JPH10330617A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition, excellent in releasability from a mold during the forming process, while keeping the properties of a polyarylene sulfide resin (high rigidity and resistance to heat). SOLUTION: This resin composition comprises (a) 40 to 100 wt.% of a polyarylene sulfide resin and (b) 60 to 0 wt.% of a norbornene-based resin (wherein, (a)+(b)=100 wt.%), incorporated with (c) 0 to 30 pts.wt. of a copolymer containing a straight-chain type functional group mainly composed of an unsaturated compound unit having an olefin unit and at least one type of functional group selected from the group consisting of carbgxyl, acid anhydride, oxazoline and epoxy groups, (d) 0.01 to 40 pts.wt. of a silicone polymer composed of a polyorganosiloxane and silica, and (e) 0 to 400 pts.wt. of a filler, the weight parts being based on 100 pts.wt. of the total amount of the components (a) and (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition having high rigidity and high heat resistance, and excellent in releasability from a mold during molding.

[0002]

2. Description of the Related Art Polyarylene sulfide resin is a thermoplastic resin having excellent heat resistance, chemical resistance, electrical properties, mechanical properties, dimensional stability and the like. It is used as a sealing material for components. However, recently, as molded products have been miniaturized and miniaturized, mold release from the mold during injection molding has been poor, and various release agents have been studied, but are not always sufficient.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and it has been found that, while maintaining the physical properties (high rigidity and high heat resistance) of polyarylene sulfide resin, An object of the present invention is to provide a thermoplastic resin composition having excellent releasability from a mold.

[0004]

According to the present invention, there are provided (a) 40 to 100% by weight of a polyarylene sulfide resin and (b) 60 to 0% by weight of a norbornene-based resin.
(C) an olefin unit and at least one selected from the group consisting of a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group with respect to 100 parts by weight of the total amount of (a) + (b) = 100% by weight]. 0 to 30 parts by weight of a linear functional group-containing copolymer (hereinafter also referred to as “(c) functional group-containing copolymer”) mainly composed of an unsaturated compound unit having a functional group of Silicone polymer consisting of siloxane and silica (hereinafter "(d) silicone polymer"
The present invention provides a thermoplastic resin composition comprising 0.01 to 40 parts by weight of (e) and 0 to 400 parts by weight of a filler (e).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) component; (a) polyarylene sulfide resin,
The main structural unit is a general formula; -Ar-S- (wherein, Ar
Represents a divalent aromatic, and S is a sulfur atom). Examples of the divalent aromatic constituting the polyarylene group include p-phenylene group, m-phenylene group, 2,6-naphthalene group, 4,4'-biphenylene group, p, p'-bibenzyl group, and these. And the like, as a typical example. Of these,
Poly-p-phenylene sulfide (PPS) having a nucleus-unsubstituted p-phenylene group is preferred from the viewpoint of moldability.

In the present invention, it is necessary that the polyarylene sulfide resin (a) contains at least 70 mol% of the above structural units in one molecule. If this constituent unit is less than 70 mol%, undesired results such as a decrease in the crystallinity of the obtained polyarylene sulfide resin, a low glass transition temperature, and poor physical properties of the molded product are produced. Further, in the present invention, if the polyarylene sulfide resin (a) is less than 30 mol% in one molecule, an aromatic group having a trivalent or higher bond, such as a 1,2,4-bonded phenylene nucleus, , An aliphatic group, a hetero atom-containing group, or the like. Further, (a)
The terminal group of the polyarylene sulfide resin is not particularly limited, but it is preferable that the thiol group (SH group) contains at least 80 mol%. Further, (a) the polyarylene sulfide resin includes a linear type, a semi-crosslinked type, and a crosslinked type.
Each of them can be used alone or in combination according to the purpose.

Further, as the polyarylene sulfide resin (a), a modified polyarylene sulfide resin or a mixture of a modified polyarylene sulfide resin and a polyarylene sulfide resin can be used. Examples of the modified polyarylene sulfide resin include resins modified with functional groups such as an epoxy group, an amino group, a carboxyl group, an acid anhydride group, an oxazoline group, a vinyl group, an acryloyl group, a methacryloyl group, an isocyanate group, and a mercapto group. Can be used, and an epoxy group-modified polyarylene sulfide resin and an amino group-modified polyarylene sulfide resin are particularly preferable. These functional groups react with the ester in the (b) norbornene-based resin to form a block copolymer of a polyarylene sulfide resin and a norbornene-based resin, thereby increasing the compatibility between the two and resulting resin composition. In addition to improving the physical properties of the product, it is possible to reduce the anisotropy of physical properties and moldability, which are disadvantages of the polyarylene sulfide resin.

The method for producing the polyarylene sulfide resin (a) includes a condensation reaction of a dihalogenated aromatic compound and a diol aromatic compound, a condensation reaction of a monohalogenated aromatic thiol, or a dihalogenated compound and an alkali sulfide. Alternatively, a method utilizing a desalination condensation reaction of an alkali hydrosulfide and an alkali or a hydrogen sulfide and an alkali compound is exemplified, but the method is not limited thereto. In the present invention, (a) the viscosity of the polyarylene sulfide resin is usually 300 ° C.
At a strain rate of 1,000 sec ^-1 , 100 to 4,000
0 poise.

(A) The amount of the polyarylene sulfide resin is 40 to 100% by weight in the components (a) and (b).
Preferably 40 to 99% by weight, more preferably 50 to 99% by weight.
97% by weight. If it exceeds 40% by weight, the heat resistance decreases. (B) Even though the norbornene-based resin is not used, sufficient releasability can be obtained, but the releasability is further improved by adding the norbornene-based resin.

Component (b): The (b) norbornene-based resin of the present invention is a polymer derived from a specific monomer represented by the following general formula (I).
Is included. Ring-opening polymer of specific monomer Ring-opening copolymer of specific monomer and copolymerizable monomer Hydrogenated polymer of the above ring-opening (co) polymer Free of the above ring-opening (co) polymer Hydrogenated copolymer after cyclization by Delkraft reaction Saturated copolymer of specific monomer and unsaturated double bond-containing compound

[0011]

Embedded image

[In the general formula (I), each of R ^{1 to} R ⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group. It may be different. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a monocyclic or It may form a polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. ]

Specific examples of the specific monomer represented by the general formula (I) include bicyclo [2.2.1] hept-2-
Ene, tricyclo [5.2.1.0 ^2,6 ] -8-decene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene, pentacyclo [6.5.1.1 ^3,6 . 0
^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.1 ^{2,5. 19,12} . 0 ^8,13] -3-pentadecene, tricyclo [4.4.0.1 ^{2, 5]} -3-undecene, 5-methylbicyclo [2.2.1] hept -2
-Ene, 5-ethylbicyclo [2.2.1] hept-2
-Ene, 5-methoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-
Cyanobicyclo [2.2.1] hept-2-ene,

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Ethoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-
Dodecene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, dimethanooctahydronaphthalene, ethyltetracyclododecene, 6-ethylidene-2-tetracyclododecene, trimethanooctahydronaphthalene,

Pentacyclo [8.4.0.1 ^2,5 . 1
^9,12 . 0 ^8,13] -3-hexadecene, heptacyclo [8.7.0.1 ^3,6. 1 ^10,17 . 1 ^12,15 . 0 ^2,7 .
0 ^{11, 16]} -4-eicosene, heptacyclo [8.8.
0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ]
-5-heneicosene, 5-ethylidenebicyclo [2.
2.1] Hept-2-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

5-fluorobicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [2.2.
1] Hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2
-Ene, 5,6-difluorobicyclo [2.2.1] hept-2-ene, 5,5-bis (trifluoromethyl)
Bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5-trifluoromethylbicyclo [2 2.2.1] hept-2-ene,

5,5,6-trifluorobicyclo [2.
2.1] Hept-2-ene, 5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6,6-tetrafluorobicyclo [2.
2.1] Hept-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5-difluoro-6,6-bis ( Trifluoromethyl) bicyclo [2.2.1] hept-2
-Ene, 5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-5-trifluoromethylbicyclo [2 2.2.1] hept-2-ene,

5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-
Chloro-5,6,6-trifluorobicyclo [2.2.
1] Hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-tri Fluoromethoxybicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,

8-fluorotetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-difluoromethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8,8-difluorotetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-Dodecene, 8,8-bis (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
8,9-Tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
8,9,9-tetrafluorotetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8, 8, 9, 9
-Tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
8-difluoro-9,9-bis (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] -3-dodecene, 8,8,9-trifluoro-9
-Trifluoromethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10] -3-dodecene, 8,8,9- trifluoro-9-trifluoromethoxy tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8, 8, 9
-Trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-chloro-8,
9,9-trifluorotetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dichloro-
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
(2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene and the like.

Among these, from the viewpoint of heat resistance of the obtained polymer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]
-3-pentadecene is preferred, and from the viewpoint of compatibility with the component (a), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0} ] -3-
Dodecene is most preferred. The above-mentioned specific monomers do not necessarily need to be used alone, and a ring-opening copolymerization reaction can be performed using two or more kinds.

Also, polybutadiene, polyisoprene,
In the presence of an unsaturated hydrocarbon-based polymer containing a carbon-carbon double bond in the main chain, such as a styrene-butadiene copolymer, an ethylene-nonconjugated diene copolymer, and polynorbornene, a specific monomer is used. Ring-opening polymerization may be performed. And
The hydrogenated product of the ring-opening copolymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Copolymerizable Monomer> The (b) norbornene-based resin may be obtained by subjecting the above-mentioned specific monomer to ring-opening polymerization alone. It may be a copolymer obtained by ring-opening copolymerization with a hydrophilic monomer. Specific examples of the copolymerizable monomer used in this case include cyclobutene, cyclopentene, cycloheptene, cyclooctene, bicyclo [2.2.1] hept-2-ene, and tricyclo [5.2.1.0. ^{Cycloolefins such as 2,6} ] -3-decene, 5-ethylidene-2-norbornene and dicyclopentadiene can be mentioned. further,
In the presence of an unsaturated hydrocarbon polymer containing a carbon-carbon double bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene polymer, polynorbornene, etc. The monomer may be subjected to ring-opening polymerization. The hydrogenated ring-opening polymer obtained in this case is useful as a raw material for a norbornene-based resin having high impact resistance.

<Unsaturated Double Bond-Containing Compound> Further, in order to obtain a norbornene resin comprising a saturated copolymer,
Examples of the unsaturated double bond-containing compound used together with the specific monomer include ethylene, propylene, butene, and the like.

<Ring-opening polymerization catalyst> In the present invention, a ring-opening polymer of a specific monomer, a ring-opening copolymer of a specific monomer and a copolymerizable monomer, and a ring-opening (co) polymer After cyclization of a hydrogenated polymer and a ring-opening (co) polymer by a Friedel-Crafts reaction, a ring-opening polymerization reaction for obtaining a hydrogenated copolymer is performed in the presence of a metathesis catalyst.

The metathesis catalyst comprises (i) at least one compound selected from the group consisting of W, Mo and Re, and (i)
i) Deming periodic table group IA element (eg, Li, N
a, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.),
A compound of a group IIIA element (eg, B, Al, etc.), a group IVA element (eg, Si, Sn, Pb, etc.) or a group IVB element (eg, Ti, Zr, etc.) A catalyst comprising a combination with at least one selected from those having a carbon bond or the element-hydrogen bond. In this case, in order to enhance the activity of the catalyst, an additive described later (iii) may be added.

Representative examples of W, Mo or Re compounds suitable as component (i) include WCl ₆ , MoCl
₅ , ReOCl _{3 and the} like, the compounds described in JP-A-1-132626, 8th column, lower left column, line 6 to item 8, upper right column, line 17 can be mentioned.

As a specific example of the component (ii), nC ₄ H ₉ L
i, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl,
(C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl
₂ , JP-A Nos. 1-13 such as methylalumoxane, LiH, etc.
No. 2,626, No. 8, right upper column, line 18 to item 8, lower right column, line 3 can be mentioned. As typical examples of the component (iii) as an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used. Further, JP-A-1-132626, No. 8, right lower column, The compounds shown in line 16 to item 9, upper left column, line 17 can be used.

With respect to the amount of the metathesis catalyst used, the molar ratio of the component (i) to the specific monomer is "component (i): specific monomer", usually from 1: 500 to 1: 50,000. , Preferably 1: 1,000 to 1: 10,000
The range is 0. The ratio of the component (i) to the component (ii) is such that (i) :( ii) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio. The molar ratio of the component (i) to the component (iii) is such that (iii) :( i) is 0.
005: 1 to 15: 1, preferably 0.05: 1 to 7:
1 range.

In the present invention, as a catalyst for synthesizing a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound, at least one selected from a titanium compound, a zirconium compound and a vanadium compound is used. And an organoaluminum compound as a co-catalyst. Here, as the titanium compound, titanium tetrachloride,
Examples of titanium trichloride and the like and zirconium compounds include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride. Further, as the vanadium compound, a vanadium compound represented by the following general formula or an electron donating adduct thereof is used. VO (OR) _a X _b or V (OR) _c X _d [where R is a hydrocarbon group and X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3,0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4. ]

As the electron donor, alcohol,
Phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, nitrogen-containing compounds such as ammonia, amines, nitriles, isocyanates And an electron donor. Further, as the organoaluminum compound as the co-catalyst, at least one selected from compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond is used. In the above description, for example, when a vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atoms to vanadium atoms (Al / V) is 2 or more, and preferably 2 to 5
0, particularly preferably in the range of 3-20.

<Solvent for Polymerization Reaction> Examples of the solvent (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) used in the ring-opening polymerization reaction include, for example, pentene, hexane, heptane, octane ,
Nonane, alkanes such as decane, cyclohexane, cycloheptane, cyclooctane, decalin, cycloalkanes such as norbornane, benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbons such as cumene, chlorobutane, bromohexene, methylene chloride, Compounds such as dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene, such as halogenated alkanes and aryl algenides;
Ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, saturated carboxylic esters such as dimethoxyethane, dibutyl ether, tetrahydrofuran, ethers such as dimethoxyethane, and the like, and these alone or They can be used in combination. Of these, aromatic carbons are preferred. The amount of solvent used is "solvent: specific monomer (weight ratio)"
Is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.

<Molecular Weight Control Agent> The molecular weight of the norbornene resin can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight control agent must be present in the reaction system. Adjust with. Here, suitable molecular weight regulators include, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include α-olefins such as -heptene, 1-octene, 1-nonene, and 1-decene, and styrene, of which 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.05 mol, per 1 mol of the specific monomer to be used in the ring-opening polymerization reaction.
It is 2 to 0.5 mol. The molecular weight of the norbornene resin used in the present invention, the intrinsic viscosity [η] _inh is 0.2 to
Those having a range of 5.0 are preferred.

<Hydrogenation catalyst> The ring-opened polymer obtained as described above can be hydrogenated using a hydrogenation catalyst. The hydrogenation reaction is carried out in a usual manner, that is, by adding a hydrogenation catalyst to a solution of the ring-opening polymer, and adding a normal pressure to the solution.
300 atm, preferably 3 to 200 atm of hydrogen gas
The reaction is carried out at a temperature of from 200 to 200C, preferably from 20 to 180C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of the heterogeneous catalyst include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or granular. These hydrogenation catalysts have a ring-opening polymer: hydrogenation catalyst (weight ratio) of 1: 1 × 10 ⁻⁶ to
Used at a ratio of 1: 2. As described above, the hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its characteristics do not deteriorate even by heating during molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

(B) The compounding amount of the norbornene resin is as follows:
60 to 0% by weight, preferably 6% by weight in the components (a) and (b)
0 to 1% by weight, more preferably 50 to 3% by weight. If it exceeds 60% by weight, the heat resistance decreases. Norbornene-based resin can obtain sufficient release properties even without it,
The addition improves the releasability.

Component (c); (c) the functional group-containing copolymer comprises an olefin unit, a carboxyl group, an acid anhydride group,
A linear functional group-containing copolymer mainly comprising an unsaturated compound unit having at least one functional group selected from the group consisting of an oxazoline group and an epoxy group;
No. 306287, paragraph 5, column 7, line 29 to paragraph 5, item 8
Polymers having a multilayer structure (graft structure) as disclosed in column 44, line, are not preferred because of reduced compatibility. This component (c) is a block copolymer or a random copolymer. Here, (c) the functional group-containing copolymer is, for example, a binary, ternary or multi-component copolymer of an olefin with an unsaturated compound having the above functional group and, if necessary, another unsaturated compound. It is. (C) As the olefin in the functional group-containing copolymer, ethylene,
Propylene is preferred, particularly preferably ethylene. Examples of unsaturated compounds containing a carboxyl group include acrylic acid, methacrylic acid, and maleic acid. Examples of unsaturated compounds containing an anhydride group include maleic anhydride and itaconic anhydride. Examples of unsaturated compounds containing an oxazoline group include vinyl oxazoline. Examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether. Preferred functional groups are an epoxy group and an acid anhydride group.

(C) In the functional group-containing copolymer, the amount of the olefin is usually 60 to 99.5% by weight, the amount of the unsaturated compound having a functional group is usually 40 to 0.5% by weight, The amount of the saturated compound is usually from 0 to 39.5% by weight. As the method for producing the component (c), any of the well-known methods such as a chain transfer method and an ionizing radiation irradiation method may be used, but the most preferable method is described in JP-A-64-42.
No. 256, paragraph 9, lower left column, first row to paragraph 10, upper left column, ninth
The method described in the line. The amount of the component (c) used is (a)
0 to 30 parts by weight, preferably 0.1 to 20 parts by weight, particularly preferably 3 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (b). If it exceeds 30 parts by weight, heat resistance will be reduced.

Component (d) The component (d) of the present invention is a silicone polymer comprising a polyorganosiloxane and silica. Here, the polyorganosiloxane in the average composition formula _{R 'e SiO (4-e} ) / 2 [wherein, e is 1.900 or more, a positive number of 2.100 or less, preferably e is 1.950 When e is less than 1.900 or more than 2.100, the effect of mold release is small. R ′ is selected from an unsaturated group and / or a phenyl ketone group, a hydrogen atom, a hydroxyl group, an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an amide group, an aminoxy group, an epoxy group, a mercapto group, and an ester group. And the remaining R 'is a hydrocarbon group having 1 to 15 carbon atoms (excluding an unsaturated group) and / or a fluorine group substituent. Average degree of polymerization of 20 to 10,000
Is a polyorganosiloxane. This polyorganosiloxane may be crosslinked. As a cross-linking method, a method of cross-linking by a reaction with 3 to 4 lower alkoxysilanes or the like or a usual peroxide cross-linking method is preferable.

Examples of the unsaturated group include a vinyl group,
Examples include an allyl group, a vinyloxy group, an acryloxy group, a methacryloxy group, and a maleimide group. The remaining R ′ bonded to the silicon atom is a hydrocarbon group having 1 to 15 carbon atoms, specifically, an alkyl group having 1 to 7 carbon atoms,
14 substituted or unsubstituted aryl groups, having 7 to 10 carbon atoms
And a methyl group, a phenyl group and the like are preferable. The average degree of polymerization of the polyorganosiloxane is from 20 to 10,000, preferably from 50 to 10,000.
It is 7,000, more preferably 500-6,000. When the average degree of polymerization is less than 20, the effect of releasing is small, and when it exceeds 10,000, the effect of releasing is small.

On the other hand, silica is a silicic acid or silicate filler, such as silicic anhydride by a dry method, hydrated silicic acid and a synthetic silicate by a wet method, colloidal silica, and fumed silica. The composition of the polyorganosiloxane and silica is preferably 10 to 200 parts by weight, more preferably 30 to 150 parts by weight of silica, based on 100 parts by weight of the polyorganosiloxane. If the amount of silica is less than 10 parts by weight, the polyorganosiloxane bleeds out on the surface of the resin molded product to make it white, and the effect of the releasability is reduced. On the other hand, when the amount of silica exceeds 200 parts by weight, the effect of the releasability is reduced.

In order to improve the bond between the polyorganosiloxane and the silica, a commonly used alkoxysilane compound may be added. The alkoxysilane compound is
It is an alkoxysilane compound having one or more epoxy groups, amino groups, isocyanate groups, hydroxyl groups or mercapto groups in the molecule. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3 , 4-ethoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-
(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyltriethoxysilane, N
-Phenylaminomethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3-piperazinopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-hydroxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3
-Mercaptomethyldimethoxysilane and the like. The addition amount of the alkoxysilane compound is 0 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the polyorganosiloxane.

The amount of the silicone polymer (d) of the present invention is 0.01 to 100 parts by weight of (a) + (b).
It is 40 parts by weight, preferably 0.1 to 30 parts by weight.
If the amount is less than 0.01 part by weight, there is no effect on the release property.
If it exceeds 0 parts by weight, the heat resistance will be poor. (D) To prepare the silicone polymer, use a kneader, a Banbury mixer, an extruder, a mixing roll, and the like.
It is preferable in terms of cost to add silica, polyorganosiloxane, and other additives such as a silane coupling agent and a cross-linking agent according to the purpose, knead them, and powderize them.

(E) Filler: The thermoplastic resin composition of the present invention further comprises (e) a filler, whereby the thermoplastic resin composition is more excellent in heat resistance and dimensional accuracy of the obtained molded article. It can be. (E) Examples of the filler include a fibrous material having an aspect ratio (average length L / average system D) of more than 1 and 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 is set to 20 to 500.
It is preferable that If the aspect ratio is less than 20,
The anisotropy is small but the stiffness is not high, while 50
If it exceeds 0, the rigidity increases, but the anisotropy increases, which is not practical. In order to improve the anisotropy,
The aspect ratio of the fibrous filler is less than 20, preferably 1
0 or less. Further, the average diameter of the fibrous filler is preferably from 0.1 to 250 μm, and if it is less than 0.1 μm, the rigidity does not increase, while if it exceeds 250 μm, impact resistance and appearance deteriorate. On the other hand, the powdery filler has an average particle diameter of 100 μm or less, preferably about 60 μm or less. When a powdery filler is used, a molded article having a good appearance can be obtained.

Among them, examples of the fibrous filler include inorganic fibers such as glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber and metal fiber, and inorganic fibers such as potassium titanate whisker and zinc oxide whisker. Whiskers and carbon fibers. In addition, as powdery fillers, wollastonite,
Silicates such as sericite, kaolin, mica, clay, pentonite, asbestos, talc and alumina silicate, alumina, metal compounds such as silicon chloride, magnesium oxide, zirconium oxide and titanium oxide, calcium carbonate, magnesium carbonate, dolomite, etc. Carbonate, calcium sulfate, sulfate such as barium sulfate, glass beads, boron nitride, silicon carbide, silica and the like, and these may be hollow. These fillers can be used in combination of two or more, and can be used after being pretreated with a silane coupling agent as needed. Examples of the silane coupling agent include vinyl silane, acryl silane, amino silane, epoxy silane, chloro silane, mercapto silane, peroxy silane, and the like.

(E) The proportion of the filler used is (a) to
It is 0 to 400 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the total amount of the component (b). If the amount exceeds 400 parts by weight, the moldability and impact resistance are reduced.

If necessary, other thermoplastic resins or elastomers may be added to the resin composition of the present invention in an amount of about 50 parts by weight or less based on 100 parts by weight of the resin composition of the present invention. As other thermoplastic resins or elastomers, specifically, styrene resin, vinyl chloride resin, acrylic resin, polyphenylene ether resin, polycarbonate resin, polyester resin, polyamide resin, polyether sulfone resin, polysulfone resin, polyimide Resin, polyetherimide resin, hydrogenated styrene-butadiene (block, random) copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, ethylene-propylene rubber, and the like can be given.

The resin composition of the present invention may contain a flame retardant, if necessary. Examples of the flame retardant include halogen-based flame retardants, non-halogen-based flame retardants, metal oxides and inorganic flame retardants. Among them, examples of the halogen-based flame retardant include ammonium bromide, tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, hexabromocyclododecane, bis (bromoethyl ether) tetrabromobisphenol A, brominated polycarbonate, brominated polycarbonate, Brominated flame retardants such as polystyrene, chlorinated paraffin, chlorinated polyethylene, chlorinated flame retardants such as organochlorinated flame retardants (hetic acid, dechlorane plus, phthalic anhydride tetrachloride), tris (chloropropyl) phosphate, Halogen-containing phosphoric acid esters such as tris (2,3-dibromopropyl) phosphate are exemplified. These halogen-based flame retardants include Sb ₂
The combined use of O ₃ increases the flame retardant effect. Non-halogen flame retardants include triphenyl phosphate, cresyl diphenyl phosphate, and aromatic diphosphate represented by the following general formula (II).

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[In the general formula (II), R ^{5 to} R ⁶ are the same or different and are a lower alkyl group, R ^{7 to} R ⁸ are the same or different and are a hydrogen atom or a lower alkyl group, and Y is —CH
_{2 -, - C (CH 3} ) 2 -, - S -, - SO 2 -, - O
And-, -CO-, and -N = N-, k represents 0 or 1, and n represents an integer of 0 to 4. ], Melamine, cyanuric acid, melamine cyanurate, tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
-Triazines such as isocyanurate, guanidines such as 1,3-diphenylguanidine and 1,3-di-o-tolylguanidine, thiazoles such as 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole , Dithioacid salts such as zinc dimethyldithiocarboxylate, zinc diethyldithiocarboxylate, zinc N-ethyl-N-phenyldithiocarboxylate, 2- [2-hydroxy-3- (3,4,5,6-tetra- Benzotriazoles such as hydrophthalimide-methyl) -5-methylphenyl] benzotriazole, 2- (2-hydroxy-3,5-tert-butylphenyl) benothriazole, and nitrogen such as derivatives or / and salts thereof And the like.

The phosphorus-based flame retardant preferably has a melting point of 100 ° C. or higher, particularly preferably 160 ° C. or higher. If the melting point of the phosphorus-based flame retardant is less than 100 ° C., the impact resistance and heat resistance of the resulting composition may be significantly reduced, which is not preferable. The nitrogen-based flame retardant preferably has a melting point of 140 ° C. or higher, particularly preferably 160 ° C.
Or more and / or the sublimation point is preferably 20
The temperature is 0 ° C or higher, particularly preferably 280 ° C or higher. If the melting point of the nitrogen-based flame retardant is less than 140 ° C., the impact resistance, heat resistance, and flame retardancy of the resulting composition may be reduced,
If the sublimation point is less than 200 ° C., the flame retardancy may be significantly reduced. The non-halogen flame retardant may be a phosphoric acid amide compound bonded to a phosphoric acid group.

Other metal oxides and inorganic flame retardants include silicone compounds typified by polyorganosiloxanes such as dimethyl silicone rubber and methyl hydrogen polysiloxane; guanidine derivatives such as guanidine phosphate; boric acid; Examples include zinc oxide, novolak resin, antimony oxide, sodium antimonate, magnesium hydroxide, and aluminum hydroxide.
These flame retardants can be used alone or in combination of two or more.

The proportion of the flame retardant used is preferably from 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).
0 parts by weight, more preferably 1 to 50 parts by weight, particularly preferably 2 to 40 parts by weight, if less than 0.1 part by weight,
In some cases, flame retardancy cannot be improved.
If the amount exceeds 00 parts by weight, heat resistance and rigidity may decrease.

Further, an antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6- is added to the resin composition of the present invention.
Dimethylphenol, 2,2-methylene-bis (4-methyl-6-t-butylphenol), tris (di-nonylphenyl phosphite); an ultraviolet absorber such as p-
Butylphenyl salicylate, 2,2'-dihydroxy-4-methoxy-benzophenone, 2- (2'-dihydroxy-4'-m-octoxyphenyl) benzotriazole, "TINUVIN320" (manufactured by Ciba-Geigy), "TINUVIN329" ( A lubricant such as paraffin wax, stearic acid, hydrogenated oil, stearamide, methylene bis stearamide, m-butyl stearate, ketone wax,
Octyl alcohol, hydroxystearic acid triglyceride and the like may be added in necessary amounts.

Further, a nucleating agent may be added to the resin composition of the present invention. As the crystal nucleating agent, an inorganic substance,
Any organic substance can be used. Inorganic substances include simple substances such as zinc powder, aluminum powder, graphite, and carbon black; metal oxides such as zinc oxide, magnesium oxide, alumina, titanium dioxide, manganese dioxide, silicon dioxide, and iron tetroxide; and boron nitride. Inorganic salts such as nitrides, sodium carbonate, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, barium sulfate, calcium phosphate,
Clays such as talc, kaolin, clay, clay and the like can be used. In addition, as organic substances, organic salts such as calcium oxalate, sodium oxalate, calcium benzoate, calcium phthalate, calcium tartrate, and magnesium stearate, heat-resistant polymers, and crosslinked products of heat-resistant polymers are used. be able to.

Of these crystal nucleating agents, preferred are boron nitride; clays such as talc, kaolin, clay and clay; and heat-resistant polymers having a crosslinked or branched structure. Some of the crystal nucleating agents may overlap with the filler (e), but these substances can fulfill both functions. The amount of the crystal nucleating agent to be used is preferably 0.002 to 5 parts by weight, more preferably 0.02 to 100 parts by weight of the polyarylene sulfide resin (a).
If the amount is less than 0.002 parts by weight, the effect of increasing the crystallization rate may not be sufficient. On the other hand, if it exceeds 5 parts by weight, the heat resistance and the flexural modulus may be undesirably reduced. Since the nucleating agent can control the crystallization rate of the polyarylene sulfide resin (a), the crystallization is terminated when the resin composition enters the mold by injection molding, thereby reducing the formation of burrs. can do.
Further, since the crystal nucleating agent is a low molecular compound, it also has an effect as a plasticizer, and can improve the fluidity and moldability of the resin composition of the present invention in a molten state.

Further, a sliding agent may be added to the resin composition of the present invention for the purpose of improving slidability. As the sliding agent, both inorganic and organic substances can be used. As inorganic sliding agents, inorganic fibers such as glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, carbon fiber,
Inorganic whiskers such as potassium titanate whiskers, silicone carbide whiskers, carbon graphite whiskers, silicon nitride whiskers, α-alumina whiskers, zinc oxide whiskers, particulate glass, ceramics, carbon and scaly mica, glass, etc. Chromium such as inorganic powder and molybdenum disulfide,
Molybdenum, tungsten (VIA group metal) sulfide, and the like can be given.

Examples of the organic sliding agent include organic fibers such as polyamide fiber, wholly aromatic polyamide fiber (aramid fiber), polyester fiber and cellulose fiber, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether. Copolymer, tetrafluoroethylene / hexafluoropropylene copolymer,
Fluorocarbon polymers such as tetrafluoroethylene / ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene / ethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride;
Examples include polymer powders such as ultra-high molecular weight polyethylene particles, polyarylene thioether ketone particles, and aromatic polyester particles, and lubricating oils such as silicone oil, aromatic oil, fluorine oil, hardened oil, polyethylene wax, and ethylene bis stearamide. .

The resin composition of the present invention comprises a single-screw extruder,
It is obtained by using a mixer such as a multi-screw extruder, a Banbury mixer, a kneader, and a mixing roll, and further mixing the components (a) to (e) and, if necessary, an organic phosphorus compound and other additives. Examples of the method for producing the resin composition of the present invention are as follows: a method of mixing the components with a mixer, and then melt-kneading at 240 to 360 ° C. using an extruder to obtain a granulated product; Examples thereof include a method in which each component is directly melt-kneaded in a molding machine to obtain pellets. In addition, there is a method in which a resin component is kneaded using a twin-screw extruder, and then a filler is added later to form a pellet.

The resin composition of the present invention thus obtained is
Especially excellent heat resistance, Vicat softening temperature is 180 ~ 330
° C, preferably 210-300 ° C. When the Vicat softening temperature is lower than 180 ° C, heat resistance and rigidity are low, while
If the temperature exceeds 330 ° C., the moldability, especially the fluidity, will be poor. Here, in order to adjust the Vicat softening temperature of the resin composition of the present invention, the ratio of (a) the polyarylene sulfide resin and (b) the norbornene-based resin is changed, or the component (c) which is a compatibilizer, The amount of the component (d) or other additives, such as a thermoplastic resin or an elastomer, may be varied.

The resin composition of the present invention is formed into a molded product by applying various known molding methods such as injection molding, compression molding, extrusion molding, and blow molding. . The resin composition of the present invention is used as an automotive component, for example, a cylinder head cover, an underhood component, a clean fan, a radiator tank, a relay cap, a window screen, and the like, as an electronic component.
For example, light emitting diodes (visible light diodes, infrared light emitting diodes, optical communication light emitting diodes), transistors, integrated circuits, phototransistors, EPROMs, photocouplers, photointerrupters, packages such as CCDs, capacitors, LC filter cases, tact SWs, slides For OA supply parts such as SW, for example, heat shield of copier, printer parts, motor parts, etc.
As electric and home appliance parts, for example, FDD carriage / bearing, optical disk optical pickup base, VTR / cylinder base, rotary connector, motor brush holder / commutator, electromagnetic cooker coil base,
For microwave oven parts (stirrer shaft, tray, turntable ring), dryer nozzle, steam iron valve, condenser lens case for optical fiber, etc., as mechanical parts, for example, watch board, chemical pump case
It can be used for various applications such as impellers, gear pumps, rheometers, general-purpose engine carburetors and heat insulators.

A preferred embodiment of the present invention is as follows. (A) The polyarylene sulfide resin is poly-p-
A thermoplastic resin composition which is phenylene sulfide. (B) The specific monomer constituting the norbornene resin is 8
-Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene. (C) A thermoplastic resin composition wherein the functional group-containing copolymer is an ethylene-epoxy group-containing unsaturated compound and an acid anhydride group-containing unsaturated compound copolymer, more preferably an ethylene-glycidyl methacrylate copolymer.

[0066]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples are as follows.

Glass transition temperature differential scanning calorimeter [manufactured by Seiko Instruments Inc., SSC-
580] in a nitrogen atmosphere from normal temperature to a heating rate of 2
It was measured at 0 ° C./min. Hydrogenation rate In the case of hydrogenated homopolymer, 60 MHz, ¹ H-N
It was measured by MR. Heat resistance (Vicat softening temperature) Measured at a load of 1 kgf and a heating rate of 50 ° C./hour using a test piece having a thickness of １ ／ ″ according to JIS K7206.

Formability (MFR) Melt flow rate (MFR) was measured at 300 ° C. × 10 kgf according to JIS K7210. The unit is g / 10 minutes. Impact resistance (Izod impact strength) test piece (1/4 "x 1/2" x 5/2 ", notched)
Was used to measure the Izod Impact according to ASTM D790. Unit is kg
f · cm / cm. Release resistance test Using a injection molding machine with a mold clamping force of 40 ton,
When molding at a molding temperature of 320 ° C. and a mold temperature of 130 ° C., a molded product was ejected from the mold and the force applied to the pin was measured, and this was defined as the mold release resistance value. It can be said that the lower the release resistance value, the better the release property.

REFERENCE EXAMPLE Each component was prepared for producing a resin composition. (A) Component Linear polyphenylene sulfide (PPS): LN-1 manufactured by Topren Co., Ltd. was used.

(B) Component (b-1) Norbornene Resin I As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 250 parts of 1-hexene as a molecular weight regulator, and 500 parts of toluene
Were charged into a nitrogen-replaced reaction vessel and heated to 80 ° C. 0.58 parts of a toluene solution of triethyl aluminum (1.5 mol / L) as a polymerization catalyst,
Denaturing WCl ₆ with butanol and methanol, t
Add 2.5 parts of a WCl ₆ solution (concentration: 0.05 mol / L) in which the molar ratio of butanol to methanol and tungsten is 0.35: 0.3: 1, and heat at 80 ° C. for 3 hours. After stirring, a polymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

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4,000 parts of the obtained polymer solution was put into an autoclave, and RuHCl (CO) [P (C ₆
H ₅ ) ₃ ] ₃ was added in an amount of 0.48, and the hydrogen gas pressure was increased to 100.
A hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution, hydrogen gas was released to obtain a hydrogenated polymer solution. The polymer solution was coagulated with a large amount of methanol and dried to isolate the polymer. The glass transition temperature (Tg) of this polymer is 170 ° C., and the hydrogenation rate is substantially 100%.
And gel permeation chromatography (G
The weight average molecular weight (Mw) in terms of polystyrene measured by PC) was 55,000.

(B-2) Norbornene-based resin II As a specific monomer, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-Dodecene (300 parts) in cyclohexane (2,000)
And 10 parts of 1-hexene was added as a molecular weight regulator, and the internal temperature was maintained at 30 ° C. To this solution, 100 parts of a 15% solution of triethylaluminum in cyclohexane,
50 parts of triethylamine and 20% of titanium tetrachloride
100 parts of a cyclohexane solution was added, and a ring-opening polymerization reaction was performed for 2 hours. The polymerization conversion of this reaction was 95%.

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To 500 parts of the cyclohexane solution of the obtained ring-opening polymer, 1 part of palladium-carbon was added, and the mixture was charged into an autoclave. The hydrogen pressure was 70 kg / cm ² ,
The hydrogenation reaction was performed at 40 ° C. for 3 hours. After cooling the obtained reaction solution, hydrogen gas was released to obtain a hydrogenated polymer solution. The polymer solution was coagulated in a large amount of methanol and dried to isolate the polymer. The glass transition temperature (Tg) of this resin is 142 ° C., and the hydrogenation rate is 9
It was 9.9% or more, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) was 59,500.

(B-3) Norbornene Resin III A reaction vessel equipped with a stirring blade, a gas inlet tube, a thermometer and a dropping funnel is sufficiently replaced with nitrogen gas, and the inside of the reaction vessel is dehydrated and dried by molecular sheep. 2,500 ML of toluene. Under a flow of nitrogen, pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene 75
Parts, 25 mmol of ethyl aluminum suzuki chloride and 2.5 mmol of dichloroethoxyoxovanadium were added to the dropping funnel. Through a gas introduction tube, a mixed gas of 200 L / hr of dry ethylene and 400 L / hr of nitrogen was passed through a flask maintained at 10 ° C. for 10 minutes.

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From the dropping funnel, dichloroethoxyoxovanadium was added dropwise to start the copolymer reaction, and the copolymerization reaction was carried out at 10 ° C. while passing the above mixed gas.
After a lapse of 30 minutes, 30 ml of methanol was added to the reaction solution to stop the polymerization reaction. Subsequently, the polymer solution was coagulated in a large amount of methanol and dried to isolate a norbornene-based saturated copolymer. The glass transition temperature (Tg) of this polymer is 135 ° C., and the intrinsic viscosity [η] _inh measured in decalin at 130 ° C. is 0.62 dl /.
g.

(C) Component (c-1); Lexpearl RA manufactured by Nippon Petrochemical Co., Ltd.
3150 (ethylene-glycidyl methacrylate copolymer) (d) Component silicone polymer; DC4-7051 (manufactured by Toray Dow Corning Silicone Co., Ltd.)
0%, silica 50 to 30%, epoxy group-containing silane coupling agent-treated product) polyethylene wax; Hoechst Industry Co., Ltd.
Manufactured by Toray Dow Corning Silicone Co., Ltd., Trefil E-730S silicone oil; dimethyl silicone oil [viscosity =
1,000 cSt (25 ° C.)] (e) Component glass fiber; aspect ratio = 230, manufactured by Asahi Fiberglass Co., Ltd., 03MAFT523

Examples 1 to 5 and Comparative Examples 1 to 7 The pellets were melt-kneaded at 310 ° C. using a 40 mmφ twin screw extruder at the compounding formulations shown in Tables 1 and 2, and formed into pellets.
Using the obtained pellets, injection molding was performed under the above injection conditions to obtain test pieces for evaluation. The evaluation results are shown in Tables 1 and 2.

According to Table 1, the resin composition of the present invention is
By blending a silicone polymer, a norbornene-based resin, a specific functional group-containing copolymer, etc. with PS,
It can be seen that the releasability, which is a problem in PS, is improved, and the heat resistance, the Izod impact strength, and the like are suppressed to practically acceptable levels. In particular, it can be seen that when a norbornene-based resin is added, the releasability is further improved. In contrast, as apparent from Table 2, Comparative Examples 1 to
No. 7 is an example in which the mixing ratio of the component (a) and the component (b), various release agents and amounts, or the component (e) is mixed in a large amount, but sufficient release properties and physical properties are obtained. You can see that it has not been done.

[0082]

[Table 1]

[0083]

[Table 2]

* 1) Polyethylene wax [manufactured by Hoechst Industry Co., Ltd., PE190] * 2) Silicone rubber powder [manufactured by Toray Dow Corning Silicone Co., Ltd., Trefil E-730S] * 3) Silicone oil (dimethyl silicone oil) * 4) Silicone polymer [DC4-7051 manufactured by Dow Corning Toray Silicone Co., Ltd.] * 5) Molding could not be performed due to poor fluidity.

[0085]

The thermoplastic resin composition of the present invention has high rigidity, excellent impact resistance, and high heat resistance by adding a specific silicone polymer to a polyarylene sulfide resin. Excellent release from the mold.

Claims (1)

[Claims] (A) polyarylene sulfide resin 4
0 to 100% by weight and (b) norbornene resin 60
0% by weight [(a) + (b) = 100% by weight]
(C) an olefin unit and an unsaturated compound unit having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group. 0 to 30 parts by weight of a linear functional group-containing copolymer, (d) a silicone polymer comprising polyorganosiloxane and silica 0.01 to
A thermoplastic resin composition comprising 40 parts by weight and (e) 0 to 400 parts by weight of a filler.