SOLUTION: This curable polyphenylene ether-based resin composition comprises (a) a low-molecular weight polyphenylene ether reactional product obtained by reacting a modified polyphenylene ether with a phenolic compound in the presence of a reactional initiator, (b) triallyl isocyanurate and/or triallyl cyanurate, (c) a graft copolymer resin of a rubber-like elastic body with acrylonitrile and a vinyl aromatic compound and (d) silica. The amounts of the components based on 100 pts.wt. of the sum of the components (a) and (b) are 1-99 pts.wt. of the component (a), 99-1 pt.wt. of the component (b), 1-90 pts.wt. of the component (c) and 1-38,000 pts.wt. of the component (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable polyphenylene ether resin composition containing silica and a graft copolymer resin of a rubber-like elastic material, acrylonitrile and a vinyl aromatic compound. Furthermore, the present invention relates to a composite material comprising the resin composition and a substrate, a film comprising the resin composition, a laminate comprising a film comprising the resin composition and a metal foil, and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, miniaturization, high performance, and multifunctionality of electronic devices have been promoted, and printed wiring boards used for these devices have also been required to have higher densities by fine patterns. Along with this, in multilayer printed wiring boards, internal connections have been changed to not only through through holes but also inner and surface via holes. In addition, as the speeding up of equipment progresses, shortening of wiring patterns becomes unavoidable,
As the diameter of the via structure has been reduced, a structure that can be arranged at an arbitrary position in the multilayer wiring board has been required. Under such circumstances, recently, via holes can be formed at arbitrary locations inside and on the surface with a fine pattern, the shortest distance wiring is possible, and the approach to a build-up multilayer wiring board having a high wiring density has been activated. In addition, as a method of forming a conductor circuit on a build-up multilayer wiring board, a resin-coated copper foil obtained by laminating an uncured resin film on a copper foil is laminated on the circuit, cured, and etched on the surface of the copper foil. A subtractive method for forming a conductor circuit is widely used. However, this method has a problem that a so-called undercut occurs due to etching due to the thickness of the copper foil, it is difficult to obtain a high-precision fine pattern, and it is difficult to cope with high density. For this reason, as an alternative to the subtractive method, an additive method of directly laminating an uncured resin film without a copper foil on a circuit, curing the film, and forming a conductor circuit by electroless plating on the cured film has attracted attention. . Conventionally, a thermosetting resin, particularly an epoxy resin, has been used as a resin used for the insulating layer. Although it has various performances in a well-balanced manner, it has become impossible to cope with electrical characteristics, heat resistance and water absorption with the recent improvement in performance of electronic devices. As a new material for solving this problem, polyphenylene ether-based resins have recently attracted attention and have been applied. However, polyphenylene ether-based resin has insufficient adhesion to the copper plating film that forms the conductor circuit compared to the epoxy resin, and particularly when the conductor circuit is formed by the additive method, the plating film is easily removed from the insulating layer. There is a problem that peeling may occur.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a printed wiring having sufficient adhesion to a copper plating film forming a conductor circuit after curing without impairing the excellent dielectric and mechanical properties of the polyphenylene ether resin. Providing a resin composition suitable for forming a board insulating layer, in particular, a resin composition suitably used for a printed wiring board insulating layer capable of forming a high-density conductive circuit utilizing the advantages of the additive method The purpose is to provide things.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin forming a matrix of an insulating layer has an incompatible double resin. After dispersing the rubber component containing the bond into particles, the rubber component is dissolved and removed using an oxidizing agent to form a concave portion, and the copper plating film and the insulating layer that form a conductive circuit by the anchor effect due to this are formed. Have been found to improve the adhesiveness of the film, and have led to the present invention. That is, the present invention provides: (A) a low-molecular-weight polyphenylene ether reaction product obtained by reacting a reaction product of a polyphenylene ether with an unsaturated carboxylic acid or an acid anhydride thereof and a phenolic compound in the presence of a reaction initiator; ) Triallyl isocyanurate and / or triallyl cyanurate, (c) a graft copolymer resin of a rubber-like elastic material and acrylonitrile and a vinyl aromatic compound, and (d) silica; ) Sum of ingredients 100
1 to 99 parts by weight of component (a), based on parts by weight,
A curable polyphenylene ether-based resin composition comprising 99 to 1 part by weight of the component (b), 1 to 90 parts by weight of the component (c), and 1 to 38000 parts by weight of the component (d); . 2. a curable composite material comprising the curable polyphenylene ether-based resin composition of (1) and a base material (e); 3. a cured composite material obtained by curing the curable composite material of the above item 2; 4. a curable film comprising the curable polyphenylene ether-based resin composition of the above 1; 5. a cured film obtained by curing the curable film of 4 above; 6. A curable laminate obtained by laminating the curable film and the metal foil according to 4 above; 7. a cured laminate obtained by curing the curable laminate of 6 above; 8. a curable composite comprising the curable composite material of 2 above and / or the curable film of 4 above and / or the curable laminate of 6 above; A cured composite obtained by curing the curable composite of the above item 8. Hereinafter, the present invention will be described in detail. The polyphenylene ether used in the present invention is represented by the following general formula (1).

[0005]

Embedded image Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula (A) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Examples of the aryl group include a phenyl group. Examples of the halogen atom include bromine and chlorine. Representative examples of Q shown in the general formula (1) include a compound group represented by the following four types of structural formula units represented by the following chemical formula 2.

[0006]

Embedded image Specific examples include structural units shown in Chemical Formulas 3 and 4 below.

[0007]

Embedded image

[0008]

Embedded image In the polyphenylene ether chain represented by J in the above general formula (1), in addition to the unit represented by the general formula (A), a unit represented by the following general formula (B) is contained. Is also good.

[0009]

Embedded image Preferred examples of the polyphenylene ether represented by the general formula (1) used in the present invention include poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol, and poly (2,6-dimethyl-1,4-phenylene ether). (2,6-dimethyl-1,4-phenylene ether) styrene graft copolymer, 2,6-dimethylphenol and 2,3
A copolymer of 6-trimethylphenol, a copolymer of 2,6-dimethylphenol and 2,6-dimethyl-3-phenylphenol, and the presence of a polyfunctional phenol compound represented by the following chemical formula 6, A polyfunctional polyphenylene ether obtained by polymerization under the following conditions, for example, JP-A-63-301222, JP-A-1-297428
And copolymers containing the units of the general formulas (A) and (B) as disclosed in JP-A No. 10-260, 1988.

[0010]

Embedded image (In the formula, Q represents a residue of a polyfunctional phenol compound having 2 to 6 phenolic hydroxyl groups in one molecule and having a polymerization-inactive substituent at an ortho position and a para position of the phenolic hydroxyl group, and m represents The molecular weight of the polyphenylene ether described above is such that the viscosity number ηsp / C measured with a chloroform solution of 5 g / l at 30 ° C. is in the range of 0.1 to 1.0. Can be used well. Examples of the unsaturated carboxylic acid and its acid anhydride used in the present invention include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaric anhydride, citraconic anhydride and the like. . Particularly, maleic anhydride and fumaric acid can be used most preferably. The reaction is carried out by heating the polyphenylene ether and the unsaturated carboxylic acid or anhydride thereof in a temperature range of 100 to 390 ° C. At this time, a radical initiator may coexist. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be more easily performed and is suitable for the purpose of the present invention.

The ratio of the unsaturated carboxylic acid or its anhydride is 100 parts by weight of polyphenylene ether.
It is from 0.01 to 5.0 parts by weight, preferably from 0.1 to 3.0 parts by weight. In the present invention, the low-molecular-weight polyphenylene ether obtained by redistributing the modified polyphenylene ether (hereinafter abbreviated as “modified PPE”) thus obtained with a phenolic compound in the presence of a reaction initiator is used. The reaction product is used. When the resin composition of the present invention using such a low molecular weight polyphenylene ether reaction product is used for an insulating layer in a build-up method, the resin can be sufficiently poured into a circuit without leaving a void in a laminating step. In particular, even when the inner layer circuit has a fine wire structure required to have sufficient fluidity, when the resin composition containing a low molecular weight polyphenylene ether reaction product of the present invention is used, the resin is added to the circuit without leaving voids in the laminating step. You can pour enough. The phenolic compound used for producing the low-molecular-weight polyphenylene ether reaction product is a phenolic compound represented by the following chemical formula 7, that is, a compound having one or more phenolic hydroxyl groups.

[0012]

Embedded image Specific examples of the phenolic compound include, for example, 2-
Methylphenol, 3-methylphenol, 4-methylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol,
2,4,6-trimethylphenol, 2-methyl-6
Allylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-4-allylphenol, 2-allylphenol, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and phenol novolak, cresol Novolak and the like, preferably 2,3-xylenol, 2,4-xylenol, 2,5
-Xylenol, 2,6-xylenol, bisphenols, phenol novolak and cresol novolak. As a reaction initiator used for producing a low molecular weight polyphenylene ether reaction product, a peroxide represented by the following formula 8 can be preferably used.

[0013]

Embedded image Specific examples of the peroxide represented by Chemical formula 8 include diacyl peroxides such as benzoyl peroxide, 4,4-di-butylbenzoyl peroxide or other aryl-substituted derivatives, dilauryl peroxide, and acetyl. Benzoyl peroxide, acetylcyclohexylsulfonyl peroxide, diphthaloyl peroxide and the like, as peroxydicarbonates,
For example, diacetyl peroxydicarbonate, di-n
-Propyl peroxydicarbonate, diisopropyl peroxide, bis (4-t-butylcyclohexyl)
Peroxydicarbonate and the like, as peroxy acids, for example, perbenzoic acid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid and other substituted derivatives of perbenzoic acid,
Peroxyacetic acid, peroxypropanoic acid, peroxybutanoic acid, peroxynonanoic acid, peroxide decanoic acid,
Diperoxyglutaric acid, diperoxyadipic acid, diperoxyoctane diacid, diperoxynonane diacid, diperoxide decane diacid, monoperoxyphthalic acid, etc., and further peroxysulfuric acid, monoperoxydisulfuric acid,
Inorganic peroxyacids such as peroxyphosphoric acid and peroxydiphosphoric acid and their corresponding salts, and peroxycarboxylic acid esters such as t-butylperformate, t-butylperacetate, t-butylperoxyisobutyrate, and t-peroxynonanoic acid
Butyl, t-butyl monoperoxymaleate, dipar-
Examples include t-butyl oxyphthalate, di-t-butyl diperoxyadipate, and 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane. Specific examples of the radical generating compound that is another reaction initiator used in the present invention include quinones and diphenoquinones, such as benzoquinone and 2,2′-6,6′-.
And tetramethyldiphenoquinone (TMDQ). When producing the low molecular weight polyphenylene ether reaction product (a), the modified PPE and the phenolic compound are redistributed in an organic solvent in the presence of a reaction initiator.

The conditions of the redistribution reaction are as follows:
While stirring the modified PPE, the phenolic compound and the reaction initiator, the temperature is 60 to 120 ° C., preferably 70 to 11 ° C.
Heating is performed at 0 ° C. for about 10 to 300 minutes. In addition, as an organic solvent to be used, aromatic hydrocarbon solvents such as toluene, benzene, and xylene are exemplified. Regarding the mechanism of this reaction, when a modified PPE is reacted with a phenolic compound in the presence of a reaction initiator, it is considered that the modified PPE is radicalized first, and a redistribution reaction in which a straight chain is cut proceeds. It is considered that the molecular weight of the modified PPE is reduced. However, when the modified PPE is modified with maleic anhydride, for example, the phenolic hydroxyl group is lost at some ends due to the binding of maleic anhydride, and the terminal remains unaffected by the reduction in molecular weight. It is thought that. Therefore, it is considered that it is possible to reduce the molecular weight without impairing the mechanical properties as a film and, consequently, to reduce the melt viscosity (for the structure of maleic anhydride-modified PPE, see JHG
lans and M.S. K. Akkapeddi, Ma
cromolecules 1991, 24, 383-
386). The ratio of terminal modification is preferably 0.01 or more and less than 90, and more preferably 1 or more and less than 80 based on several hundred terminals. If the ratio of the terminal modified is less than 0.01, the molecular weight is remarkably reduced, and the mechanical properties of the film are unfavorably affected. In addition, the number of denatured ends is 90
If the number is more than one, the effect of lowering the molecular weight by the redistribution reaction is small, and a resin composition having good melting properties cannot be obtained, which is not preferable. The modified PPE, the phenolic compound and the reaction initiator used in the production of the low-molecular-weight polyphenylene ether reaction product (a) were prepared in a modified PPE1
The phenolic compound is contained in an amount of 0.5 to 6 parts by weight based on 00 parts by weight.
Parts by weight, preferably 0.5 to 4.5 parts by weight, and the reaction initiator in the range of 2 to 10 parts by weight, preferably 2.5 to 7.5 parts by weight. Next, triallyl isocyanurate and / or triallyl cyanurate, which is the component (b) used in the present invention, is a trifunctional monomer represented by the following formula 9.

[0015]

Embedded image In the present invention, triallyl isocyanurate and / or
Alternatively, triallyl cyanurate exerts effects as a plasticizer and a crosslinking agent. The component (a) described above,
The mixing ratio of the component (a) and the component (b) among the two components of the component (b) is based on 100 parts by weight of the sum of both components.
Component (a) is 1 to 99 parts by weight, preferably 10 to 70 parts by weight, and component (b) is 99 to 1 part by weight, preferably 90 to 90 parts by weight.
30 parts by weight. If the amount of the component (b) is less than 1 part by weight, the resin is thermally softened, and the melting characteristics required for embedding the circuit layer cannot be obtained, and poor adhesion occurs. If the amount is more than 99 parts by weight, the dielectric constant and the dielectric loss tangent increase, which is not preferable. (C) of the curable polyphenylene ether-based resin composition of the present invention
The rubbery elastomer used as the component and the graft copolymer resin of acrylonitrile and a vinyl aromatic compound are a copolymer of acrylonitrile and a vinyl aromatic compound and / or a copolymer of acrylonitrile and a vinyl aromatic compound. A copolymer with a polymerizable compound is used as a matrix phase, and a rubber-like elastic body contains a graft rubber phase obtained by graft copolymerization of acrylonitrile and a styrene-based compound in an island-like state. As the rubber-like elastic body, those having a double bond such as a conjugated diene rubber are preferable, and examples thereof include polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, styrene-butadiene block copolymer, and polystyrene. Examples include isoprene and natural rubber. When a rubber-like elastic body containing no conjugated double bond such as a hydrogenated product of an ethylene-propylene copolymer or a styrene-butadiene block copolymer is used, it is difficult to be etched by an oxidizing agent and the anchor effect is reduced. However, plating adhesion tends to be poor, which is not preferable. The vinyl aromatic compound includes, for example, styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, t-butylstyrene and the like, and one or more of these may be used in combination, or may be used in combination with these. Polymerizable vinyl compounds such as methyl methacrylate, acrylonitrile, methacrylonitrile, butyl acrylate, and maleic anhydride may be used in combination.

The graft copolymer resin of the rubber-like elastic material and acrylonitrile and a vinyl aromatic compound used in the present invention can be used in the presence of a rubber-like polymer in the form of a monomer containing acrylonitrile and a styrene-based compound as main components. It is well known that the polymer can be produced by a method such as bulk polymerization, solution polymerization, bulk suspension polymerization or emulsion polymerization in the presence or absence of a radical polymerization initiator, and it is also industrially produced. ing. Further, the graft rubber layer and the continuous phase resin may be separately polymerized and combined. In the component (c) used in the present invention, the proportion of the rubber-like elastic body to acrylonitrile and the vinyl aromatic compound in the rubber-like elastic body unit is 25 to 35% by weight, preferably 30 to 3% by weight.
The range is 5% by weight, the acrylonitrile unit is 7 to 40% by weight, preferably 7 to 20% by weight, and the vinyl aromatic compound unit is 25 to 68% by weight, preferably 45 to 63% by weight. If the rubber-like elastic body unit is less than 25% by weight, the anchor effect is reduced due to insufficient etching by the oxidizing agent, and the plating adhesion tends to decrease, which is not preferable. On the other hand, if the content exceeds 35% by weight, the etching is excessive and the surface condition of the plated surface deteriorates, which is not preferable. On the other hand, if the acrylonitrile unit is less than 7% by weight,
Rather, electroless plating deposition is difficult, and the adhesion tends to decrease, which is not preferable. If it exceeds 40% by weight,
Etching with an oxidizing agent becomes difficult and plating adhesion tends to decrease, which is not preferable. Representative examples of the graft copolymer resin of a rubber-like elastic material and acrylonitrile and a vinyl aromatic compound include ABS resin and ABS resin.
And a mixed resin of AS and AS.

The mixing ratio of the component (c) described above is as follows:
The amount is 1 to 90 parts by weight, preferably 1 to 80 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). If the component (c) is less than 1% by weight, the adhesion of the plating cannot be obtained due to insufficient anchor effect, and if it exceeds 90% by weight, the etching will be excessive and the surface condition of the plating surface will not only deteriorate, but also the inner layer circuit will be deteriorated. -Fluidity becomes insufficient at the time of lamination on the substrate, and especially when the inner layer circuit / substrate has a fine wire circuit, the flow between the circuits is insufficient, which is not preferable. Silica used as component (d) of the present invention, the curable polyphenylene but ether is blended for the purpose of imparting dimensional stability to the cured product of the resin composition, chemically silicon dioxide of the present invention (SiO ₂ ). The shape of the silica may be spherical, crushed, or a mixture thereof, and is not particularly limited. Also, the average particle size is not particularly limited as long as it is equal to or less than the thickness of the cured product formed by the curable polyphenylene ether-based resin composition of the present invention,
It is preferably from 0.1 μm to 3 μm. The silica used in the present invention for improving the adhesion at the interface between the silica and the resin, and for obtaining a good dispersion state in the curable polyphenylene ether-based resin composition of the present invention by making the silica surface hydrophobic. Is preferably treated with a silane coupling agent. Examples of such a silane coupling agent include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, and the like. However, there is no particular limitation. The amount of the silane coupling agent to be treated is not particularly limited either, and although it depends on the specific surface area of the untreated silica, it is preferably 0.1 to 5% by weight based on the untreated silica. When the treatment amount is less than 0.1% by weight, sufficient dispersibility cannot be obtained, and when the treatment amount is more than 5% by weight, aggregation of silicas occurs on the contrary, which is not preferable. A more preferred range of the treatment amount is 0.3 to 2% by weight.

The mixing ratio of the component (d) is from 1 to 380 based on 100 parts by weight of the sum of the components (a) and (b).
00 parts by weight, preferably 1 to 1000 parts by weight, more preferably 5 to 300 parts by weight. When the amount of the component (d) is less than 1 part by weight, the thermal expansion characteristic of the cured product formed by the curable polyphenylene ether-based resin composition of the present invention is insufficient. It is not preferable because the fluidity of the material becomes too low. As a method of mixing the components (a), (b), (c) and (d), a solution mixing method in which the four components are uniformly dissolved / dispersed in a solvent is preferable. Further, in order to further improve the dispersibility of the rubber-like elastic material in the component (c), a high-speed mixer such as a homogenizer is used, and then in order to further improve the dispersibility of the component (d), a planetary method is used. It is preferable to use a dispersing machine such as a ball mill, a bead mill, and a three-roll mill. Examples of the solvent used in the solution mixing method include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated solvents such as dichloromethane, chloroform, and trichloroethylene; and THF and the like. These may be used alone or in combination. it can. Curable polyphenylene ether-based resin composition of the present invention,
As described below, a crosslinking reaction is caused by heating or the like to cause curing, but a radical initiator may be used for the purpose of lowering the reaction temperature or promoting the crosslinking reaction of the unsaturated group. . The amount of the radical initiator used in the curable polyphenylene ether-based resin composition of the present invention,
The amount is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight based on 100 parts by weight of the sum of the components (a) and (b). Representative examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butyl peroxide, t-butyl cumene Ruperoxide, α, α-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t- Butyl peroxyisophthalate, t-butyl peroxybenzoate, 2,2-bis (t-butyl peroxy)
Butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, etc. Oxides.

The curable polyphenylene ether of the present invention
The resin composition can impart desired performance according to its use.
Fillers and additives in an amount that does not impair the original performance for the purpose of
Additives can be compounded and used. The filler is fibrous
Powder or carbon black,
Lumina, talc, mica, glass beads, glass hollow spheres, etc.
Can be mentioned. As additives, antioxidants,
Heat stabilizer, antistatic agent, plasticizer, pigment, dye, colorant, etc.
Is mentioned. Also, with the aim of further improving flame retardancy
Chlorine, bromine, phosphorus, nitrogen and silicon flame retardants
And Sb_TwoO_Three, NbSbO_Three・ 1 / 4H _TwoO and other flame retardant aids
Agents can be used in combination. Curable polyphenylene of the present invention
Curable composite comprising a lenether-based resin composition and a substrate
Cured material of the material, of the curable film comprising the resin composition
Cured body, curable film and metal foil comprising the resin composition
The cured product of the curable laminate consisting of
By curing the phenylene ether resin composition
It is obtained. The method of curing is optional, heat,
A method using light, an electron beam, or the like can be employed. heating
If curing is performed by using a radical initiator,
80-300 ° C., more preferably 120-300 ° C.
~ 250 ° C. The curing time is 1 minute to 1
0 hour, more preferably 1 minute to 5 hours. Next, the book
The curable composite material of the invention and the cured product thereof will be described.
You. The curable composite material of the present invention comprises: (a) polyphenylene
Reaction between ether and unsaturated carboxylic acid or its anhydride
Reaction product with phenolic compound in the presence of initiator
Low molecular weight polyphenylene ether obtained by reacting
Reaction product, (b) triallyl isocyanurate and
And / or triallyl cyanurate, (c) rubbery elasticity
Of Acrylonitrile with Acrylonitrile and Vinyl Aromatic Compound
A graft copolymer resin, (d) silica, and (e) a base material.
Consists of

As the base material of the component (e), cloths, chopped mats, surfing mats and other various glass cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths; polyvinyl alcohol fibers, polyester fibers, acrylic fibers, Liquid crystal fibers such as wholly aromatic polyamide fibers, aromatic polyester fibers, and polybenzazole fibers,
Woven or non-woven fabric obtained from synthetic fibers such as polytetrafluoroethylene fiber; natural fibers such as cotton cloth, linen, felt; carbon fiber cloth; kraft paper, cotton paper;
Cellulose-based natural cellulosic fabrics such as paper-glass mixed fiber paper are used alone or in combination of two or more. The proportion of the component (e) in the curable composite material of the present invention is from 5 to 90 parts by weight, based on 100 parts by weight of the sum of the components (a), (b), (c) and (d). Preferably it is 10 to 80 parts by weight, more preferably 20 to 70 parts by weight. When the amount of the component (e) is less than 5 parts by weight, the dimensional stability and strength of the curable composite material after curing are insufficient, and when the amount is more than 90 parts by weight, the dielectric properties of the cured product of the curable composite material are poor. Absent. In the curable composite material of the present invention, a coupling agent can be used, if necessary, for the purpose of improving the adhesiveness at the interface between the resin composition layer and the substrate. As the coupling agent, those usually used such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and a zircoaluminate coupling agent can be used. Examples of the method for producing the curable composite material of the present invention include a method of uniformly dissolving / dispersing the curable polyphenylene ether-based resin composition of the present invention in a solvent, impregnating the substrate, and then drying. As the solvent used here, in addition to the aromatic hydrocarbon solvent and the halogen solvent used in the production of the resin composition of the present invention described above,
Ketone solvents, dimethylformamide, dimethylsulfoxide and the like can be mentioned, and these are used alone or as a mixture.

The impregnation is performed by dipping, coating, etc.
It is done. Repeat the impregnation several times as necessary
In this case, a plurality of components having different compositions and concentrations can be used.
Repeat the impregnation using the solution and finally the desired resin
It is also possible to adjust the composition and the amount of resin. The present invention
The cured product of the curable composite material is the cured product thus obtained.
By curing the conductive composite material by a method such as heating
It is obtained. Although the manufacturing method is particularly limited,
Instead of, for example, stacking multiple curable composite materials
And apply heat and pressure to bond the layers together and heat cure at the same time.
To obtain a cured product having a desired thickness. Ma
The combination of the cured product and the cured product
It is also possible to obtain a cured product having a new layer structure. Lamination
Forming and curing are usually performed simultaneously using a hot press or the like,
Both may be performed independently. That is,
Uncured or semi-cured cured product obtained by lamination molding
Heat-treating or otherwise treating the composite material
Therefore, it can be cured. Laminate molding and curing
Is a temperature of 80 to 300 ° C. and a pressure of 0.1 to 500 kg / c.
m ^TwoFor a time in the range of 1 minute to 10 hours,
Degree 150-250 ° C, pressure 1-100kg / cm^Two,Time
It can be performed in a range of 1 minute to 5 hours.

Next, a method for producing a curable film comprising the curable polyphenylene ether-based resin composition of the present invention will be described. As a method for forming a film of the curable polyphenylene ether-based resin composition, any method may be used, but a preferable method is, for example, a method in which a varnish obtained by dissolving / dispersing the resin composition in a solvent such as a PET film is used. After applying to a coating substrate, a method of drying the coating substrate may be used. A suitable solvent is selected according to the selection of the resin composition. Examples of the solvent used for adjusting the varnish of the curable polyphenylene ether-based resin composition include aromatic hydrocarbons such as benzene, toluene, and xylene; halogen-based solvents such as dichloromethane, chloroform, and trichloroethylene; and THF. These can be used alone or as a mixture. Examples of a method of applying a varnish comprising a curable polyphenylene ether-based resin composition and a solvent include a method using an apparatus such as an air coater, a blade coater, a rod coater, a knife coater, a gravure coater, a reverse coater, and a cast coater. Examples of the method for drying the coating film include a method using a device such as hot air drying, roll heating drying, infrared drying, and far infrared drying. These devices are used alone or in combination of two or more. May be used. The drying temperature is 60-90 ° C., preferably 7
0-85 ° C.

The thickness of the film of the curable polyphenylene ether-based resin composition is not particularly limited.
0 μm is preferred, and more preferably 30 to 100 μm. When the film thickness is extremely small, it becomes difficult to perform the lamination build-up method. The curable film of the present invention is obtained by peeling off a PET film or the like after manufacturing as described above. The curable laminate in which the film of the curable polyphenylene ether-based resin composition of the present invention is a resin-coated metal foil formed on the surface of a metal foil, the coating substrate is changed to a metal foil such as a copper foil, and the same as above. Can be manufactured. that time,
The roughened electrolytic copper foil manufactured and sold for manufacturing a wiring board can be used as it is for manufacturing a resin-coated copper foil for a multilayer wiring board. The thickness of the metal foil is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 10 μm from the viewpoint of ease of handling.
The range is 0 μm. The curable composite of the present invention is obtained by laminating the above-mentioned curable composite material, a curable film, and a resin-attached metal foil in an arbitrary layer configuration. As a method for producing the cured composite of the present invention, for example, the curable composite material of the present invention and / or the curable film of the present invention and / or the curable laminate of the present invention are laminated in a layer structure according to the purpose. And a method in which each layer is adhered to each other under heat and pressure, and simultaneously cured by heat.

Next, a build-up substrate using the curable film of the present invention will be described. The substrate used in the present invention is not particularly limited, and examples thereof include a double-sided copper-clad laminate, a single-sided copper-clad laminate, an aluminum plate, and an iron plate. When a double-sided copper-clad laminate or a single-sided copper-clad laminate is used, a circuit pattern may be created on a substrate in advance. The curable film of the present invention is adhered to these substrates by heating and pressing to form an insulating layer, and then a circuit pattern is formed by ordinary electroless copper plating or electrolytic copper plating. At that time, by treating with an oxidizing agent such as permanganate, chromate, chromate, ozone, etc., the rubber-like elastic body in the component (c) is dissolved and removed (roughened), and is used for electroless plating. A recess that can be an anchor is formed. Thereby, the adhesion between the copper plating film forming the conductor circuit and the insulating base material can be improved. Before or after the treatment with the oxidizing agent, plasma treatment or the like may be performed. After the circuit pattern is formed in this way, the curable film of the present invention is further heated and pressed and bonded, and a circuit pattern is formed in the same manner as described above, whereby a build-up substrate can be manufactured. Curable polyphenylene ether-based resin composition of the present invention,
Excellent dielectric properties, heat resistance, dimensional stability after curing,
Shows adhesion to copper plating films and can be used as dielectric materials, insulating materials, heat-resistant materials, etc. in the fields of the electronics industry, space and aircraft industries, etc.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. In the following examples, the following were used as each component. <Low molecular weight polyphenylene ether reaction product> Poly (2,6-dimethyl-1,4-
100 parts by weight of phenylene ether), 1.5 parts by weight of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Nippon Oil & Fats Co., Ltd.)
Was dry-blended at room temperature, and extruded with a twin-screw extruder at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm to produce a modified polyphenylene ether resin.
100 parts by weight of the modified polyphenylene ether resin,
2,6-xylenol 0.8 as a phenolic compound
Parts by weight, 3 parts by weight of bis (4-t-butylcyclohexyl) peroxydicarbonate as a reaction initiator and 550 parts by weight of toluene as a solvent,
A redistribution reaction was carried out while stirring at 3 ° C. for 3 hours. The obtained reaction product was reprecipitated with the same volume of methanol as toluene used, washed with three times the amount of methanol and dried to obtain a low molecular weight polyphenylene ether reaction product. The number average molecular weight of this low molecular weight polyphenylene ether reaction product measured by gel permeation chromatography was 12
000. <Polymerization initiator> 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (manufactured by NOF CORPORATION, perhexin 2)
5B: trade name) <Graft copolymer resin of rubber-like elastic body and acrylonitrile and vinyl aromatic compound> ABS resin (Styrac ABS A6450, B7241: trade name, manufactured by A & M Styrene Co., Ltd.) <Silica> Spherical silica (average particle size: 0.5 μm; Co., Ltd.)
Admafine SO-C2 (trade name, manufactured by Admatechs) is used as a raw material and treated with silane coupling agent γ-methacryloxypropyltrimethoxysilane (KBM503, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) (treatment) 0.8% by weight). <Flame retardant> Melamine phosphate (manufactured by Sanwa Chemical Co., Ltd., P-720)
2: trade name) as a raw material, and treated with γ-methacryloxypropyltrimethoxysilane (KBM503: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent (treatment amount: 1.0% by weight). thing.

[0026]

Examples 1 to 3 The above low-molecular-weight polyphenylene ether reaction product [component (A)] and ABS resin [component (C)]
At a composition ratio shown in Table 1 in toluene at 80 ° C.
After stirring for an hour, the mixture was further stirred at 15,000 rpm for 10 minutes using a homogenizer (HF93, manufactured by SMT Co., Ltd.). After adding triallyl isocyanurate [component (B)] at the composition ratio shown in Table 1, silica [(D) component] and a flame retardant were added at the composition ratio shown in Table 1, and a wet bead mill ( Using an SC mill manufactured by Mitsui Mining Co., Ltd., the mixture was dispersed at 80 ° C. for 1 hour. Finally, a polymerization initiator was added at the composition ratio shown in Table 1 to prepare a varnish. Then, after apply | coating on a 100-micrometer-thick PET film with a blade coater, it dried at 60 degreeC for 15 minutes with an air oven, and obtained the curable film. The resin thickness of the obtained curable film was 40 μm. The curable film obtained by peeling the PET film is sandwiched between mat surfaces of a copper foil (Furukawa Electric Co., Ltd., F2-WS; 12 μm), laminated and cured by a vacuum press molding machine to a thickness of about 80 μm. Was prepared. The curing conditions were as follows: the temperature was raised at 3 ° C./min, and the temperature was maintained at 200 ° C. for 1 hour. The pressure is 30kg / cm
^{And 2} . Various physical properties of this cured product were measured by the following methods. 1. The dielectric constant and the dielectric loss tangent were measured at 1 MHz. The measuring device is an impedance analyzer 4192ALF
(Manufactured by Yokogawa Hewlett-Packard Co., Ltd.). 2. Solder heat resistance: 60 m of cured product from which half of the copper foil has been removed
It was cut into m-squares, floated in a solder bath at 260 ° C. for 120 seconds, and visually observed for changes in appearance. 3. Glass transition temperature and coefficient of thermal expansion: A sample cut from the cured product from which the copper foil had been removed was measured by the TMA method.

Further, the above-mentioned curable film was laminated and cured on both sides of a polyphenylene ether laminate having a thickness of 0.8 mm so that PET became the surface. Lamination and curing were carried out in a vacuum press molding machine at 180 ° C. and 10 kg / cm ² for 10 minutes, followed by curing in an oven at 180 ° C. for 1 hour. Using the sample from which the PET film was peeled, plasma treatment, roughening treatment (oxidizing agent treatment), electroless copper plating, and electrolytic copper plating were performed in the following steps, and the plating peel strength was measured.

(Plasma Treatment Step) Using a capacitive RIE apparatus, the substrate was treated with oxygen gas at a pressure of 45 to 48 Pa and an RF power of 100 W for 5 minutes. (Roughening step) The surface of the cured product was immersed in a swelling solution (Maccutizer 9204, trade name, manufactured by Japan McDermid Co., Ltd.) at 35 ° C. for 3 minutes and in a potassium permanganate solution at 80 ° C. for 10 minutes. , And then neutralized solution (Nippon MacDermid Co., Ltd., Macutizer 9279: trade name)
And washed with water and dried. After the roughening treatment, the surface of the sample was observed with a scanning electron microscope (SEM).
The formation of a concave portion, which seems to have dissolved and removed the rubber-like elastic material therein, was observed.

(Electroless Plating Step) A palladium catalyst (manufactured by Shipley) is applied to the roughened resin insulating layer, and the surface is activated by an accelerator (manufactured by Shipley). (McDermid Co., Ltd.) for 20 minutes, washed with water and dried. (Copper sulfate plating process) The cured product after electroless plating is
After immersion in an electrolytic plating solution (sulfuric acid-copper sulfate) at a current of 1 A / dm ² for 1 hour, baking was performed at 150 ° C. for 60 minutes to form a 20 μm thick conductor layer. 4. Plating peel strength: The adhesive strength between the cured product obtained by the above method and the copper plating layer was measured by the method of JIS-C-6481. Table 3 shows the above results.

[0030]

Comparative Examples 1 to 3 As shown in Table 2, the same operations as in Example 1 were repeated except that the amount of the ABS resin was changed, and each evaluation was performed. After the roughening treatment, the surface of the sample was observed with a scanning electron microscope (SEM). As a result, in Comparative Example 1, no recess was formed. In Comparative Examples 2 and 3, the surface of the plating was extremely rough. Table 4 shows the results.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

According to the curable polyphenylene ether-based resin composition of the present invention, it is possible to obtain a cured film having excellent adhesion to a copper plating film forming a conductor circuit,
In particular, it is suitably used for a printed wiring board insulating layer capable of forming a high-density conductive circuit utilizing the advantages of the additive method. In addition, it has a low coefficient of expansion after curing, and is excellent in heat resistance and dielectric properties.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/36 C08K 3/36 5/3492 5/3492 C08L 55/02 C08L 55/02 (72) Inventor Shozo Kinoshita 1-3-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in Asahi Kasei Kogyo Co., Ltd. (reference) AB07 AB08 AB09 AB10 AB11 AB28 AD02 AD42 AD52 AD53 AE01 AF06 AG03 AG16 AG17 AG18 AG19 AG20 AH02 AH22 AJ04 AK14 AL13 4F100 AA20A AB01B AB17 AB33 AB33B AK51A AK54A AK74 AK74A AL04A BA02 BA07 CA08 EH46J07 J08 EBJ4B EU196 FD017 FD146 GF00 GQ00 4J005 AA23 BD00

Claims (9)

[Claims] 1. A low-molecular-weight polyphenylene ether reaction obtained by reacting (a) a reaction product of a polyphenylene ether with an unsaturated carboxylic acid or an acid anhydride thereof and a phenolic compound in the presence of a reaction initiator. Product,
(B) triallyl isocyanurate and / or triallyl cyanurate, (c) a graft copolymer resin of a rubbery elastomer and acrylonitrile and a vinyl aromatic compound, and (d) silica, Component (a) is 1 to 9 based on 100 parts by weight of the sum of component (b).
A curable polyphenylene ether-based resin comprising 9 parts by weight, 99 to 1 parts by weight of the component (b), 1 to 90 parts by weight of the component (c), and 1 to 38000 parts by weight of the component (d). Composition. 2. A curable composite material comprising the curable polyphenylene ether-based resin composition according to claim 1 and (e) a base material. 3. A cured composite material obtained by curing the curable composite material according to claim 2. 4. A curable film comprising the curable polyphenylene ether-based resin composition according to claim 1. 5. A cured film obtained by curing the curable film according to claim 4. 6. A curable laminate obtained by laminating the curable film according to claim 4 and a metal foil. 7. A cured laminate obtained by curing the curable laminate according to claim 6. 8. A curable composite comprising the curable composite material according to claim 2 and / or the curable film according to claim 4 and / or the curable laminate according to claim 6. 9. A cured composite obtained by curing the curable composite according to claim 8.