JPH04161454A - Polyphenylene oxide-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of providing laminated boards remarkably improved in bleeding properties, adhesion to metallic foils and moldability by blending triallyl isocyanurates (prepolymer) with a crosslinking polymer, toluene, etc. CONSTITUTION:A resin composition is obtained by blending a polyphenylene oxide with triallyl isocyanurates, prepolymer thereof, a crosslinking polymer and toluene and trichloroethylene as solvents. The toluene is blended as a reaction solvent in polymerizing the triallyl isocyanurates into the prepolymer and the trichloroethylene is blended as a diluting solvent. Furthermore, a flame retardant is blended. The polyphenylene oxide preferably has about 50000 weight-average molecular weight (Mw) and 4.2 molecular weight distribution (Mw/Mn).

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a polyphenylene oxide resin composition used for manufacturing laminates.

[Conventional technology]

For circuit boards such as printed wiring boards used in precision instruments, electronic computers, communication devices, etc., there are increasing demands for faster calculation processing, higher reliability, higher circuit density, and smaller size.
In order to meet these demands, multilayering of circuits and miniaturization of circuits are rapidly progressing. Conventionally, epoxy resin, epoxy resin,
Polyimide resin, fluororesin which is a low dielectric constant resin, polybutadiene resin, etc. are used. However, these resins cannot sufficiently satisfy the various properties required for high-density wiring boards, and for this reason polyphenylene oxide has come to be used. This polyphenylene oxide is a resin that has a relatively high glass transition temperature, low dielectric constant, and low dielectric loss. In order to further enhance the low dielectric constant properties of this polyphenylene oxide, triallyl in cyanurates are blended with polyphenylene oxide.

[Problem to be solved by the invention]

However, when manufacturing a laminate using a polyphenylene oxide resin composition prepared by blending triallyl isocyanurate with polyphenylene oxide, triallyl isocyanurate is
Alternatively, it is blended as a prepolymer, but when it is blended with a monomer, there is a problem with bleedability, and when it is blended with a prepolymer, there are problems with the adhesion with metal foil and moldability. The present invention has been made in view of the above points, and an object of the present invention is to provide a polyphenylene oxide resin composition that has improved bleeding properties, adhesion properties, and moldability.

[Means to solve the problem]

The polyphenylene oxide resin composition according to the present invention is characterized by being blended with polyphenylene oxide, triallyl isocyanurates, a prepolymer of triallyl isocyanurates, a crosslinkable polymer, and toluene and trichloroethylene as solvents. It is something. The present invention will be explained in detail below. The polyphenylene oxide used in the present invention is
For example, it is represented by the following general formula (1), and specific examples include poly(2,6-dimethyl-1,4-)unilene oxide) and poly(3,5-dimethyl-1,4-). −
(phenylene oxide), etc. RR (wherein R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms,
Each R may be the same or different) The molecular weight of this polyphenylene oxide is not particularly limited, but the weight average molecular weight (M w )
is about 50,000, molecular weight distribution M w / Mn = 4.2
(Mn is number average molecular weight) is preferable. Such polyphenylene oxides, such as poly(2
, 6-dimethyl-1,4-phenylene oxide) is
It can be obtained by subjecting 2.6-xylenol to an oxidative coupling reaction with an oxygen-containing gas and methanol in the presence of a catalyst. Here the catalyst is #! l) Compound, N'. N'-di-ter-butylethylenediamine, butyldimethylamine, hydrogen bromide, and the like can be used. Further, methanol can be used by adding 2 to 15% by weight of water based on methanol so that the total amount of water and methanol becomes a mixed solvent of 5 to 25% by weight. Further, as the triallyl isocyanurates used in the present invention, triallyl isocyanurate and triallyl cyanurate can be used. Further, triallyl in cyanurates are those in which a monomer and a prepolymer are used in combination. A prepolymer of triallyl isocyanurates can be prepared by solution polymerization or bulk polymerization of monomers of triallyl in cyanurates. Solution polymerization is superior to bulk polymerization because the reaction is milder and the molecular weight can be easily adjusted. In this solution polymerization, triallyl cyanurate monomer and/or triallyl cyanurate monomer are dissolved in a solvent, a radical polymerization initiator is mixed in, and the mixture is reacted with stirring until an appropriate molecular weight is reached, followed by heating if necessary. It can be implemented by At this time, it is preferable to carry out the reaction using a reflux vessel and under a reaction atmosphere in which oxygen is not present, for example, under a flowing atmosphere of nitrogen.Here, in the present invention, the triallyl isocyanurate monomer Toluene is used as a solvent in which the monomers are dissolved and reacted. Toluene is preferred because it has little effect on the reaction. The use of carbon tetrachloride, dichloromethane, trichloroethane, etc. as a solvent has been considered, but chlorinated solvents are not preferred because they have a large effect on the reaction. In addition to these, it is also possible to use benzene, xylene, methanol, ethanol, acetone, methyl ethyl ketone, heptane, etc. Examples of the radical polymerization initiator include benzoyl peroxide, 2.
5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxybenzoate, dicumyl peroxide, etc. can be used. Next, a specific example of producing a triallyl isocyanurate prepolymer by polymerizing a triallyl isocyanurate monomer will be shown. (Production Example 1) 11 parts by weight of benzoyl peroxide and 600 parts by weight of toluene were added to 280 parts by weight of triallyl isocyanurate monomer, and the mixture was boiled for 6 hours under a nitrogen atmosphere using a reactor equipped with a stirrer and a reflux condenser. By reacting, a toluene solution of triallyl isocyanurate monomer and triallyl isocyanurate prepolymer was obtained. As a result of analysis, the reaction rate was 30%, and the number average molecular weight of triallylisocyanurate in the solution was about 3,000. (Production Example 2) Add 10 parts by weight of dicumyl peroxide and 527 parts by weight of toluene to 225 parts by weight of triallyl isocyanurate monomer, and then react in the same manner as in Production Example 1 above to form triallyl in cyanurate monomer and triallyl. A toluene solution of incyanurate prepolymer was obtained. The number average molecular weight of triallyl in cyanurate was about 4,000. In addition, triallyl cyanurate and triallyl in cyanurate are chemically structurally isomers, and in order to exhibit similar reactivity and polymer properties, they were prepared in the same manner as in Production Examples 1 and 2. It is also possible to react by mixing both triallyl isocyanurate and triallyl cyanurate. The number average molecular weight of the triallylisocyanurate monomer and prepolymer produced as described above is preferably set to 10,000 or less. In addition, in the present invention, examples of crosslinkable polymers include:
1. Modification by 2-polybutadiene, 1.4-polybutadiene, polystyrene, styrene-butadiene copolymer, maleic modification or acrylic modification or epoxy modification 1.
2-polybutadiene, rubbers, etc. can be used, and these can be used alone or in combination of two or more. The state of these polymers may be elasmer or rubber. In combination with these crosslinkable polymers, the following crosslinkable monomers can also be blended. That is, acrylates such as ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallylisocyanurate, ethylene glycol dimethacrylate, Polyfunctional monomers such as divinylbenzene and diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene and paramethylstyrene, and polyfunctional epoxies can be blended as crosslinking monomers, and these can be used alone. or two or more types can be used in combination. By blending a crosslinkable monomer in this manner, properties such as crosslinkability, adhesion, and heat resistance can be improved. Furthermore, in the present invention, a flame retardant and a flame retardant auxiliary agent can be blended together with the flame retardant. In this case, the flame retardant must be such that the dielectric constant of the polyphenylene oxide resin composition after addition does not exceed 40, and that its flame retardancy is V-1 or As such flame retardants, it is preferable to use those that can reduce the level to -0. or an aliphatic group), or a brominated polycarbonate flame retardant side represented by the following formula, CH,○ (in the formula, R represents hydrogen, an aromatic group, or an aliphatic group), or a brominated polycarbonate represented by the following formula. Bisphenol flame retardant, Hy CH. (In the formula, R1 and R2 each represent hydrogen, an aromatic group, an aliphatic group, or any group represented by the following formula -0-CH
2-CH=CH2 -O-Co-CH=CH2 -O-Co-C=CH2 □ CH. OCH2CH20Co CH=CH2-0-CH2-
CH2-0-Co-C=CH2 exposed CH. Furthermore, flame retardants of brominated cyanuric acid compounds represented by the following formula can be exemplified. These flame retardants may be used alone or in combination. By using a flame retardant aid together with this flame retardant, a synergistic effect can be brought about in improving flame retardancy. As this flame retardant aid, for example, antimony oxide (antimony trioxide, antimony pentoxide), zirconium oxide, sodium antimonate, etc. can be used. These alone are
Alternatively, two or more types can be used in combination. Incidentally, the flame retardant aid may be used as a flame retardant in some cases. Further, when using a flame retardant aid, it is preferable to disperse it in an organic solvent for ease of handling. Polyphenylene oxide based monomers, prepolymers, crosslinkable polymers, crosslinkable monomers used as necessary, flame retardants or flame retardants and flame retardant aids are blended with polyphenylene oxide as described above. A resin composition can be prepared, and at this time an initiator can be further added. As this initiator, the following two types can be selected depending on whether the polyphenylene oxide resin composition is an ultraviolet curing type or a thermosetting type. Of course, it goes without saying that it is not limited to these. First, as ultraviolet curing photoinitiators (that is, those that generate radicals when irradiated with ultraviolet light), benzoin,
Benzyl, allyldiazonium fluorobalate, benzyl methyl ketal, 2,2-jethoxyacetophenone, benzoyl inbutyl ether, p-ter-butyltrichloroacetophenone, benzyl (0-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, Benzophenone, Michlageton, tetraethylthiuram sulfide, azobisisobutyronitrile, and the like can be used. In addition, as thermosetting initiators (that is, those that generate radicals by heat), dicumyl peroxide, te
rt-butylcumyl peroxide, benzoyl peroxide, di-tert-dibutyl peroxide, 2
．． 5-dimethyl-2,5-di(tert-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, α, α'
-bis(tert-butylperoxy-m-isopropyl)benzene [1,4 (or 1,3>-bis(tert)
peroxides such as t-butylperoxyisopropyl) benzene, 1-hydroxycyclohexylphenyledone, 2-hydrolex-2-methyl-1-phenyl-propan-1-one, 1-(4- isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, methylbenzoylformate, 4,4-bisdimethylaminobenzophenone (Michlerageton), benzoin methyl ether, methyl-〇-benzoylbenzoate, α-Azyloxime ester, Biscumyl manufactured by NOF Corporation, etc. can be used. These initiators can be used alone or in combination of two or more. Further, an ultraviolet curing initiator and a thermosetting initiator can also be used together. The above polyphenylene oxide, triallylisocyanurate monomers and prepolymers, crosslinkable polymers,
The blending ratio of the crosslinking monomer, flame retardant, flame retardant aid, and reaction initiator is 5 to 95% by weight of polyphenylene oxide;
Triallyl isocyanurate monomer and prepolymer 1 to 95% by weight, crosslinkable polymer and crosslinkable monomer each 1 to 90% by weight, flame retardant 1 to 95% by weight, flame retardant aid 1
-50% by weight and 0-10% by weight of initiator are common. Note that the dielectric properties of the polyphenylene oxide resin composition according to the present invention can be changed by further blending various inorganic fillers. Examples of such inorganic fillers include titanium oxide ceramics, barium titanate ceramics, lead titanate ceramics, strontium titanate ceramics, calcium titanate ceramics, lead zirconate ceramics, etc. , or a combination of multiple types can be used. The above-mentioned polyphenylene oxide resin composition is used as a varnish that is diluted and dispersed with a solvent. ,
Resin solid content ranges from 10 to 13% by weight based on solvent)
It is preferable to adjust so that Here, in the present invention, trichlorethylene (triclene) is used as this dilution solvent. As mentioned above, in the present invention, toluene is used as a reaction solvent for reacting triallylisocyanurates, but if toluene is also used as a dilution solvent, the viscosity of the varnish of the resin composition increases and it becomes waxy. There is a risk of For this reason, in the present invention, trichlene is used as a diluent solvent that is free from the risk of such an increase in viscosity. Therefore, it is preferable to react the triallylisocyanurates with a toluene solvent, remove a portion (or all) of the toluene by distillation under reduced pressure, and then dilute with trichlene. The proportion of toluene in the varnish is 20
It is preferable to remove it so that it is less than % by weight. In addition to trichlene, trichloroethane,
It is also possible to use halogenated hydrocarbons such as chloroform, methylene chloride, and chlorobenzene, aromatic hydrocarbons such as benzene, toluene, and xylene, acetone, carbon tetrachloride, and the like alone or in combination. Next, the production of a laminate using a polyphenylene oxide resin composition prepared as a varnish as described above will be explained. First, a base material is immersed in a varnish of a polyphenylene oxide resin composition to impregnate and adhere to the base material, and then the solvent is removed by drying, etc., and the resin composition is half-coated. It is cured to B stage and prepreg is created. Examples of this base material include resin-impregnated loss-like materials such as glass cloth, aramid cloth, polyester cloth, and nylon cloth;
Mat-like materials, nonwoven fabrics, kraft paper, linter paper, and other papers made of these materials can be used. Further, the amount of the polyphenylene oxide resin composition impregnated into the base material is preferably adjusted to about 30 to 80% by weight as solid content. In the prepreg prepared in this way, if a bleed phenomenon occurs in which the low molecular weight triallylisocyanurate compounded in the polyphenylene oxide resin composition bleeds onto the surface of the prepreg, the prepreg may be stored in a loaded state. There is a risk that the prepregs may stick to each other when doing so, but the product of the present invention, in which triallyl isocyanurate is reacted with a toluene solution, has good bleedability (less occurrence of bleed).
, there is no risk of prepregs adhering to each other. Layer multiple sheets of prepreg prepared as described above, and if necessary, layer metal foil for circuit formation on one or both sides, and in some cases, layer a circuit board for the inner layer, and press it while heating. By doing so, a laminate can be manufactured. As the metal foil, for example, copper foil, aluminum foil, etc. can be used, but one with a smooth adhesive surface and good conductivity is preferable. The temperature and pressure during heat pressing are not particularly limited, but the heating temperature is higher than the glass transition temperature of the resin, for example 160 to 30
The temperature is preferably in the range of about 0°C, and the pressure is 30 to 80 kg.
A range of about /c1 is preferable. In addition, when crosslinking is carried out by placing the polyphenylene oxide resin composition in a dryer and heating it, the heating temperature and heating time may vary depending on the initiator, since the crosslinking reaction depends on the reaction temperature of the initiator, etc. For example, the temperature is 150-300°C and the time is 10-60°C.
It's a minute.

【Example】

Next, the present invention will be specifically explained using examples. 1λ↓ Prepare a toluene solution of triallylisocyanurate monomer and prepolymer by reacting triallylisocyanurate in a toluene solvent in the same manner as in <Production 11 MI). And this is 40~50℃, 300mH
It was distilled under reduced pressure under the conditions of g to remove part of the toluene and diluted with trichlene. The composition of this diluted solution (referred to as triallyl isocyanurate solution A) is: - Triallylisocyanurate monomer: 10% by weight - Triallylisocyanurate prepolymer: 30% by weight
Weight% Toluene: 10% by weight Trichlorene: 501% by weight. Furthermore, the weight average molecular weight of the triallyl isocyanurate monomer and prepolymer in this diluted solution was 12,000.
．． The number average molecular weight is 3000, and M w / M n
= 4. Next, while stirring, 30 parts by weight of polyphenylene oxide, 5 parts by weight of styrene-butadiene copolymer, 20 parts by weight of flame retardant, and 1.5 parts by weight of reaction initiator were added to 100 parts by weight of this solution, and the mixture was further stirred thoroughly. At the same time, the mixture was defoamed to obtain a flame-retardant polyphenylene oxide resin composition. A prepreg with a resin content of 60% by weight is produced by impregnating a glass cloth with the polyphenylene oxide resin composition obtained as described above using an impregnating device and drying it by heating at a temperature of 110°C for 7 minutes. I got it. Four sheets of this prepreg were stacked together, and electrolytic copper foil with a thickness of 18 μm was stacked on each side of the prepreg, and the temperature was 200℃ and 50kg/c.
■By molding for 30 minutes under the heat pressing conditions of 2.
A double-sided copper-clad laminate was obtained. In the same manner as in Production Example 1 above, triallyl isocyanurate was reacted in a toluene solvent to prepare a toluene solution of triallyl isocyanurate monomer and prepolymer. Then, this was distilled under reduced pressure at 40 to 50° C. and 300 mHg to remove a portion of toluene and diluted with trichlene. The composition of this diluted solution (referred to as triallyl isocyanurate solution B) is: - Triallyl isocyanurate monomer...15% by weight - Triallyl isocyanurate prepolymer...25
Weight% Toluene: 5% by weight Triclene: 55% by weight. Furthermore, the weight average molecular weight of the triallyl in cyanurate monomer and prepolymer in this diluted solution was 12,000,
The number average molecular weight is 3000, and M w / M n
= 4. A flame-retardant polyphenylene oxide resin composition was obtained in the same manner as in Example 1 with the other formulations shown in the table. Further, a laminate was produced in the same manner as in Example 1. Yutanji Hise 5 Using triallyl isocyanurate solution A or triallyl isocyanurate solution B, a flame-retardant polyphenylene oxide-based resin composition was prepared in the same manner as in Example 1 with the formulation shown in the table, and further in accordance with Example 1. A laminate was produced in the same manner. Triallyl cyanurate is used instead of triallyl isocyanurate, and triallyl cyanurate is reacted with the triallyl cyanurate monomer in a toluene solvent in the same manner as described above (Production Example 1). A toluene solution of the polymer was prepared. Then, heat this at 40 to 50℃.
Part of the toluene was removed by distillation under reduced pressure at 300 mHg, and the mixture was diluted with trichlene. The composition of this diluted solution (referred to as triallyl cyanurate solution C) is: - triallyl cyanurate monomer... 15% by weight - triallyl cyanurate prepolymer... 25% by weight - toluene... 5% by weight・Trichlene: 55% by weight. Furthermore, the weight average molecular weight of the triallyl cyanurate monomer and prepolymer in this diluted solution is 12,000, the number average molecular weight is 3,000, and M w / M n =
It was 4. A flame-retardant polyphenylene oxide resin composition was obtained in the same manner as in Example 1 with the other formulations shown in the table. Further, a laminate was produced in the same manner as in Example 1. Sai1 Takumi Yoji A Triallylisocyanurate monomer and triallylisocyanurate prepolymer were used and blended as shown in the table to obtain a flame-retardant polyphenylene oxide resin composition. Further, a laminate was produced in the same manner as in Example 1. In the table, PPO manufactured by General Electric Co., Ltd. was used as the polyphenylene oxide, and Nluprene T406 manufactured by Asahi Kasei Industries, Ltd. was used as the styrene-butadiene copolymer. In addition, in the table, "GX-6145J has the formula (
l, m, n= of BrI, Br1 Br, , in 5)
The flame retardant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
50J is R = H, B r m in the above formula (2)
, B r n m. A flame retardant manufactured by Daiichi Kogyo Seiyaku Co., Ltd. where n=5 was used as rPB.
P is the reaction initiator Perbutyl P manufactured by Nihon Yushi Kogyo Co., Ltd.
, rP25BJ indicates the reaction initiator Perhexine 25B manufactured by Nihon Yushi Kogyo Co., Ltd., respectively. In each of the above Examples and Comparative Examples, the dielectric constant, dielectric loss tangent, copper foil peel strength, and flame retardance of the laminates were measured, and the varnish stability of the polyphenylene oxide resin composition and the prepreg Bleedability 5 Moldability was measured and cost was calculated. Here, the relative permittivity, dielectric loss tangent, and copper foil peel strength were measured based on JIS C6481, and the flame retardance was measured based on UL standards. In addition, varnish stability is determined by the presence or absence of viscosity increase when the varnish of polyphenylene oxide resin composition is left to stand, bleedability is determined by whether or not adhesion occurs between prepregs, and moldability is determined by whether or not the prepregs adhere to each other. Evaluation is made by observing the surface of the laminate after removing it by etching, and the cost is determined by relative comparison.
Slightly poor quality was indicated by △, and poor quality was indicated by ×. These results are shown in the following table.As shown in the previous table, the bleed properties of Comparative Examples 1 and 4, which contained only triallylisocyanurate monomer as triallylisocyanurate, were poor, and those containing only polyphenylene oxide prepolymer The compounded Comparative Example 2 had poor adhesion with copper foil and moldability, but the samples of each Example, in which triallyl isocyanurates were reacted in toluene and diluted with trichlene, showed no bleed. It is confirmed that the material has good properties in terms of properties, adhesion with copper foil, and moldability, as well as excellent dielectric constant, Mt tangent, flame retardance, and cost.

【Effect of the invention】

As mentioned above, in the present invention, polyphenylene oxide, triallylisocyanurates, prepolymers of triallylisocyanurates, crosslinkable polymer, and toluene and trichloroethylene as solvents are blended, so that bleedability is reduced. Triallylisocyanurates make it possible to improve electrical performance such as low dielectric properties without deteriorating performance such as adhesiveness or adhesion.

Claims (3)

[Claims] (1) A polyphenylene oxide resin composition comprising polyphenylene oxide, triallyl isocyanurates, a prepolymer of triallyl isocyanurates, a crosslinkable polymer, and toluene and trichloroethylene as solvents. (2) The polyphenylene oxide resin composition according to claim 1, wherein toluene is blended as a reaction solvent when triallyl isocyanurate is polymerized into a prepolymer, and trichlorethylene is blended as a diluent solvent. . (3) The polyphenylene oxide resin composition according to claim 1 or 2, further comprising a flame retardant.