JPH0692533B2 - Novel flame retardant composite material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant composite material, and more specifically, a composite material comprising a curable and flame-retardant polyphenylene ether resin composition and a base material. Regarding

Furthermore, the present invention relates to a cured flame-retardant composite material obtained by curing the flame-retardant composite material, and a laminate comprising the cured flame-retardant composite material and a metal foil.

The composite material and the laminate have excellent flame retardancy, chemical resistance, and dielectric properties, and can be advantageously used as materials in the electric and electronic fields.

[Conventional technology]

In recent years, there has been a remarkable trend toward miniaturization and high density of mounting methods in the field of electronic devices for communication, consumer use, industrial use, etc., and accordingly, better heat resistance in terms of materials,
Dimensional stability, electrical characteristics, and flame retardancy are being demanded. For example, as a printed wiring board, a copper-clad laminate having a thermosetting resin such as a phenol resin or an epoxy resin as a base material has been conventionally used. Although these have various performances in a well-balanced manner, they have the drawback of poor electrical characteristics, especially dielectric characteristics in the high frequency region. Polyphenylene ether has recently attracted attention as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

Polyphenylene ether is an engineering plastic with excellent mechanical and electrical properties, and has relatively high heat resistance. However, when it is intended to be used as a printed circuit board material, extremely high heat resistance of solder is required, so that the heat resistance inherent to polyphenylene ether cannot be said to be sufficient. That is, polyphenylene ether is 20
When it is exposed to a high temperature of 0 ° C or higher, it deforms, causing a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for circuits. Further, polyphenylene ether has strong resistance to acids, alkalis and hot water, but has extremely weak resistance to aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds and is soluble in these solvents.

From the viewpoint of flame retardancy, it is hard to say that polyphenylene ether has sufficient flame retardance to withstand the requirements as a printed circuit board material.

As one of methods for improving the heat resistance and chemical resistance of polyphenylene ether, a method of introducing a crosslinkable functional group into the chain of polyphenylene ether and further curing it to use it as a cured polyphenylene ether has been proposed.

Specific examples include polymers of 2-allyl-6-methylphenol or 2,6-diallylphenol.
Polymer Science, Vol. 49, p. 267 (1961). U.S. Pat.Nos. 3,281,393 and 34,2062 include:
Copolymers of 2,6-dimethylphenol and 2-allyl-6-methylphenol or 2,6-diallylphenol are disclosed. Further, US Pat. No. 4,634,742 discloses vinyl group-substituted polyphenylene ether.
Furthermore, the present inventors have previously invented a polyphenylene ether substituted with a propargyl group or an allyl group, and a polyphenylene ether containing a triple bond or a double bond, and that these are curable, and the resulting cured product is obtained. Have been found to be insoluble in aromatic hydrocarbon solvents and halogen-substituted hydrocarbon solvents and have excellent dielectric properties (Japanese Patent Application Nos. 64-69628 and 64-69629, Japanese Patent Application Laid-Open No. 1-69629).
See 113425 and 1-143426). However, none of the above curable polyphenylene ethers has been improved at all in terms of flame retardancy.

As a material that imparts chemical resistance and flame retardancy to polyphenylene ether at the same time, the present inventors have subsequently invented a functionalized polyphenylene ether resin composition composed of a reaction product of a polyphenylene ether resin and allyl bromide or propargyl bromide. (Japanese Patent Application 1-52041
No. 1-53703). However, these cured products have (1) swelling and warping although they are insoluble when they are boiled with trichloroethylene, and therefore their chemical resistance is not sufficiently improved to be used as a printed circuit board material. There was a problem that the improvement of sex was insufficient.

[Problems to be Solved by the Invention]

In view of the above circumstances, the present invention aims to provide a novel composite material having excellent chemical resistance and flame retardancy while taking advantage of the excellent dielectric properties of polyphenylene ether.

[Means for Solving the Problems]

The present inventors have accomplished the present invention as a result of solving the above problems and earnestly studying to obtain a material suitable as a laminated material. The present invention comprises the following three inventions.

That is, a first aspect of the present invention is a flame-retardant composite material comprising a curable flame-retardant resin composition and a substrate, wherein the curable flame-retardant resin composition comprises (a) a polyphenylene ether resin and A functionalized polyphenylene ether resin composition comprising a reaction product of allyl bromide and / or propargyl bromide, wherein bromine and allyl groups and / or propargyl groups are covalently bonded to the polyphenylene ether resin, and the content of bromine is Is 1% by weight or more and 30% by weight or less, and the content of the allyl group and / or propargyl group defined by the following formula is 0.1% by mole or more and 100% by mole or less, a functionalized polyphenylene ether resin composition.

(B) Triallyl isocyanurate and / or triallyl cyanurate (c) Brominated flame retardant represented by the following formula (In the formula, m and n are integers of 1 to 5 and 4 ≦ m + n ≦ 10.) And (d) an antimony-based flame retardant auxiliary is contained, and the sum of (a) and (b) is included. 98 to 40 parts by weight of component (a) and 2 to 60 parts of component (b) based on 100 parts by weight
1 part by weight to 40 parts by weight of the component (c) and 0.1 parts by weight of the component (d).
Disclosed is a flame-retardant composite material, characterized in that the content is -40 parts by weight.

A second aspect of the present invention is a cured flame-retardant composite material comprising a flame-retarded resin composition cured product and a substrate, wherein (i) the flame-retarded resin composition cured product is a functionalized polyphenylene ether resin. A cured product obtained by curing a composition and a resin composition comprising triallyl isocyanurate and / or triallyl cyanurate, and containing a bromine-based flame retardant and an antimony-based flame retardant represented by the following formula And (In the formula, m and n are integers of 1 to 5 and 4 ≦ m + n ≦ 10.) (Ii) The flame-retardant composite material is mixed with chloroform at 23 ° C. for 12 hours.
The chloroform extraction rate after time treatment is 0.01% by weight or more and 10% by weight or less based on the cured product of the flame-retardant resin composition, and (iii) the unit represented by the following structural formula in the chloroform extract ( I) and / or (II), and (III)
Is included.

A cured flame-retardant composite material is provided.

(In the formula, R represents an allyl group and / or a propargyl group.) A third aspect of the present invention is a cured flame-retardant composite material and a metal foil in which a cured product of the flame-retardant resin composition and a substrate are combined. (I) the flame-retardant resin composition cured product cures a functionalized polyphenylene ether resin composition and a resin composition comprising triallyl isocyanurate and / or triallyl cyanurate. It is a cured product obtained by, and contains a brominated flame retardant and an antimony flame retardant auxiliary represented by the following formula, (In the formula, m and n are integers of 1 to 5, and 4 ≦ m + n ≦ 10.) (Ii) Chloroform extraction rate when the laminate is treated with chloroform at 23 ° C. for 12 hours is flame retardant. 0.01 wt% or more and 10 wt% or less based on the cured resin composition cured product,
And (iii) the unit (I) and / or (II) represented by the above structural formula in the chloroform extract, and (II
A laminated body characterized by including I) is provided.

The above three inventions will be described in detail below.

The functionalized polyphenylene ether resin composition used as the component (a) of the flame-retardant composite material according to the first aspect of the present invention is a resin composition comprising a polyphenylene ether resin and a reaction product of allylpromide and / or propargyl bromide. It is a thing.

The polyphenylene ether resin used here is represented by the following general formula.

QJ-H] _p (IV) In the formula, p is an integer of 1 or 2, and J is a polyphenylene ether chain substantially composed of units represented by the following general formula: Q represents a hydrogen atom when p is 1, has two phenolic hydroxyl groups in one molecule when p is 2, and has a polymerization-inert substituent at the ortho and para positions of the phenolic hydroxyl group. Represents a residue of a functional phenolic compound. Q
A typical example of is a group of compounds represented by the following two general formulas.

[In the formula, A ₁ and A ₂ represent the same or different linear alkyl groups having 1 to 4 carbon atoms, X represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aromatic hydrocarbon residue and an aromatic hydrocarbon residue thereof, and substituted derivatives, the aralkyl group and the substituted derivatives thereof, oxygen, sulfur, sulfonyl group, a carbonyl group, two phenyl groups attached directly a _2, ortho coupling position of a ₂ and X is all phenolic hydroxyl groups and Indicates para position. ] As a specific example, Etc.

A particularly preferable example of the polyphenylene ether resin of the general formula (IV) is poly (2,6-dimethyl-1,4-phenylene ether) obtained by oxidative polymerization of 2,6-dimethylphenol alone. Also, 2,6-dimethylphenol and 2,
A copolymer obtained from the copolymerization of 3,6-trimethylphenol is also a preferred example.

The molecular weight of the polyphenylene ether resin of the general formula (IV) is not particularly limited, and it can be used from low molecular weight to high molecular weight, especially the viscosity number η _sp / C measured at 30 ° C in a 0.5 g / dl chloroform solution. Those with a value of 0.2 to 1.0 can be used satisfactorily.

From the polyphenylene ether resin of the general formula (IV) (a)
The method for producing the functionalized polyphenylene ether resin composition of the component is not particularly limited, and examples thereof include the methods disclosed in Japanese Patent Application Nos. 1-52041 and 1-53703. That is, there may be mentioned a method comprising a step of metallizing the polyphenylene ether resin of the general formula (IV) with an organic metal, followed by substitution reaction with allyl bromide and / or propargyl bromide.

The structure of the functionalized polyphenylene ether resin composition thus obtained is determined by nuclear magnetic resonance (hereinafter abbreviated as NMR) spectrum measurement to be at least the following units represented by three to four structural formulas. It has been found to be substantially composed.

(In the formula, R represents an allyl group and / or a propargyl group.) Similarly, according to the measurement of NMR spectrum, bromine and allyl group and / or propargyl group contained in the functionalized polyphenylene ether resin composition were Both are covalently bonded to the polyphenylene ether resin skeleton, bromine is substantially derived from the structure of (III), and the allyl group and / or propargyl group is substantially of the structure of (I) and (II). It is known to be derived from.

For details of the structure of the functionalized polyphenylene ether resin composition and the formation mechanism thereof, see Japanese Patent Application No. 1-52041.
No. 1-53703.

The content of bromine in the functionalized polyphenylene ether resin composition used as the component (a) of the present invention is in the range of 1% by weight or more and 30% by weight or less, more preferably 1% by weight or more, based on the resin composition. It is in the range of 20% by weight or less. The content of the allyl group and / or propargyl group defined by the following formula is in the range of 0.1 mol% or more and 100 mol% or less, more preferably 0.5 mol% or more and 50 mol% or less.

When the content of bromine is less than 1% by weight, a large amount of flame retardant must be used in combination to improve flame retardancy, which is not preferable. Conversely 30
If it exceeds 5% by weight, the thermal stability decreases, which is not preferable. Further, when the content of the allyl group and / or propargyl group is less than 0.1 mol%, the chemical resistance after curing is insufficiently improved, which is not preferable. On the contrary, if it exceeds 100 mol%, it becomes very brittle after curing, which is not preferable.

The molecular weight of the functionalized polyphenylene ether resin composition used as the component (a) of the present invention is not particularly limited, and low to high molecular weight compounds can be used.
Viscosity number η _sp measured at 30 ℃ in 0.5g / dl chloroform solution
Those with / C in the range of 0.2 to 1.0 can be used satisfactorily.

The triallyl isocyanurate and / or triallyl cyanurate used as the component (b) of the flame-retardant composite material according to the first aspect of the present invention is a trifunctional monomer represented by the following structural formula.

In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate may be used alone, or both may be mixed and used at an arbitrary ratio.

The brominated flame retardant used as the component (c) of the flame retardant composite material of the present invention is a brominated diphenyl ether represented by the following structural formula.

(In the formula, m and n are integers of 1 to 5, and 4 ≦ m + n ≦ 10.) Specific examples of the flame retardant include tetrabromodiphenyl ether, hexabromodiphenyl ether, octabromodiphenyl ether, and deca. Examples include bromodiphenyl ether and the like.

Specific examples of the antimony-based flame retardant aid used as the component (d) of the flame-retardant composite material of the present invention include Sb ₂ O ₃ and S
b ₂ O ₅ , NaSbO ₃ · 1 / 4H ₂ O, etc., among which Sb ₂
O ₃ is preferably used.

The base material used in the flame-retardant composite material of the present invention includes various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat; ceramic fiber cloth, asbestos city, metal fiber cloth and other synthetic or natural materials. Inorganic fiber cloth; woven or non-woven cloth obtained from synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber; cotton cloth,
Natural fiber cloths such as linen cloth and felt; carbon fiber cloths; natural cellulosic cloths such as kraft paper, cotton paper, paper-glass mixed woven paper, etc. may be used alone or in combination of two or more kinds.

Among the above four components (a) to (d), the blending ratio of the component (a) and the component (b) is based on the sum of the two components (a).
The component is in the range of 98 to 40% by weight, more preferably 95 to 60% by weight, and the component (b) is in the range of 2 to 60% by weight, more preferably 5 to 40% by weight. If the amount of the component (b) is less than 2% by weight, the chemical resistance is not sufficiently improved, which is not preferable. vice versa
If it exceeds 60% by weight, the dielectric properties and flame retardancy are deteriorated, and it becomes a very brittle material after curing, which is not preferable.
Furthermore, when it is combined with a base material as described later, it becomes a material with a sticky surface, which is not preferable.

The blending ratio of the flame retardant (c) component is selected according to the blending ratio of the (a) component and the (b) component and the amount of the base material, but the sum of the (a) component and the (b) component is 100. 1 to 4 parts by weight
It is used in an amount of 0 part by weight, more preferably 5 to 30 parts by weight. If the amount of component (c) is less than 1 part by weight, flame retardancy is not imparted, which is not preferable. On the other hand, if the amount exceeds 40 parts by weight, the dielectric properties, chemical resistance and mechanical properties are deteriorated, which is not preferable.

The blending ratio of the flame retardant aid (d) component is selected according to the amount of the (c) component, but the sum of the (a) component and the (b) component is 10
It is used in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 0 parts by weight. If the amount of component (d) is less than 0.1 parts by weight, flame retardancy is not improved, which is not preferable. On the other hand, if the amount exceeds 40 parts by weight, the dielectric properties, chemical resistance and mechanical properties are deteriorated, which is not preferable.

The method of blending the above components and forming a composite with the substrate is not particularly limited, but preferably (a) to
A method of uniformly dissolving or dispersing the component (d) in a solvent, impregnating the base material, and then drying. Impregnation is usually done by dipping or coating. Impregnation can be repeated multiple times as needed, and in this case it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and amount. Is.

Preferable solvents include halogen-substituted hydrocarbons such as dichloromethane, chloroform and trichloroethylene, aromatic hydrocarbons such as benzene, toluene and xylene, and single or mixed solvents.

The blending ratio of the base material and the resin component in the flame-retardant composite material of the present invention is not limited, but the base material 5 to 90% by weight, more preferably 10 to 80% by weight, further preferably 20 to 70% by weight. % To 95% by weight of the resin component, more preferably
The amount is preferably 90 to 20% by weight, more preferably 80 to 30% by weight. When the base material is less than 5% by weight, the dimensional stability and strength of the composite material after curing are insufficient, and the base material is 90% by weight.
If it exceeds 5% by weight, the dielectric properties and flame retardancy of the composite material deteriorate, which is not preferable.

The method for curing the flame-retardant composite material of the present invention is arbitrary, and a method using heat, light, electrons or the like can be adopted. A radical initiator may be contained as a catalyst for the purpose of lowering the temperature at that time or accelerating the crosslinking reaction. A preferred amount of the initiator is 0.1 to 10 parts by weight based on 100 parts by weight of the sum of the components (a) and (b),
More preferably, it is in the range of 0.1 to 5 parts by weight. The initiator is
If the amount is less than 0.1 parts by weight, curing is not sufficiently performed and chemical resistance becomes insufficient, which is not preferable. On the contrary, if the amount exceeds 10 parts by weight, the initiator remains and the dielectric properties are deteriorated or the material becomes brittle, which is not preferable. Representative examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 2,5-dimethyl-2,5-di (t −
Butyl peroxy) hexane-3, di-t-butyl peroxide, t-butyl cumyl peroxide, α,
α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t
-Butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butalperoxy) octane, 2,5-dimethyl-2, There are peroxides such as, but not limited to, 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltoluphenylsilylperoxide. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator.

When curing is carried out by heating, the temperature varies depending on the presence or type of the initiator and its type, but the temperature is selected in the range of 100 to 350 ° C, more preferably 150 to 300 ° C. Time is 1
Minutes to 5 hours, more preferably 1 minute to 3 hours.
The degree of this curing reaction depends on the differential scanning calorimeter and infrared absorption (hereinafter
It can be traced by a spectral method.

The flame-retardant composite material of the present invention can be used by blending an amount of a filler or an additive within a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. The filler may be fibrous or powdered, glass fiber,
Examples thereof include aramid fiber, carbon fiber, boron fiber, ceramic fiber, asbestos fiber, carbon black, silica, alumina, talc, mica, glass beads and glass hollow spheres. Further, as the additive, an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, a colorant, etc. can be blended.

Summarizing the features of the flame-retardant composite material according to the first aspect of the present invention described above, the first point is that it has excellent flame retardancy. The functionalized polyphenylene ether resin composition used in the present invention has an advantage that excellent flame retardancy can be exhibited by adding a smaller amount of flame retardant because bromine is introduced into the molecular skeleton. Further, generally, in a system in which a resin and a base are compounded, the flame retardancy is remarkably reduced as compared with the case where only the resin is used. However, in the present invention, by optimizing the combination of the flame retardant and the flame retardant auxiliary, it has succeeded in imparting excellent flame retardancy without deteriorating other physical properties at all.

The second feature of the present invention is that it is excellent in film forming property by the casting method. Almost no solvent film-forming property is observed with ordinary polyphenylene ether, whereas in the present invention, a composite material which is smooth and has no surface stickiness can be obtained and is easy to handle. The third feature of the present invention is that it is excellent in storage stability and can be stored for a long time without gelation.

The fourth characteristic of the present invention is that thermoforming is easy because the glass transition temperature is low and the fluidity is excellent due to the plasticizing effect of triallyl isocyanurate and / or triallyl cyanurate.

Next, the cured flame-retardant composite material according to the second aspect of the present invention will be described. This cured flame-retardant composite material is obtained by curing the flame-retardant composite material described as the first of the present invention by a method such as heating, and includes (a) a functionalized polyphenylene ether resin composition, ( b) triallyl isocyanurate and / or triallyl cyanurate,
A cured product of a curable flame-retardant resin composition containing (c) brominated diphenyl ether, and (d) an antimony-based flame retardant aid, and a substrate.

Regarding the fact that the resin component of the cured flame-retardant composite material is a functionalized polyphenylene ether resin composition and a cured composition of triallyl isocyanurate and / or triallyl cyanurate, for example, IR spectrum Method, solid high resolution nuclear magnetic resonance spectroscopy (so-called CP-MAS), pyrolysis gas chromatography and other analytical techniques.

The qualitative and quantitative analysis of bromine and antimony, which are flame-retardant components in the cured flame-retardant composite material of the present invention, can be carried out by a method such as a fluorescent X-ray method or an emission analysis method. After decomposing with the composite material, heat, acid or the like, it is also possible to analyze using a technique such as titration, ion chromatography, atomic absorption and the like.

A part of bromine in the cured flame-retardant composite material of the present invention is derived from brominated diphenyl ether added as a flame retardant. On the other hand, the remaining bromine is bromine covalently bonded to the polyphenylene ether skeleton constituting the cured product, and is substantially derived from the structure of the above structural formula (III). These can be verified by the analysis of the chloroform extract described below.

The preferred value range of the chloroform extraction rate of the cured flame-retardant composite material of the present invention is 0.01% by weight or more and 10% by weight or less,
It is more preferably 0.01% by weight or more and 5% by weight or less. 0.
If it is less than 01% by weight, the cured product becomes brittle, which is not preferable. On the other hand, when it exceeds 10% by weight, the chemical resistance is insufficient, which is also not preferable. The chloroform extraction rate here means the cured flame retardant composite material in chloroform at 23 ° C.
It is a value obtained by soaking for 12 hours, and is calculated according to the following formula based on the weight of the resin component excluding the base material before being soaked in chloroform.

The shape of the cured flame-retardant composite material dipped in chloroform is preferably a film or powder in consideration of the ease of removing chloroform.

Chloroform extraction rate can be measured by using deuterated chloroform instead of chloroform. In this case, it is possible to know the components of the extract and its structure by measuring the NMR spectrum of the deuterated chloroform solution of the extract. it can. This extract is a component extracted from the resin components of the flame-retardant composite material described in the first aspect of the present invention, which could not sufficiently contribute to the curing reaction in the curing process. Therefore, in the extract, as the structure derived from the component (a) in the flame-retardant composite material, the above-mentioned formula (I) and / or (I
The units represented by I) and (III) are confirmed. In addition, triallyl isocyanurate and / or triallyl cyanurate which is the component (b) is also confirmed in the extract. Furthermore, brominated diphenyl ether which is the component (c) may be confirmed in the extract.

As a means for confirming the structure of the extract, the NMR spectrum method is effective as described above, and among them, ¹ H-NMR is particularly effective. The IR spectrum method can also be used.

The method for producing the cured flame-retardant composite material of the present invention by the flame-retardant composite material described as the first of the present invention is not particularly limited. For example, a plurality of the flame-retardant composite materials are overlapped, each layer is adhered under heat and pressure, and at the same time heat-cured,
A cured flame retardant composite material having a desired thickness can be obtained.
When laminating, a resin composition formed of the resin composition comprising the components (a) to (d) described in the first aspect of the present invention in a film shape may be used in combination with the flame retardant composite material. It is also possible to obtain a cured flame-retardant composite material having a new layer constitution by combining a cured flame-retardant composite material and a flame-retardant composite material and / or a film of the above resin composition which have been adhesively cured once.

The lamination molding and curing are usually performed simultaneously by using a hot press or the like, but both may be performed independently. That is,
The uncured or semi-cured composite material obtained by laminating in advance can be cured by heat treatment or by another method. Mold and cure at a temperature of 10
0-350 ° C, pressure 0.1-1000Kg / cm ² , time 1 minute-5 hours, more preferably temperature 150-300 ° C, pressure 1-500K
It may be carried out in the range of g / cm ² and time of 1 minute to 3 hours.

The mixing ratio of the base material and the resin component in the cured flame-retardant composite material of the present invention is not particularly limited, but the base material is 5 to 90% by weight, more preferably 10 to 80% by weight, and further preferably
95 to 10% by weight, more preferably 90 to 20% by weight, further preferably 80 to 30% by weight, based on 20 to 70% by weight
It is good to say When the amount of the base material is less than 5% by weight, the dimensional stability and strength of the cured flame retardant composite material are insufficient, and when the amount of the base material is more than 90% by weight, the dielectric property and flame retardancy of the cured flame retardant composite material. Is inferior and is not preferable.

Summarizing the characteristics of the cured and flame-retardant composite material according to the second aspect of the present invention described above, the first characteristic is flame retardancy due to the effects of bromine in the polyphenylene ether skeleton, the flame retardant, and the flame retardant aid. Is.

The second feature of the present invention is chemical resistance and heat resistance obtained by curing. That is, there is no change in appearance such as swelling or warpage due to boiling in trichlorethylene,
No change in appearance was observed even when heated in the solder bath.

The third feature of the present invention is that the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether are not impaired.

The fourth characteristic is that it is excellent in mechanical strength and dimensional stability (X-Y and Z directions).

Further, since the curing reaction in the present invention occurs by an addition reaction of an allyl group or a propargyl group in the functionalized polyphenylene ether resin composition and an allyl group in triallyl isocyanurate and / or triallyl cyanurate, the curing reaction is similar to that of a polyimide resin. In addition, by-products such as water and gas due to the condensation reaction are not generated, and uniform and void-free films, sheets and molded products can be obtained.

Finally, the third embodiment of the present invention will be described. This laminate is a laminate composed of the cured flame-retardant composite material and the metal foil described above as the second aspect of the present invention. Examples of the metal foil used in the present invention include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200
μm, more preferably 5 to 100 μm.

The method for obtaining the laminate of the present invention is not particularly limited, but for example, a plurality of the flame-retardant composite material of the first aspect of the present invention and a metal foil are laminated in a layered structure according to the purpose, and heated under pressure. It can be obtained by bonding each layer and at the same time performing heat curing. At this time, the metal foil can be attached to the surface layer or can be used as an intermediate layer.
Further, the resin composition formed of the components (a) to (d) described in the first aspect of the present invention, which is formed into a film, may be used in combination with the flame retardant composite material. Furthermore, it is also possible to obtain a laminate having a new layer structure by laminating the laminates that have been adhesively cured once, or laminating the laminate and the metal foil via the resin composition film or flame retardant composite material. Is. An adhesive may be used to bond the metal foil. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited thereto.

The lamination molding and curing are usually performed simultaneously by using a hot press or the like, but both may be performed independently. That is,
The uncured or semi-cured laminate obtained by laminating in advance can be cured by heat treatment or another method. Mold and cure at a temperature of 100
To 350 ° C, pressure 0.1 to 1000 Kg / cm ² , time 1 minute to 5 hours, more preferably temperature 150 to 300 ° C, pressure 1 to 500 Kg /
It may be carried out in the range of cm ² and time of 1 minute to 3 hours.

The mixing ratio of the base material and the resin component in the laminate of the present invention is not particularly limited, but the base material is 5 to 90% by weight, more preferably 10 to 80% by weight, further preferably 20 to 70% by weight.
On the other hand, the resin component is 95 to 10% by weight, more preferably 90 to
The amount is preferably 20% by weight, more preferably 80 to 30% by weight.

When the amount of the base material is less than 5%, the dimensional stability and strength of the laminate are insufficient, and when the amount of the base material is more than 90% by weight, the dielectric properties and flame retardancy of the laminate are poor, which is not preferable.

Since the laminated body of the present invention is a laminated body composed of the cured flame-retardant composite material and the metal foil described as the second of the present invention, its characteristics and the analysis method are as described in the second section of the present invention. Is.

The characteristics of the laminated body which is the third aspect of the present invention described above are the same as the characteristics of the cured flame-retardant composite material described in the second aspect of the present invention.

That is, the first feature is flame retardancy, the second is chemical resistance and heat resistance, the third is excellent dielectric properties, the fourth is mechanical strength and dimensional stability, and the fifth is The point is that a molded product that is uniform and void-free can be obtained.

In addition to these, the laminate of the present invention was also excellent in adhesiveness to the metal foil.

All of the above features show that this laminate can be advantageously used as a printed circuit board material, especially as a material for multilayer boards.

〔Example〕

Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, but the scope of the present invention is not limited to these examples.

Example 1 Functionalized polyphenylene ether resin composition Viscosity number η _sp measured at 30 ° C. in a 0.5 g / dl chloroform solution
/ C is 0.56 and 210 g of poly (2,6-dimethyl-1,4-phenylene ether) is dissolved in 7.0 l of tetrahydrofuran (hereinafter abbreviated as THE), and n-butyllithium (1.5 mol / l, hexane solution) ) Add 300 ml and add 40
The reaction was carried out at 0 ° C for 3 minutes. Subsequently, 38 ml of allyl bromide was added, and the mixture was stirred at 40 ° C for another 30 minutes. Finally 2.8 liters of water
A mixed solution of 2.8 l of methanol and methanol was added to precipitate a polymer. After repeating filtration and washing with methanol 5 times, 80 ℃
After vacuum drying for 14 hours, a white powdery polymer was obtained.
The analytical values of this polymer are summarized in Table 1. Each value was obtained by the following method.

1. Viscosity number η _{sp /} C: Chloroform solution at 30 ℃, 0.5g / dl 2. Bromine content: fluorescent X-ray method 3. Allyl group content: ¹ H-NMR flame retardant composite material Polymer obtained by the above method 140 g, triallyl isocyanurate (hereinafter abbreviated as TAIC) 7.4 g, 2,5 as an initiator
-Dimethyl-2,5-di (t-butylperoxy) hexyne-3 (Perhexin 25B manufactured by NOF CORPORATION) 4.4 g, tetrapromodiphenyl ether (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
SR-900) 14.7 g, Sb ₂ O ₃ PATOX-M) manufactured by Nippon Seiko Co., Ltd. 2.
9 g was uniformly dissolved and dispersed in 800 ml of trichlorethylene. A glass cloth having a basis weight of 48 g / m ² was immersed in this solution for impregnation, air-dried at 23 ° C. for 12 hours, and further vacuum dried at 80 ° C. for 8 hours. The weight fraction of glass cloth of the obtained curable composite material was 35%. This flame-retardant composite material had excellent surface smoothness and was non-sticky. Further, even when left at room temperature for 3 months, gelation did not occur and it was excellent in long-term storage stability.

Laminated bodies are laminated with a predetermined number of flame-retardant composite materials obtained by the above method,
Put 35μm copper foil on both sides and heat compress it from room temperature to 200 ℃ at a pressure of 100Kg / cm ² by a press molding machine,
After holding for 30 minutes, the mixture was cooled to obtain a laminate having a thickness of about 1.6 mm.
The physical properties of this laminate are summarized in Table 2. The measurement of each physical property was performed by the method described below.

1. Chloroform extraction rate A part of the laminate was ground and powdered, immersed in chloroform at 23 ° C for 12 hours, and the weight before and after that was calculated according to the following formula.

2. Flame retardance A test piece having a length of 127 mm and a width of 12.7 mm was cut out and tested in accordance with the test method of UL-94.

3. Trichlorethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the weight increase 5 minutes after removal was calculated from the following formula. Further, the change in appearance was visually observed.

4. Dielectric constant and dielectric loss tangent were measured at 1MHz.

5. Solder heat resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, floated in a solder bath at 260 ° C for 120 seconds, and the change in appearance was visually observed.

6. Copper foil peeling strength A test piece with a width of 25 mm and a length of 100 mm is cut out from the laminate, and after making a parallel cut with a width of 10 mm on the copper foil surface, 50 mm / min in the direction perpendicular to the surface. The copper foil was continuously peeled off at the speed of, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown.

As shown in Table 2, all physical properties were good.

On the other hand, in order to confirm the structure of the resin component after curing, the following analysis was performed.

First, FT-IR (diffuse reflection method) of the powdered laminate was measured to confirm the presence of the polyphenylene ether skeleton. The attribution of the main peak was as follows.

At the same time, the absorption of the carbonyl group due to TAIC was confirmed at 1700 cm ^-1 .

Moreover, in the measurement of pyrolysis gas chromatography (pyrolysis condition: 590 ° C., 4 seconds), TAIC and 2-methylphenol, which is a pyrolysis product specific to polyphenylene ether, 2,6
-Dimethylphenol, 2,4-dimethylphenol and 2,4,6-trimethylphenol were confirmed. The gas chromatograph peaks were identified using commercially available reagents as standards, retention time, mass spectrum, and FT-IR.
This was done by comparing the spectra.

The powdered laminate was then placed in deuterated chloroform (CDCl ₃ ) to give 2
Soaking was performed at 3 ° C for 12 hours for extraction. This deuterated chloroform solution was transferred to an NMR sample tube and ¹ H-NMR was measured. As a result, the peaks and T characteristic of the above structural formulas (I) to (III) and T were measured.
The peak of the AIC allyl group was confirmed. The attributions of the main peaks are as follows.

Examples 2 to 7 Functional polyphenylene ether resin composition The analytical values are summarized in Table 1. All were prepared by the same method using the same polymer as in Example 1.

Flame-retardant composite material Example 1 with the composition shown in Table 1 using the above polymer
Impregnation was performed in the same manner as in. The following flame retardants were used.

Hexabromodiphenyl ether: Mitsui Toatsu Co., Ltd.
HB-60P Octabromodiphenyl ether: manufactured by Ethyl Corporation Saytex 111 Decabromodiphenyl ether: manufactured by Asahi Glass Co., Ltd. AFR1
[021] In Example 2, a glass cloth having a basis weight of 105 g / m ² was used, and in Examples 3 to 5, a glass cloth having a basis weight of 48 g / m ² was used.
The unit weight is 205 g / m ² of glass cloth, and the unit weight is 1 in Example 7.
05 g / m ² of quartz cloth was used.

In all cases, the film forming property and the storage stability were good.

Cured Flame Retardant Composite Material and Laminate The flame retardant composite material obtained above was press cured as in Example 1. In Example 5, no copper foil was used, and in other cases, 35 μm copper foil was used for both surface layers, and heat compression was performed at a pressure of 100 Kg / cm ² and the temperature and time shown in Table 2.

The physical properties were measured according to the methods described in Example 1, and good values were obtained as summarized in Table 2.

Also, the structural analysis of the resin component after curing could be performed in the same manner as in Example 1 by using FT-IR, pyrolysis gas chromatography, and ¹ H-NMR.

Examples 8,9 Functionalized polyphenylene ether resin composition 2,2-bis (3,5-dimethyl-4-hydroxyphenyl)
Polyphenylene ether having hydroxyl groups at both ends obtained by oxidative polymerization of 2,6-dimethylphenol in the presence of propane (viscosity number η _sp /c=0.40 measured at 30 ° C, 0.5g / dl chloroform solution) ) 210 g was dissolved in THF 7.0 l,
-Butyllithium (1.5 mol / l, hexane solution) (350 ml) was added, and the mixture was reacted under a nitrogen atmosphere at 40 ° C for 5 minutes. Subsequently, 40.0 ml of propargyl bromide was added, and the mixture was stirred at 40 ° C for another 30 minutes. Post-treatment was carried out in the same manner as in Example 1 to obtain a white powdery polymer. The analytical values of this polymer are summarized in Table 1.

Flame-retardant composite material Using a glass cloth having a basis weight of 48 g / m ² , impregnation was performed in the same manner as in Example 1 with the composition shown in Table 1. Both films had good film-forming properties and storage stability.

Cured Flame Retardant Composite Material and Laminate The flame retardant composite material obtained above was press molded and cured in the same manner as in Example 1. Pressure is 100Kg / cm ² , temperature, time,
The presence or absence of copper foil is as shown in Table 2.

Next, the physical properties were measured according to the method described in Example 1, and the second
As shown in the table, both obtained good values.

Also, the structural analysis of the fat component after curing could be performed in the same manner as in Example 1 by using FT-IR, thermal decomposition gas chromatography, and ¹ H-NMR.

Comparative Examples 1 and 2 As shown in Table 1, the same measurement was repeated without using the flame retardant and the flame retardant auxiliary. In Comparative Example 2, using only the flame retardant,
No flame retardant aid was used. The flame retardancy was remarkably inferior in all cases.

Comparative Example 3 The reaction condition of n-butyllithium in Example 1 was set to 40.
The reaction was performed in exactly the same manner except that the temperature was changed from 3 minutes to 40 ° C. for 1 hour. The analytical values of the obtained polymer are shown in Table 1. No bromine was detected in this polymer as determined by fluorescent X-ray method. Using this polymer, a laminate was prepared with the same composition and method as in Example 3, and the physical properties were measured. The results are summarized in Table 2. Although the same amount of flame retardant was used, the flame retardancy was inferior to that of Example 3.

Of the cured flame-retardant composite materials or laminates obtained in Examples 1 to 9 above, the tensile strength, the bending strength, and the linear expansion coefficient (X-Y direction and Z) of the two types of Examples 2 and 9 were used. Direction) was measured. The results are summarized in Table 3. All had sufficient strength and were excellent in dimensional stability.

[Effects of the Invention] When the features of the flame-retardant composite material according to the first aspect of the present invention are summarized, firstly, the point of excellent flame retardancy can be mentioned. The functionalized polyphenylene ether resin composition used in the present invention has an advantage that excellent flame retardancy can be exhibited by adding a smaller amount of flame retardant because bromine is introduced into the molecular skeleton. Further, generally, in a system in which a resin and a base material are combined, the flame retardancy is significantly reduced as compared with the case where only the resin is used. However, in the present invention, by optimizing the combination of the flame retardant and the flame retardant auxiliary, it has succeeded in imparting excellent flame retardancy without deteriorating other physical properties at all.

The second feature of the present invention is that it is excellent in film forming property by the casting method. For example, poly (2,6-dimethyl-
Generally, widely used polyphenylene ethers such as 1,4-phenylene ether) have almost no solvent film-forming property, so that even if mixed with triallyl isocyanurate and / or triallyl cyanurate, a complex surface is obtained. You cannot get the material. On the other hand, with the functionalized polyphenylene ether resin composition used in the present invention, a composite material having excellent surface properties could be obtained because of its extremely excellent film-forming property. Moreover, there was no stickiness on the surface and it was easy to handle.

The third feature of the present invention is that it has excellent storage stability.
It could be stored at room temperature for 3 months without gelation.

The fourth feature of the present invention is that the glass transition temperature is low and the fluidity is excellent, so that thermoforming is easy to perform. This is because triallyl isocyanurate and / or triallyl cyanurate exerts an effect as a plasticizer.

Summarizing the cured and flame-retardant composite material according to the second aspect of the present invention,
First and foremost is its excellent flame retardancy. For this,
It is as described as the first feature of the flame-retardant composite material.

The second feature of the present invention is chemical resistance and heat resistance obtained by curing. That is, there is no change in appearance such as swelling or warp due to boiling in trichlorethylene,
No change in appearance was observed even when heated in a solder bath at ℃.

The third feature of the present invention is that the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether are not impaired.

The fourth feature of the present invention is that it is excellent in mechanical strength and dimensional stability (XY direction and Z direction).

Furthermore, since the curing reaction in the present invention occurs by an addition reaction of an allyl group or propargyl group in the functionalized polyphenylene ether resin composition and an allyl group in triallyl isocyanurate and / or triallyl cyanurate, the curing reaction is similar to that of a polyimide resin. In addition, by-products such as water and gas due to the condensation reaction are not generated, and uniform and void-free films, sheets and molded products can be obtained.

Finally, as the characteristics of the laminated body which is the third aspect of the present invention, the characteristics of the second cured flame-retardant composite material of the present invention are directly applied. That is, the first feature is excellent flame retardancy, the second is excellent chemical resistance and heat resistance, the third is excellent dielectric properties, and the fourth is mechanical strength and dimensional stability. Can be mentioned. In addition to these, the laminate of the present invention was also excellent in adhesiveness to the metal foil.

All of the above-mentioned features of the present invention show that the present invention can be advantageously used as a low dielectric constant printed circuit board material. In particular, since it has excellent film forming properties, moldability, and dimensional stability in the Z direction, it can be advantageously used as a material for flexible substrates, three-dimensional printed substrates by injection molding, single-sided or double-sided copper-clad laminates, prepregs for multilayer substrates, and the like. . Other applications include semiconductor encapsulation materials, satellite broadcast antenna substrates, VLSI insulating films, microwave oven materials, heat-resistant adhesives, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08K 5/3477

Claims (3)

[Claims] 1. A flame-retardant composite material comprising a curable flame-retardant resin composition and a base material, wherein the curable flame-retardant resin composition comprises (a) a polyphenylene ether resin and allyl bromide and / Or a functionalized polyphenylene ether resin composition comprising a reaction product of propargyl bromide, wherein bromine and allyl groups and / or propargyl groups are covalently bonded to the polyphenylene ether resin, and the bromine content is 1% by weight. % Or more and 30% by weight or less, and the content of allyl group and / or propargyl group defined by the following formula is 0.1 mol% or more and 100 mol% or less, and a functionalized polyphenylene ether resin composition and (B) triallyl isocyanurate and / or triallyl cyanurate, and (c) a brominated flame retardant represented by the following formula, and (In the formula, m and n are integers of 1 to 5 and 4 ≦ m + n ≦ 10.) And (d) an antimony-based flame retardant auxiliary is contained, and the sum of (a) and (b) is included. 98 to 40 parts by weight of component (a) and 2 to 60 parts of component (b) based on 100 parts by weight
1 part by weight to 40 parts by weight of the component (c) and 0.1 parts by weight of the component (d).
Flame-retardant composite material, characterized in that it is up to 40 parts by weight. 2. A cured flame-retardant composite material comprising a cured product of a flame-retardant resin composition and a substrate, wherein (i) the cured product of the flame-retarded resin composition is a functionalized polyphenylene ether resin composition. And a cured product obtained by curing a resin composition comprising triallyl isocyanurate and / or triallyl cyanurate, and containing a bromine-based flame retardant and an antimony-based flame retardant represented by the following formula: Cage, (In the formula, m and n are integers of 1 to 5 and 4 ≦ m + n ≦ 10.) (Ii) The flame-retardant composite material is mixed with chloroform at 23 ° C. for 12 hours.
Chloroform extraction rate after time treatment is 0.01 wt% or more and 10 wt% or less based on the flame-retardant resin composition cured product, and (iii) a unit represented by the following structural formula in the chloroform extract (I) and / or (II), and (III)
Is included. A cured flame-retardant composite material characterized by the following. (In the formula, R represents an allyl group and / or a propargyl group.) 3. A laminate comprising a cured flame-retardant composite material obtained by compounding a cured product of the flame-retardant resin composition and a substrate, and (i) curing the flame-retardant resin composition. Is a functionalized polyphenylene ether resin composition and a cured product obtained by curing a resin composition comprising triallyl isocyanurate and / or triallyl cyanurate, and a brominated flame retardant represented by the following formula: Contains antimony flame retardant aid, (In the formula, m and n are integers of 1 to 5, and 4 ≦ m + n ≦ 10.) (Ii) Chloroform extraction rate when the laminate is treated with chloroform at 23 ° C. for 12 hours is flame retardant. 0.01 wt% or more and 10 wt% or less based on the cured resin composition cured product,
And (iii) the units (I) and / or (II) and (III) represented by the following structural formula in the chloroform extract:
Is included. A laminated body characterized by the above. (In the formula, R represents an allyl group and / or a propargyl group.)