JPH03181548A - Resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent heat-resistance and flame-retardance and suitable for the production of laminated sheet for electric use by compounding an allyl ester resin with a specific amount of a specific halogen-containing compound. CONSTITUTION:The objective composition is produced by compounding (A) 20-85wt.% (preferably 25-80wt.%) of an allyl ester resin with (B) 80-15wt.% (preferably 75-20wt.%) of an addition-type flame-retarding compound containing bromine or chlorine (e.g. monobromobenzene, bromophenone or chlorinated paraffin).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a resin for laminates suitable for manufacturing electrical laminates used particularly for electrical equipment, electronic equipment 2g, communication equipment 2, etc. Regarding the composition.

``Prior Art'' Typical resins used in electrical laminates are fer/fell resin, epochene resin, and unsaturated polyester resin, which are used in combination with various base materials.

However, phenolic resin has problems with the generation of reaction by-products during curing and the removal of solvents, so EBOKI/131. As with the fingers, there is a problem with removing the solvent. Unsaturated polyester resin does not have these problems and is a radical curing type and easy to use, but it also has poor heat resistance, fl, M! It is difficult to obtain a laminate with a well-balanced combination of both properties, and is currently a major challenge.

For example, as shown in Japanese Patent Publication No. 1-13418, unsaturated polyester resin N'N containing aliphatic bromine and/or alicyclic bromine and aromatic bromine in the unsaturated polyester resin is Although some proposals have been made, it cannot be said that the problem has been fully resolved.

``Problems to be Solved by the Invention'' The problem of the present invention is to provide a radical-curable laminate resin composition suitable for manufacturing electrical laminates that has both high flame retardancy and excellent heat resistance. The purpose is to provide.

"Means for Solving the Problems" As a result of efforts made by the present inventors to achieve these objectives, the present inventors have found that by using a resin We completed this research by discovering that it is possible to make electrical laminates and other laminates with clear flammability.

That is, the gist of the present invention is that allyl ester resins 20 to 85
wt%, additions containing bromine or chlorine j1! ! There is a resin phase composition 51'yJ for disease-prone boards which contains 80 to 15 wt% of a flame retardant compound.

The present invention will be explained in detail below.

The allyl ester resin referred to in the present invention refers to saturated polysalt J, (
Consisting of acid and 1rl poly(f+15) alcohol, allyl ester + polyester wood ζW5,
(This refers to the resin that produces

Examples of the above-mentioned saturated polybasic acids include di-salts), (acids such as orthophthalic acid, orthophthalic anhydride, isophthalic acid, phthalic acids such as terephthalic acid, tetrahyphthalic acid, methyltetrahydrophthalic acid, and endomethylenethiol).
・Hydrophthalic acids such as rahydrophthalic acid, methyleth, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhex→hydrophthal Qti, TiU, their acid anhydrides, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, etc. , tetrabromophthalic acid, tetrachlorophthalic acid, chlorendic acid, and halogenated dibasic acids such as acid hydrates thereof. Examples of trifunctional or higher-functional polybasic acids include trimellitic acid, viromenotic acid, and acid anhydrides thereof. These can be used alone or in combination.

In addition, the above-mentioned saturated polyhydric alcohols include ethylene glycol, 1, 2-7" propylene glycol, 14-butanediol, 1., 6-hexa/fall, neopentyl glycol, 1, 4-7 chlorohexanedimethanol, In addition to alcohols of the general formula H○ (CHRCH, O) containing aliphatic, alicyclic or aromatic compounds such as baraxylene glycol, H (R is 11 or C,
, l-(, , , m is an integer of 1 to 5, rl is an integer of 2 to 10) dihydric alcohols obtained by addition reaction of alkylene oxides such as ethylene oxide and propylene oxide. Examples of trihydric or higher polyhydric alcohols include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and polyhydric alcohols such as penquerythritol and norbitol. Examples include aliphatic, alicyclic, or aromatic halogenated polyhydric alcohols containing a halogen atom such as , cyphroneopentyl glycol, and tetrafluorobisphenol A with ethylene oxide.These include ( 11 can be used alone or in combination.

On the other hand, the additive type flame retardant compound containing bromine or chlorine as used in the present invention is a compound having one or several bromine atoms or chlorine atoms in the molecule, and is an additive type fat that does not radically combine. Refers to group-based, alicyclic, and aromatic hydrocarbon compounds. For example, substituted heynes such as monobromobenzene, dibromohenocene, triflomobenzene, and bromochlorobenzene; Substituted diphenyl ethers such as bromnophenyl ether, pentabrom diphenyl ether, hexabrom diphenyl ether, octafrom diphenyl ether, decabrom diphenyl ether, tetrabromo bisphenol A1, ethylene oxide adduct to tetrabromo bisphenol, tetrachlorobisphenol A1 brominated epoxy compound, Ethyl bromide, propyl bromide, butyl bromide, amyl bromide, hex/rubromide, octyl bromide, lauryl bromide, 7'bromopropane, dibromodecane, tetrachromomethane, tetrabromobutane, hexabromo/chlordodecane, dibromoneopentyl glycol, /bromo Propatool, shrimp bromohydrin, bromotoluene, pentabromotoluene, furomoki/ren, bromonaphthalene, chlorinated halafine,
Examples include, but are not limited to, chlorinated polyethylene, chlorinated polypropylene, perchloropentane clodecane, chlorendic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride M, fii polystyrene, polysifromof J nyl oxide, etc. do not have. These can be used either as a single insect or as a combination of insects.

Methods for producing allyl ester resins are already known, and are described, for example, in Mochiyori No. 63-262217. For example, allyl ester resin is produced by charging the diallyl ester of a saturated dibasic acid such as diallyl terephthalate 1 and a saturated polyhydric alcohol together with a transesterification catalyst into a reactor and reacting without distilling off the allyl alcohol. . A more industrially effective method is to use methyl terephthalate instead of diallyl terephthalate;
I (alkyl ester of acid, allyl alcohol, >
Reaction 2 with fr 7 alcohol and transesterification catalyst
It can be obtained by charging it into HH and reacting it while distilling off by-product alcohol such as methanol.

Also, depending on the reaction temperature]\π such as hydroquinone
In this case, a λ inhibitor may be present during reaction C. In this way, allyl ester 1 is added to the end of polyester.
．． It is possible to produce an allyl ester resin having (

The types of allyl ester resins that can be used in the resin composition of the present invention may be one type or a mixture of two or more types. By selecting various types of polyhydric acid and saturated polyhydric alcohol, it is possible to obtain a composition for a laminate with good electrical properties, flame retardance, etc. while maintaining heat resistance.

According to the study of the present inventor, by blending an additive type flame retardant compound containing bromine or chlorine, self-extinguishing property due to bromine or the chlorine can be expressed, while the same Because it is used in combination with N twisting agents, the degree of heat resistance deterioration such as voltage control characteristics, which is often a problem with N twisting agents, is small, and the laminates such as electrical laminates have excellent properties. can do.

The mixing ratio of the allyl ester resin and the additive flame retardant compound containing bromine or chlorine to be blended into the resin composition of the present invention can be adjusted as appropriate depending on the needs of the laminate performance, but it is preferably 20 to 85 wt% for allyl ester 461 tlM. for,
Additive flame retardant compound containing bromine or chlorine 80-15w
(%, more preferably allyl ester resin 25-80
QF is preferably 75 to 20 wt % of an additive flame retardant compound containing bromine or chlorine based on the wt %. Addition containing more than 80 wt% of bromine or chlorine to less than 20 wt% of allyl ester resin! j-1! , it is inconvenient to produce sufficient laminate strength when a female combustion compound is blended,
Furthermore, when an additive flame retardant compound containing less than 15 wt% of bromine or chlorine is blended with an allyl ester resin of more than 85 wt%, it is difficult to exhibit a high degree of flame retardancy. For example, in the case of paper yarn laminates, lamination after copper foil etching (when the resin content in the ash is 40 to 60 wt%,
By setting the resin to contain at least 4 to 5 wt% of aliphatic bromine, it is possible to exhibit a high degree of flame retardant effect, and it is suitable for laminating electrical laminates with poor mechanical and electrical properties. It is L″iJ ability to get a board.

Furthermore, in addition to the allyl ester resin and the additive type flame retardant compound containing bromine or chlorine, a phosphorus-based flame retardant can also be used in the resin composition of the present invention. Phosphorus 'f! 4 Twisting agents include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate-1, l-riphenyl phosphate,
Examples include tricresyl phosphate, tris (chlorethyl) phosphate, tris (dichloropropyl) phosphate, talenyl diphenyl phosphate, triphenyl decasphite, and the like. It is also possible to use antimony compounds such as antimony trioxide and antimony pentoxide, and non-synthetic flame retardants such as zinc borate and aluminum hydroxide.

Furthermore, in the resin composition of the present invention, in addition to 1. L allyl ester resin and the additive type flame retardant compound containing bromine or chlorine, a crosslinking monomer capable of carrying Rancal polycarbonate may be used as necessary. Any of the known ones can be used; for example, diallyl phthalates such as diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate; styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene; , fromstyrene, and substituted styrenes such as divinylbenzene (
Methyl acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (meth)
Acrylic acid or methacrylic esters such as ben/ru acrylate, fromated phenyl (meth)acrylic ester: ethylene glycol cyclo(meth)acrylate, 4-butanediol/(meth)acrylate]・
, totrimethylolpropane tocri(meth)acrylate, diacrylated inanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin(meth)acrylate-1-, neopentyl glycol di(meth) Acrylate, vinyl multifunctional acrylic acid or methacrylic esters such as bisphenol A di(meth)acrylate; polyurethane (meth)acrylate, polyether (meth)acrylate, epichlorohydrin-modified bisphenolba/(meth)acrylate, ethylene/oxide Vinyl polyfunctional oriconisters such as modified bisphenol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate are included.

Two or more of these crosslinking monomers may be used in combination depending on the purpose. By blending such a crosslinking monomer, it is possible to lower the viscosity of the allyl ester resin, which is originally a solid or viscous shell, and without having to prepare a prepreg using a solvent or the like. This is preferable because it allows the manufacturing process of the laminate to be simplified.

The resin composition of the present invention can be cured using a general-purpose organic peroxide, and may be used together with the organic peroxide or alone, such as a polymerization initiator that is sensitive to light, a polymerization initiator that is sensitive to radiation, or an electron beam. Known polymerization initiators can also be used.

Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone biside and acetylacetone oxide, I,1-bis(i-butylvaquine)3,3.5-)limethylcyclohexane, n-
Peroxide/ketals such as butyl-4,4-bis([butylperoquine)valerate], hydroperoxide compounds such as t-butylhydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and sheet t-butyl peroxide. oxide, dicumyl peroxide, 2,5-dimethyl-2,5-7(+-butyl peroxide/dialkyl peroxides such as hexane, lauroyl peroxide, benzoyl peroxide, etc.), di-1so-propyl Peroxy 7 carbonate, Dimyristyl carbonate, Bis(4-t-butyl/chlorohexyl/
Examples include peroxydicarbonates such as peroxydicarbonate, peroxyesters such as t-butyl peroxy/bibarate, t-funalperoxy 7-2-ethylhexanoate, and t-butyl peroxy/benzoate. . These can be one type or a mixture of two or more types,
It can be used depending on the type of resin and curing conditions.

In the present invention, it is also possible to further enhance the performance of the laminate by using fillers, reinforcing materials, mold release agents, coloring agents, curing agents, accelerators, stabilizers, etc. in combination with the resin composition as necessary. .

The resin composition of the present invention can be used in the production of laminates such as electrical laminates according to known isotropy. That is, a plurality of base materials are impregnated with the above-mentioned resin composition, and a plurality of 3D base materials are laminated, and in the case of a metal foil-clad laminate, metal foil is coated with a blue tint agent on one or both sides in advance, or is not coated. Electrical laminates can be produced by stacking, heating, curing, and forming without a bed or under pressure. At this time, the metal foil may be attached after the impregnated laminated base material is cured and molded. The above-mentioned base material can be the same as the base material used for conventional electrical laminates, such as glass base materials such as glass fiber cloth and glass non-woven fabric, kraft paper,
Refers to cellulose-based paper base materials such as linter paper and Konoton paper, and inorganic fiber-based materials in the form of or strips. When paper is used as the base material, from the viewpoint of d content and quality, paper mainly composed of cellulose fibers having a density of 0.3 to 0.7 g/cm3 when air-dried, such as kraft paper, is preferable.

Before impregnating these base materials with the resin composition of the present invention, they are pre-dry treated with N-methylol compounds such as urea resins, melamine resins, and guanamine resins, phenolic resins, and phosphoric acid soaking agents. By this, 1
It is also possible to aim for the direction -L of the air characteristics.

As the metal foil, electrolytic copper foil is commercially available for the purpose of forming a copper foil clad fa layer for electric circuits, and it is preferable to use this from the viewpoints of 61 etchability, etching resistance, and mounting resistance. . The thickness of the metal foil is preferably about 10 to 100 μm.

Metal foil and resin e&? In order to effectively achieve adhesion between two substrates, it is preferable to use an adhesive, and as a bonding agent, it is preferable to use an adhesive that does not generate unnecessary side reaction products during the curing process.
It is preferable to use it in an IT state or a semi-liquid state. From this point of view, acrylate adhesives, epoxy adhesives, epoxy acrylate adhesives, isonanate adhesives,
Alternatively, various modified adhesives may be used.

The thickness of the laminate thus obtained depends on the type of base material,
Although it varies depending on the composition of the cured compound resin acid and the use of the laminate, it is usually 0.5 to 5 mm. Further, the proportion of the resin composition in the laminate is 30 to 80 wt%.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples unless it departs from the gist of the present invention. Throughout this specification, all temperatures are in degrees Celsius, and parts and percentages are by weight unless otherwise specified.

"Example" Production Example 1 Production of allyl ester resin (1) Into 11 reactors equipped with a distillation apparatus, 60
0g (2,44mo(ri), propylene glycol 9
5.9 g (2,4 ]moc) After distillation, the pressure inside the reactor was reduced to 5011 ml 1 g to accelerate the distillation rate.After allyl alcohol equivalent to propylene glycol was distilled out, the reaction liquid was distilled using a thin film distiller to
Unreacted diallyl terephthalate was distilled off at 11 g of I mm while maintaining the temperature at 0'C. Pour the reaction solution into a vat, cool and crush to obtain powdered allyl ester resin (1
) to f, :, ), iko.

4] Ml 2- Notice for the manufacture of allyl ester resin (2) containing bromine Except for the conditions shown in Table 1, allyl ester resin (1
) to obtain a bromine-containing allyl ester resin (2).

Examples 1-5 I flat tl l 55 g/m2, thickness 300 μm
kraft paper with melamine resin (Japan Carbide L [5-
305) Soak in water-methanol solution and squeeze with a roller, 12
It was dried for 130 minutes at 0"C. The resulting paper base material contained 15% of melamine resin and turned blue. This paper base material was coated with the resin composition shown in Table 2. The resin solution was applied from one side of the lf wall. 7 sheets are superimposed, and one side is coated with copper foil (
MK-61) made by Mikata Metal Mining Co., Ltd.
After laminating a μm polyester film, it was heated and pressure-molded using a press machine. Heating and pressurizing conditions are 140°C
130 minutes, 30 kg/cm”. After pressing,
Heating was carried out in a hot air drying oven at 150°C for 5 hours to obtain a copper foil-clad laminate having a thickness of I and 6 mm. The test results of the copper foil clad laminate are shown in Table 3.

Comparative Examples 1 to 4 Copper foil-clad laminates were produced in the same manner as Examples 1 to 5, except that the blended resin compositions of the comparative examples shown in Table 2 were used. The test results of the copper foil clad laminate are shown in Table 3.

Comparative Example 5 Commercially available paper phenol copper foil clad laminate (thickness (,6+nm
, XPC grade) were tested for physical properties in the same manner as in the examples. The test results are shown in Table 3.

As is clear from Table 3, the electrical laminate obtained from the resin composition containing an allyl ester resin and an additive flame retardant compound containing bromine or chlorine is the unsaturated polyester resin laminate of Comparative Example 1.2. Higher heat resistance than the board, Comparative Example 5
It has better electrical properties than phenolic resin-based laminates.

"Effects of the Invention" As is clear from the above description, the resin composition for lamination of the present invention contains 20 to 85 wt% of allyl ester resin and 80 = 15 wt% of an additive flame retardant compound containing bromine or chlorine.
%, it has excellent external resistance and flame retardancy.
Furthermore, it is possible to obtain electrical laminates such as copper foil-clad laminates that fully satisfy other characteristics.

Outsourcer: Showa Denko Co., Ltd.

Claims (1)

[Claims] A resin composition for a laminate, characterized in that 80 to 15 wt% of an additive flame retardant compound containing bromine or chlorine is blended to 20 to 85 wt% of an allyl ester resin.