JPH11293108A - Polyarylene sulfide resin composition, its production and molding produced by using the polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition having excellent tight adhesivity and bonding property to various materials while keeping the physical properties of polyarylene sulfide resin. SOLUTION: This composition is composed of (A) a straight-chain polyarylene sulfide resin, (B) a graft copolymer obtained by the chemical bonding of (a) a polymer segment composed of terpene unit to (b) an olefinic copolymer segment composed of an α-olefin unit and an α,β-unsaturated acid glycidyl ester unit in a state to form a branched or crosslinked structure and (C) an inorganic filler. The adhesivity and bonding property to various materials can be increased by the use of the graft copolymer B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyarylene sulfide resin composition, and more particularly to a polyarylene sulfide resin composition having improved adhesiveness and adhesion, excellent moldability and heat resistance, and a method for producing the same. The present invention relates to a molded article using the polyarylene sulfide resin composition.

[0002]

2. Description of the Related Art In recent years, electrical and electronic equipment parts materials, automobile equipment parts materials, and chemical equipment parts materials have been required to have high heat resistance, chemical resistance and flame-retardant thermoplastic resins. ing.

[0003] Polyphenylene sulfide resin (hereinafter referred to as P
A polyarylene sulfide resin (hereinafter sometimes abbreviated as a PAS resin) typified by a polyarylene sulfide resin (which may be abbreviated as a PS resin) is one of the resins that meet this requirement, and has a high moldability, heat resistance, and a low physical property ratio to cost. Demand is increasing for good. However, molded articles made of polyarylene sulfide resin are often used by being bonded to various materials, but have poor adhesion and adhesion, such as adhesion and adhesion to metal inserts of equipment parts. Has the fundamental drawback of having a problem.

In order to solve these problems, for example, Japanese Patent Publication No. 63-11780 discloses a method of adding a polymer having adhesiveness or adhesion, such as an epoxy resin, a silicone resin, or a phenoxy resin, to a polyarylene sulfide resin. Proposed. However, although the addition of the epoxy resin can improve the chemical bonding force with the metal insert, the problem that the stress generated between the metal insert and the metal insert under heating is large because the elastic modulus is large. was there. In addition, the addition of silicone resin lowers the elastic modulus, but the effect of improving the chemical bonding force with the metal insert is not remarkable, and the addition of phenoxy resin has insufficient effects of both of these improvements. there were. Also,
The polyarylene sulfide resin composition to which such a polymer having adhesiveness or adhesion is added has a problem that molding defects are likely to occur due to high melt viscosity at the time of molding.

[0005]

As described above, the use of the polyarylene sulfide resin composition for molding machine parts presently has many problems to be solved.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and maintains a physical property of a polyarylene sulfide resin and has excellent adhesiveness and adhesion to various materials in addition to moldability and heat resistance. It is an object of the present invention to provide an arylene sulfide resin composition, a method for producing the same, and a molded article using such a polyarylene sulfide resin composition.

[0007]

The polyarylene sulfide resin composition according to claim 1 of the present invention comprises (A) a linear polyarylene sulfide resin, (B) an α-olefin unit and α, β-unsaturated resin. For the olefin-based copolymer segment (a) composed of an acid glycidyl ester unit,
The polymer segment (b) comprising a terpene unit is characterized by comprising a graft copolymer which is chemically bonded in a branched or crosslinked structure, and (C) an inorganic filler.

The polyarylene sulfide resin composition according to claim 2 of the present invention is characterized in that the (A) linear polyarylene sulfide resin is a polyparaphenylene sulfide having 70% by weight or more of a paraphenylene sulfide unit. Features.

The polyarylene sulfide resin composition according to claim 3 of the present invention is characterized in that, in the graft copolymer (B), a polymer segment (b) comprising a terpene unit is used.
Is a copolymer having a repeating unit represented by the following general formula (Formula 2).

[0010]

Embedded image (Where R ₁ is hydrogen or a lower alkyl group having 1 to 3 carbon atoms; X ₁ is —COOCH ₃ , —COOC ₂ H ₅ , —COOC ₄ H ₉ , —COOCH ₂₎
CH (C ₂ H ₅ ) represents one or more groups selected from C ₄ H ₉ , —C ₆ H ₅ , and —CN. The polyarylene sulfide resin composition according to claim 4 of the present invention is characterized in that, in the graft copolymer (B), the α-olefin unit is ethylene.

The polyarylene sulfide resin composition according to claim 5 of the present invention is characterized in that (C) the inorganic filler is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group. Features.

The polyarylene sulfide resin composition according to claim 6 of the present invention is characterized in that the inorganic filler (C) accounts for 30 to 70% by weight in the total of (A) to (C). And

The polyarylene sulfide resin composition according to claim 7 of the present invention comprises (A) a linear polyarylene sulfide resin, (B) an α-olefin unit and α, β-
A graft copolymer in which a polymer segment (b) composed of a terpene unit is chemically bonded in a branched or crosslinked structure to an olefin copolymer segment (a) composed of a glycidyl ester unit of an unsaturated acid, (A) 100
(B) 0.5 to 50 parts by weight with respect to parts by weight.

The method for producing a polyarylene sulfide resin composition according to claim 8 of the present invention is characterized in that the components (A) to (C) according to any one of claims 1 to 7 are kneaded. I do.

A molded article of the polyarylene sulfide resin composition according to the ninth aspect of the present invention is obtained by molding a metal insert using the polyarylene sulfide resin composition according to any one of the first to seventh aspects. It is characterized by the following.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.

According to the present invention, (A) a linear polyarylene sulfide resin, (B) an α-olefin unit and α,
Graft copolymer in which a polymer segment (b) composed of a terpene unit is chemically bonded in a branched or cross-linked structure to an olefin copolymer segment (a) composed of a glycidyl ester unit of β-unsaturated acid. And (C) a polyarylene sulfide resin composition comprising an inorganic filler.

Further, according to the present invention, there is provided a molded article molded using the above-mentioned polyarylene sulfide resin composition.

The (A) linear polyarylene sulfide resin (hereinafter sometimes referred to as a linear PAS resin) used in the present invention comprises a repeating unit -Ar- (provided that
Ar is an aryl group) as a main structural unit, and a typical substance thereof is a polymer having a repeating unit represented by the structural formula -Ph-S- (where Ph is a phenyl group) is 70 units.
It is a polyphenylene sulfide resin having a weight percent or more. Of course, this repeating unit may be 100% by weight. PPS resins are generally classified into substantially cross-linked, semi-cross-linked, and linear types according to the production method. In the present invention, the linear type is superior in mechanical strength. Therefore, it is suitable.

In particular, the melting point is 260 ° C. or higher, and the melt viscosity is
Temperature 300 ° C, angular velocity 10 by parallel plate method
Under a condition of 0 rad / s, a pressure of 1 to 30 Pa · s is preferably used. In the parallel plate method, a pellet having a thickness of 1 mm x a diameter of 25 mm is prepared by a hand press,
mm is placed on the lower parallel plate, the upper parallel plate is lowered, sandwiched, and held at 300 ° C. for 10 minutes, followed by measurement. For example, rheometric Scientific, Arles Measurement under (trade name) is appropriate.

The molecular weight distribution is not particularly limited, and various molecular weight distributions can be applied. If the melting point is lower than 260 ° C., the mechanical strength of the molded article is undesirably weak. Although there is no upper limit for the melting point, about 290 ° C. is a practical limit. If the melt viscosity is less than this range, the mechanical strength of the molded article is greatly reduced, and if it exceeds this range, the molding fluidity is poor and the moldability is poor.

The linear PAS resin preferred in the present invention is copolymerized with other structural units as long as it contains 70% by weight or more, preferably 90% by weight or more of a repeating unit of paraphenylene sulfide. Things may be used together. If this repeating unit is less than 70% by weight, the crystallinity, which is a characteristic of the crystalline polymer, tends to be low, and sufficient strength tends not to be obtained, resulting in poor toughness. Of course, the repeating unit of paraphenylene sulfide may be 100% by weight.

The linear PAS resin used in the present invention may contain other copolymerized units. Examples of the constituent units of the copolymer include the following chemical formulas (3), (4) and (4). 5 "," 6 "," 7 "," 8 "and the like.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

Embedded image Next, the graft copolymer used as the component (B) in the present invention comprises an olefin copolymer segment (a) composed of an α-olefin unit and a glycidyl ester unit of an α, β-unsaturated acid, and a terpene unit. Polymer segments (b) are chemically bonded in a branched or cross-linked structure.

Here, examples of the α-olefin unit which is one monomer constituting the copolymer portion of (a) include ethylene, propylene and butene-1.
Ethylene is preferably used. The glycidyl ester unit of the α, β-unsaturated acid which is another monomer constituting the component (a) is represented by the following general formula [Chemical Formula 9]. For example, glycidyl acrylate, glycidyl methacrylate Examples thereof include esters and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferably used.

[0031]

Embedded image (Here, R ₂ represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.)

Α-olefin unit (for example, ethylene)
And the glycidyl ester unit of an α, β-unsaturated acid can be copolymerized by a well-known radical reaction to obtain the olefin copolymer (a). The composition of the segment (a) is composed of α-olefin units 70 to 9
9% by weight and 30 to 1% by weight of glycidyl ester units of an α, β-unsaturated acid are preferred.

The olefin copolymer segment (a) includes a copolymer of ethylene and glycidyl methacrylate, a copolymer of ethylene, vinyl acetate and glycidyl methacrylate, and a copolymer of ethylene, ethyl acrylate and glycidyl methacrylate. And a copolymer of ethylene and glycidyl acrylate, and a copolymer of ethylene and vinyl acetate and glycidyl acrylate, among which copolymers of ethylene and glycidyl methacrylate are preferred. . The olefin copolymer may be a mixture of two types.

The shape of the olefin-based copolymer segment (a) is desirably a powder or a pellet having a particle size of about 0.1 to 5 mm. The particle size is appropriately selected depending on the mixing ratio of (a). Is preferred. If the particle size is too large, not only is it difficult to disperse during polymerization, but also there is a disadvantage that it takes a long time to impregnate the monomer constituting the graft component.

The terpene (b) is defined by the isoprene rule (C
₅ H ₈ ) _n (n is an integer of 1 or more) is a generic term for a series of compounds, where n is a generic term for two or more. For example, monoterpenes (n = 2): dipentene, α
-Pinene, β-pinene, limonene and the like. More specifically, the polymer segment (b) composed of a terpene unit is represented by the following general formulas “Chemical Formula 10”, “Chemical Formula 11”, “Chemical Formula 12”, “Chemical Formula 13”, “Chemical Formula 14”, and the like. It is a polymer of a repeating unit. Each of the hydrogenated products described here can be produced by producing a graft copolymer and then reacting with a general hydrogenation catalyst.

[0036]

Embedded image (However, X ₂ represents one or two groups selected from the right.)

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[0037]

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[0038]

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[0039]

Embedded image Therefore, as a monomer derived from the repeating unit constituting (b), dipentene represented by the following “Chemical Formula 15” or “Chemical Formula 16”
Α-pinene and “Formula 17” β-pinene.

[0040]

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[0041]

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[0042]

Embedded image Further, (b) shows “chemical 15”, “chemical 16”, “chemical 17”
In addition to the unit represented by, a monoethylenically unsaturated monomer unit copolymerizable therewith may be used. As the copolymerizable monoethylenically unsaturated monomer unit, the above “Chemical formula 2”
Can be suitably adopted.

Preferred examples of the polymer segment (b) comprising terpene units include the following. That is, a copolymer of styrene and dipentene, a copolymer of acrylonitrile and styrene and dipentene, a copolymer of methyl methacrylate and dipentene, a copolymer of ethyl acrylate and dipentene, butyl acrylate and dipentene , A copolymer of 2-ethylhexyl acrylate and dipentene, and a copolymer of butyl acrylate, methyl methacrylic acid and dipentene. Further, a copolymer of styrene and α-pinene, a copolymer of acrylonitrile and styrene and α-pinene, a copolymer of methyl methacrylate and α-pinene, and a copolymer of ethyl acrylate and α-pinene A copolymer of butyl acrylate and α-pinene, a copolymer of 2-ethylhexyl acrylate and α-pinene, and a copolymer of butyl acrylate, methyl methacrylic acid and α-pinene. It is. Further, copolymers of ethyl acrylate and β-pinene, such as a copolymer of styrene and β-pinene, a copolymer of acrylonitrile, styrene, and β-pinene, and a copolymer of methyl methacrylate and β-pinene. Polymers, copolymers of butyl acrylate and β-pinene, copolymers of 2-ethylhexyl acrylate and β-pinene, and copolymers of butyl acrylate, methyl methacrylic acid and β-pinene are included. Is done.

In (b), the amount of the polymer segment comprising terpene units is preferably 5 to 100% by weight.
It is. When these amounts are less than 5% by weight, it is not possible to sufficiently obtain the effect of improving the adhesion and adhesion to various materials.

Here, with respect to the olefin copolymer segment (a) comprising the α-olefin unit and the glycidyl ester unit of an α, β-unsaturated acid of (B) of the present invention,
The graft copolymer in which the polymer segment (b) composed of a terpene unit is chemically bonded in a branched or cross-linked structure has an effect on the adhesion and the adhesiveness because the graft structure is chemically different from the polyarylene sulfide resin. Excellent compatibility,
Further, it is considered that a polymer segment comprising a terpene unit which effectively acts on adhesion and adhesion is graft-bonded in the component.

The graft copolymer (C) in the present invention is obtained by chemically bonding the segments (a) and (b) in a branched or crosslinked structure. The presence or absence of a chemical bond can be determined by whether or not (a) and (b) can be completely extracted with a solvent capable of dissolving (a) or (b). If all of them can be separated, it is assumed that they are not chemically bonded.

In the graft copolymer (C), (a) is 40
-95% by weight, preferably 50-90% by weight.
If (a) is less than 5% by weight, the compatibility with the linear PAS resin becomes insufficient, and if it exceeds 95% by weight, the heat resistance and dimensional stability of the composition may be impaired.

The method for preparing the graft copolymer (C) may be any of the generally known methods such as a chain transfer method, but the most preferred method is as follows.

First, 100 parts by weight of the olefin polymer (a) obtained by a conventional method is suspended in water. On the other hand, one or two radical polymerizable organic peroxides represented by the following general formulas (Chemical Formula 18) or (Chemical Formula 19) are added to 5 to 400 parts by weight of at least one monoethylenically unsaturated monomer. 0.1 to 10 parts by weight of the above mixture based on 100 parts by weight of the monoethylenically unsaturated monomer, and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. in order to obtain a half life of 10 hours. Of a monoethylenically unsaturated monomer and a radically polymerizable organic peroxide in a total amount of 0.01 to 5 parts by weight. The solution is added to the aqueous suspension, and heated under the condition that decomposition of the radical polymerization initiator does not substantially occur, a monoethylenically unsaturated monomer,
A precursor is obtained by copolymerizing a radically polymerizable organic peroxide and a radical polymerization initiator in the olefin polymer (a). By kneading the precursor under melting at 100 to 300 ° C., a copolymer having a structure in which the olefin polymer segment (a) and the monoethylene polymer segment (b) are chemically bonded can be obtained. it can.

The radical polymerizable organic peroxide represented by the general formula (Formula 18) is:

[0051]

Embedded image (Wherein, R ₄ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₅ is a hydrogen atom or a methyl group, R ₆ and R ₇ are alkyl groups having 1 to 4 carbon atoms, and R ₈ is a carbon atom. Which represents an alkyl group of 1 to 12, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group of 3 to 12 carbon atoms, and m is 1 or 2).

The radically polymerizable organic peroxide represented by the general formula (Formula 19) is

[0053]

Embedded image (Wherein, R ₉ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₁₀ is a hydrogen atom or a methyl group, R ₁₁ and R ₁₂ are each an alkyl group having 1 to 4 carbon atoms, and R ₁₃ is a carbon atom. Represents an alkyl group of 1 to 12, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group of 3 to 12 carbon atoms, wherein n is 0, 1,
Or 2).

Specific examples of the radically polymerizable organic peroxide represented by the above general formula [Formula 18] include t-butylperoxy (meth) acrylo (ethoxy) ethyl carbonate, t-amylperoxy (meth) acryloyloxy ( (Ethoxy) ethyl carbonate, t-hexylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, 1,2,3,3-tetramethylbutylperoxy (meth) acryloxy (ethoxy) ethyl carbonate, cumylperoxy (meth) acryloyloxy (ethoxy) ) Ethyl carbonate, p-isopropylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, t-butylperoxyacryloyloxyethyl carbonate, and the like.

Further, as the radical polymerizable organic peroxide represented by the above-mentioned general formula (Formula 19), t-butylperoxy (meth) allyl carbonate, cumylperoxy (meth) allylcarbonate, t-butylperoxy (meth) Allyloxyethyl carbonate and the like can be exemplified. Among them, t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallylcarbonate, and t-butylperoxymethacrylcarbonate are preferable.

The method for producing the graft copolymer (B) is described in JP-A-1-131 filed by Nippon Oil & Fats Co., Ltd.
As described in JP-A-220-220 and JP-A-1-138214, graft copolymers can be produced by using known methods as they are.

The amount of the graft copolymer (B) to 100 parts by weight of the linear polyarylene sulfide resin (A) is 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight.
Parts by weight. If the amount of the component (B) is too small, it is difficult to obtain the intended effect. If the amount is too large, the rigidity and heat resistance of the composition may be impaired, and further the moldability may be impaired.

Next, the inorganic filler (C) used in the present invention
Examples include fibrous materials having an aspect ratio (average length L / average diameter D) of more than 1, beads and powder having an aspect ratio of 1. Here, in order to increase the rigidity of the obtained resin composition, the aspect ratio of the fibrous filler may be increased, but if the aspect ratio exceeds 500, the anisotropy increases, which is not practical. Examples of the fibrous filler include milled fiber glass, glass fiber, alumina fiber, inorganic fiber such as ceramic fiber and metal fiber, and carbon fiber.
As the powdery filler, amorphous silica, crystalline silica, silica such as synthetic silica, alumina, glass, titanium oxide,
Examples include calcium carbonate, clay, mica, talc, wollastonite, sericite, kaolin, mica, clay, silicon nitride, aluminum nitride and the like, which may be hollow. Particularly preferred for electric and electronic parts are milled fiber glass, silica such as amorphous silica, crystalline silica, and synthetic silica, and spherical alumina. These may be used alone or in combination of two or more. Further, it is preferable that the surface of the inorganic filler is pretreated with a coupling agent. In the case of pre-treatment with a coupling agent, treatment with a coupling agent alone may be performed, or treatment with two or more types of coupling agents may be used in combination. Particularly preferred are amino groups, or epoxy groups,
Or those treated with a coupling agent having a mercapto group. Silica includes synthetic products and natural products, both of which can be used. The shape of silica is
There are spherical and crushed shapes, both of which can be used.

It is preferable that the inorganic filler (C) is blended in an amount of 30 to 70% by weight based on the total of (A) to (C). 3
If it is less than 0% by weight, heat resistance and rigidity are low, and low stress due to a decrease in linear expansion coefficient cannot be expected. Will not be able to.

The polyarylene sulfide resin composition of the present invention may contain, if necessary, other synthetic resins, elastomers, antioxidants, crystal nucleating agents, crystallization accelerators, cups, etc., unless the object of the present invention is impaired. A ring agent, a release agent, a lubricant, a coloring agent, an ultraviolet absorber, an antistatic agent, a flame retardant, and the like can be added.

Examples of the above synthetic resin and elastomer include polyolefin resin, polyester resin, polyoxymethylene resin, polymethylpentene resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, and polyamide resin (nylon 6, nylon 66, nylon 610). ,
Aromatic nylon, nylon 46, copolymerized nylon), polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyacetal resin, polyetherimide resin, polyamideimide resin, Polyimide resin, polystyrene resin, crystalline polystyrene resin, AS resin, ABS resin, phenoxy resin, polyether nitrile resin, polytetrafluoroethylene, epoxy resin, phenol resin, silicone resin, urethane resin, terpene resin, hydrogenated terpene resin, Examples include synthetic resins such as aromatic modified terpene resins and terpene phenol resins, and elastomers such as polyolefin rubbers, olefin copolymers, and hydrogenated rubbers. These may be used alone or in combination of two or more.

As the antioxidant, phosphorus antioxidants,
And phenolic antioxidants. These may be used alone or in combination of two or more.

As the crystal nucleating agent, any of an organic substance and an inorganic substance can be used. As the inorganic substance, a simple substance such as carbon black or a clay such as talc or kaolin can be used. Examples of the organic substance include a dibenzylidene sorbitol compound, an aluminum salt of t-butylbenzoic acid, and a sodium salt of a phosphate ester. These may be used alone or in combination of two or more. Some of the above crystal nucleating agents overlap with the above filler, but these substances can fulfill both functions. Some nucleating agents are low molecular weight compounds, and may act as plasticizers. In that case, the fluidity and moldability of the resin composition of the present invention in a molten state can be improved.

Examples of the coupling agent include silane compounds, titanate compounds, and aluminum compounds, and silane compounds are particularly preferable. As the silane type, γ-aminopropyltriethoxysilane, N-β
Aminosilanes such as (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and γ-glycid Xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
Epoxysilanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (Β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylsilane such as γ-methacryloxypropyltrimethoxysilane, and epoxy-based, amino-based, vinyl-based polymer-type silane, and the like. In particular, aminosilane, epoxysilane, and mercaptosilane are preferred. These may be used alone or in combination of two or more.

As the lubricant, both an internal lubricant and an external lubricant can be used, and examples thereof include hydrocarbons, fatty acids, fatty acid amides and fatty acid esters. These may be used alone or in combination of two or more.

As the coloring agent, various known pigments or dyes can be used. Examples of the coloring agent include black pigments such as carbon black, orange pigments such as red-mouthed graphite, red dyeing pigments such as red iron oxide, and cobalt violet. Purple dyes, blue dyes such as cobalt blue, and green dyes such as phthalocyanine green can be used. More specifically,
With reference to the latest pigment handbook (edited by Japan Pigment Technical Association, published in 1977), those described in this handbook can be used.

Examples of the flame retardant include halogen-based flame retardants, phosphorus-based flame retardants, metal oxides and inorganic flame retardants. These flame retardants can be used alone or in combination of two or more.

The method for producing the polyarylene sulfide resin composition according to the present invention is generally carried out by mixing the components with a mixer such as a Henschel mixer or, if necessary, preliminarily mixing a part of the necessary components with a master batch. After mixing and mixing
A method of melting and kneading with a kneading machine such as an extruder and pelletizing is used, but is not limited thereto.

The method of molding a metal insert using the polyarylene sulfide resin composition according to the present invention is not particularly limited, and the metal insert is fixed in a mold, and injection molding, transfer molding, and potting molding are performed. And the like. A molded product can be obtained by applying various known molding processing means.
The material of the metal insert is not particularly limited, and any material obtained by combining various metals such as iron, nickel, copper, aluminum, tin, zinc, cobalt, and zirconium alone or in combination can be used. .

The molded article of the present invention can be used as an automobile part, for example, a cylinder head cover, an underhood part,
For clean fan, radiator tank, relay cap, window screen, etc., as electronic components, for example, transistors, integrated circuits, diodes, coils,
It can be used for capacitors, resistors, varistors, connectors, etc.

[0071]

The present invention will be described in more detail with reference to the following examples.

Examples 1 to 21 and Comparative Examples 1 to
6) For Examples 1 to 21, the formulations shown in Tables 2 to 4 below (the blending amounts are parts by weight), and for Comparative Examples 1 to 6,
After blending each component uniformly using a Henschel mixer according to the formulation shown in Table 5 below (the blending amount is part by weight), the mixture was extruded at a cylinder temperature of 300 ° C. using a biaxial kneading extruder having a screw diameter of 40 mm. Then, it pelletized and produced the polyarylene sulfide resin composition of Examples 1-21 and Comparative Examples 1-6. Here, Tables 2 to 5
The components used for the following are:

Linear polyarylene sulfide resin Resin A: Linear PPS resin (manufactured by Kureha Chemical Industry Co., Ltd., product number “W-202A”, melt viscosity 23 Pa · s / parallel plate method, 300 ° C., 100 rad / sec. Measurement) Resin B: Linear PPS resin (manufactured by Kureha Chemical Industry Co., Ltd., product number:
“W-203A”, melt viscosity 29 Pa · s / parallel plate method, measured at 300 ° C. and 100 rad / sec) Resin C: linear PPS resin (manufactured by Topren Corporation, product number:
“LR01”, melt viscosity 6 Pa · s / parallel plate method,
Resin D: Linear PPS resin (manufactured by Topren Corporation, product number: 300 ° C, 100 rad / sec)
“LR03”, melt viscosity 19 Pa · s / parallel plate method, measured at 300 ° C., 100 rad / sec) • Graft copolymer (Production of graft copolymer A: Production Example 1) In a stainless steel autoclave with an internal volume of 5 liters , Pure water 2500g
, And as a suspending agent, polyvinyl alcohol 2.
5 g were dissolved. 700 g of an ethylene-glycidyl methacrylate copolymer (content of glycidyl methacrylate 15% by weight, pellet form: manufactured by Nippon Petrochemical Co., Ltd.) was added thereto, and the mixture was stirred and dispersed. Separately, 1.5 g of benzoyl peroxide (trade name "Niper B," Nippon Oil & Fat Co., Ltd., 10-hour half-life 74 ° C.) as a radical polymerization initiator, and t-butylperoxymeta as a radical (co) polymerizable organic peroxide Acryloethoxyethyl carbonate (6 g) was dissolved in acrylonitrile (60 g), styrene (150 g) and dipentene (90 g), and the solution was charged into the autoclave and stirred. Next, the autoclave was heated to 60 to 65 ° C., and while stirring for 2 hours, the radical polymerization initiator, the radical (co) polymerizable organic peroxide, and the unsaturated monomer were mixed with ethylene-glycidyl methacrylate ester. The coalescence was impregnated. Then, the temperature was raised to 80 to 85 ° C., and the temperature was maintained for 7 hours to complete the polymerization, followed by washing and drying to obtain a graft copolymer precursor. This was kneaded by melting at 280 ° C. to give 70 parts by weight of the graft copolymer A [ethylene / glycidyl methacrylate copolymer (weight ratio 85/15) to the acrylonitrile-styrene-dipentene copolymer (weight ratio of 20). / 50/30) Graft copolymer obtained by graft copolymerization of 30 parts by weight: poly (E / GMA = 85/15) 70-graft-copoly (AN / ST / DP = 20/50/30) 30] was obtained. Was.

(Production of Graft Copolymers BF: Production Examples 2 to 6) The parts of 700 g of ethylene-glycidyl methacrylate copolymer, 60 g of acrylonitrile, 150 g of styrene, and 90 g of dipentene in Production Example 1 are shown in Table 1. (The numbers in Table 1 are g numbers)
It carried out similarly to manufacture example 1, and obtained graft copolymer BF.

[0075]

[Table 1] Here, from Production Example 2, the graft copolymer B [ethylene / glycidyl methacrylate ester copolymer (weight ratio 85/15) 50 parts by weight to acrylonitrile styrene dipentene copolymer (weight ratio 20/50/30) ) 50
Graft copolymer obtained by graft copolymerization of parts by weight: poly (E / GMA = 85/15) 50-graft-copoly (AN / ST / DP = 20 /
50/30) 50].

From Production Example 3, the graft copolymer C (70 parts by weight of ethylene / glycidyl methacrylate copolymer (weight ratio: 85/15): 30 parts by weight of styrene dipentene copolymer (weight ratio: 70/30)) Graft copolymer obtained by graft copolymerization of part: poly (E / GMA = 85/15) 70-
Graft-copoly (ST / DP = 70/30) 30] was obtained.

From Production Example 4, the graft copolymer D [30 parts by weight of styrene dipentene copolymer (30/7 by weight) per 70 parts by weight of ethylene / glycidyl methacrylate copolymer (85/15 by weight) A graft copolymer obtained by graft copolymerization of a part thereof: poly (E / GMA = 85/15) 70-graft-copoly (ST / DP = 30/70) 30] was obtained.

From Production Example 5, the graft copolymer E [styrene / α-pinene copolymer (70/30 by weight) was added to 70 parts by weight of ethylene / glycidyl methacrylate copolymer (85/15 by weight). Graft copolymer obtained by graft copolymerization of 30 parts by weight: poly (E / GMA = 85/15) 70
-Graft-copoly (ST / αP = 70/30) 30].

From Production Example 6, the graft copolymer F [styrene / β-pinene copolymer (70/30 by weight) was added to 70 parts by weight of ethylene / glycidyl methacrylate copolymer (85/15 by weight). Graft copolymer obtained by graft copolymerization of 30 parts by weight: poly (E / GMA = 85/15) 70-
Graft-copoly (ST / βP = 70/30) 30] was obtained.

Graft copolymer G: ethylene / glycidyl methacrylate copolymer (weight ratio 85/15)
Graft copolymer obtained by graft copolymerizing 30 parts by weight of an acrylonitrile styrene copolymer (weight ratio 30/70) with respect to 70 parts by weight (manufactured by NOF Corporation, product number "A4400"):
Poly (E / GMA = 85/15) 70-graft-copoly (AN / ST = 3
0/70) 30 Graft copolymer H: 50 parts by weight of ethylene / glycidyl methacrylate copolymer (weight ratio 85/15) to acrylonitrile styrene copolymer (weight ratio 30
/ 70) Graft copolymer obtained by graft copolymerizing 50 parts by weight (manufactured by NOF CORPORATION, product number “A4401”): poly (E / GMA =
85/15) 50-graft-copoly (AN / ST = 30/70) 50 Graft copolymer I: Styrene polymer based on 70 parts by weight of ethylene / glycidyl methacrylate copolymer (weight ratio 85/15) Graft copolymer obtained by graft copolymerizing 30 parts by weight (manufactured by NOF Corporation, product number "A4100"):
Poly (E / GMA = 85/15) 70-graft-copoly (ST = 100) 3
0 Graft copolymer J: a graft copolymer (produced by NOF Corporation) obtained by graft copolymerizing 50 parts by weight of a styrene polymer with 50 parts by weight of an ethylene / glycidyl methacrylate ester (weight ratio: 85/15) Part number "A4101"):
Poly (E / GMA = 85/15) 50-graft-copoly (ST = 100) 5
Inorganic filler A: Milled fiber (manufactured by Nippon Sheet Glass Co., Ltd., product number “REV8”, aminosilane treatment, fiber diameter 13 μm, average fiber length 70 μm, aspect ratio 5.6) Inorganic filler B: milled fiber (Japan Manufactured by Sheet Glass Co., Ltd., product number “REV12”, aminosilane treatment, fiber diameter 6 μm, average fiber length 50 μm, aspect ratio 8.3) Inorganic filler C: Milled fiber (manufactured by Nippon Sheet Glass Co., product number “REV4”, no treatment, fiber diameter 13 μm, average fiber length 70
μm, aspect ratio 5.6) Inorganic filler D: spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., product number “FB60”, average particle size 20 μm) Inorganic filler E: spherical silica (manufactured by Admatechs, product number “SO25R”, Coupling agent Coupling agent A: aminosilane-based coupling agent (γ
-Aminopropyltriethoxysilane, manufactured by Nippon Unicar, part number "A1100") Coupling agent B: Epoxysilane-based coupling agent (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone, part number "KBM403") Cup Ringing agent C: Mercaptosilane-based coupling agent (3-mercaptopropyltrimethoxysilane, manufactured by Toshiba Silicone Co., product number "TSL8380E") Coupling agent D: Vinylsilane-based coupling agent (vinyltrimethoxysilane, manufactured by Toray Silicone Co., Ltd.) , Part number "SZ6300")

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5] The physical properties of the molded articles obtained in Examples 1 to 21 and Comparative Examples 1 to 6 were evaluated by the following methods.

(1) Adhesion A The peel strength was measured in a normal state according to JIS C 6481. The test piece was 150 mm x 150 mm x
0.5mm thick copper as metal on the bottom of 5mm mold,
Or a sheet of iron or 42 alloy spread, and a pellet-shaped sample placed on it and pressed at 300 ° C.
It was prepared by cutting out according to C6481. The results were evaluated as "": not easily peeled, "x": easily peeled, and are shown in Tables 2 to 5 above.

(2) Adhesion B Using the test piece prepared with the adhesion A described above, an ultrasonic image analyzer (“M-830” manufactured by Canon Inc.) was used to measure the adhesion between the resin composition and the metal. The adhesion was evaluated. Those with peeling were regarded as defective. The obtained results are shown in Tables 2 to 5 above as (number of defectives / number of tested samples).

(3) Bending strength In accordance with ASTM D790, the resin compositions of the respective examples and comparative examples were injection-molded at a cylinder temperature of 300 ° C. and a mold temperature of 130 ° C. using a bending test piece molding die. ,
An evaluation sample was obtained. This sample was measured at 23 ° C., and the results are shown in Tables 2 to 5 above.

As can be seen from Tables 2 to 5, each of the examples had extremely excellent adhesion.

[0089]

As described above, the present invention provides (A) a linear polyarylene sulfide resin, (B) an olefin copolymer comprising an α-olefin unit and a glycidyl ester unit of an α, β-unsaturated acid. A polymer segment (b) composed of a terpene unit is branched,
Or a graft copolymer chemically bonded in a cross-linked structure,
(C) It comprises an inorganic filler, and the graft copolymer (B) can provide a polyarylene sulfide resin composition having excellent adhesion and adhesion to various materials.

By molding a metal insert using this polyarylene sulfide resin composition, a molded article of a polyarylene sulfide resin composition having excellent adhesion to the metal insert can be obtained. .

Claims (9)

[Claims] (A) a linear polyarylene sulfide resin; (B) an olefin-based copolymer segment (a) comprising an α-olefin unit and a glycidyl ester unit of an α, β-unsaturated acid; A polyarylene sulfide resin composition comprising a graft copolymer in which a polymer segment (b) composed of a terpene unit is chemically bonded in a branched or crosslinked structure, and (C) an inorganic filler. 2. The polyarylene sulfide resin composition according to claim 1, wherein the (A) linear polyarylene sulfide resin is a polyparaphenylene sulfide having at least 70% by weight of a paraphenylene sulfide unit. . 3. The (B) graft copolymer according to claim 1, wherein
The polyarylene sulfide according to claim 1 or 2, wherein the polymer segment (b) comprising a terpene unit is a copolymer including a repeating unit represented by the following general formula (1). Resin composition. Embedded image (Where R ₁ is hydrogen or a lower alkyl group having 1 to 3 carbon atoms; X ₁ is —COOCH ₃ , —COOC ₂ H ₅ , —COOC ₄ H ₉ , —COOCH ₂₎
CH (C ₂ H ₅ ) represents one or more groups selected from C ₄ H ₉ , —C ₆ H ₅ , and —CN. ) 4. In the graft copolymer (B),
The polyarylene sulfide resin composition according to any one of claims 1 to 3, wherein the α-olefin unit is ethylene. 5. The method according to claim 1, wherein the inorganic filler (C) is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group. Polyarylene sulfide resin composition. 6. The method according to claim 1, wherein the inorganic filler (C) is (A)
The polyarylene sulfide resin composition according to any one of claims 1 to 5, wherein the content of the polyarylene sulfide resin is 30 to 70% by weight of the total of (C). 7. An olefin copolymer segment (a) comprising (A) a linear polyarylene sulfide resin and (B) a glycidyl ester unit of an α-olefin unit and an α, β-unsaturated acid. The graft copolymer in which the polymer segment (b) composed of a terpene unit is chemically bonded in a branched or crosslinked structure is (B) 0.5 to 50 parts by weight with respect to (A) 100 parts by weight. The polyarylene sulfide resin composition according to any one of claims 1 to 6, wherein 8. A method for producing a polyarylene sulfide resin composition, comprising kneading the components (A) to (C) according to any one of claims 1 to 7. 9. A molded article of a polyarylene sulfide resin composition obtained by molding a metal insert using the polyarylene sulfide resin composition according to any one of claims 1 to 7.