JPH0753866A - Resin composition and molded product - Google Patents

Abstract

PURPOSE:To provide the composition comprising a polyphenylene sulfide resin, an amorphous cyclic olefinic copolymer, glass fibers having a small diameter and a filler, excellent in heat resistance, strength, rigidity, dimensional stability, moldability and surface smoothness, and useful for automotive lamp reflectors. CONSTITUTION:The composition comprises (A) 20-45wt.% of a polyphenylene sulfide resin, (B) 5-30wt.% of an amorphous cyclic olefin copolymer having a glass transition point of >=120 deg.C, (C) 0-15wt.% of glass fibers having a small fiber diameter of <=7mum, and (D) 25-75wt.%n of a non-fibrous inorganic filler, the components having been melt-kneaded. The component A preferably has, e.g. repeating units of the formula, and the component B preferably is e.g. the copolymer of an alpha-olefin such as ethylene with a cyclic olefin such as bicyclo[2.2.1]hepto-2-ene derivative. The component D is preferably calcium carbonate, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) composition having excellent heat resistance, rigidity, dimensional stability and molding processability, and a surface obtained by injection molding the resin composition. The present invention relates to a molded product having excellent smoothness and adhesion to a metal vapor deposition film.
A resin composition having the above properties obtained by melt-kneading a non-fibrous inorganic filler and, if necessary, a glass fiber having a specific fiber diameter to a resin component mainly composed of PS resin and an amorphous cyclic olefin copolymer And a molded article.

[0002]

2. Description of the Related Art It is well known that automobile parts, particularly parts in an engine room, electrical parts, functional parts, etc. are gradually replaced by metal from plastic. The main reason for this is that plastic is lighter in weight than metal, has a high degree of freedom in designing products, and can originally improve productivity by integrally molding a plurality of parts. One of the representative functional parts is a lamp reflector. As the lamp reflector, a thermosetting resin such as unsaturated polyester BMC or one made of aluminum has been mainly used conventionally. Thermosetting resin reflectors are lighter than aluminum ones, but at present the specific gravity exceeds 2.0, so further weight reduction is required, and the post treatment of molded products peculiar to thermosetting resins is required. Since there are problems such as complexity of work and work environment pollution due to dust and the like, conversion to a thermoplastic resin material is required. PPS resin has excellent heat resistance, rigidity, dimensional stability, good compatibility with fillers, and good moldability, so it has a high potential as a material for lamp reflectors, and it has been aiming for weight reduction until now. PP
A lamp reflector obtained by injection-molding a composition in which S and a specific hollow filler are combined (for example, JP-A-3-
No. 208201), a lamp reflector (for example, Japanese Patent Laid-Open No. 4-334801) obtained by injection molding a composition in which PPS and a fibrous reinforcement having a specific diameter are combined for the purpose of improving surface smoothness and strength. Has been done.

However, in these conventional techniques, there are problems such as a warp of a molded product due to a difference in molding shrinkage between a resin flow direction and a vertical direction at the time of injection molding and insufficient adhesion to an aluminum vapor deposition film in a post-processing step. At present, there is a strong demand for these improvements.

[0004]

Therefore, the present invention is directed to a thermoplastic resin composition having excellent heat resistance, rigidity, dimensional stability, and moldability, and surface smoothness and metal obtained by injection molding of the resin composition. It is an object to obtain a molded product having excellent adhesion to a deposited film.

As a result of earnest studies for solving this problem,
A resin composition and a molded product obtained by adding a non-fibrous inorganic filler and, if necessary, a glass fiber having a specific fiber diameter to a resin component mainly composed of a PPS resin and an amorphous cyclic olefin copolymer have the above-mentioned required characteristics. The present invention has been accomplished by discovering that the above conditions are sufficiently satisfied.

[0006]

That is, the present invention is as follows.
(A) 20 to 45% by weight of polyphenylene sulfide resin, (B) 5 to 30% by weight of amorphous cyclic olefin copolymer having a glass transition point of 120 ° C. or higher, and (C) fiber diameter of 7 μm.
A resin composition and a resin composition characterized by being obtained by melt-kneading the following mixture consisting of 0 to 15% by weight of thin glass fibers and 25 to 75% by weight of (D) a non-fibrous inorganic filler. It is a molded product having excellent surface smoothness obtained by injection molding.

The (A) PPS resin used in the present invention is
The repeating unit represented by the structural formula (I)

[Chemical 1] It is a polymer containing 70 mol% or more, more preferably 90 mol% or more, and if the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. Also PPS
The resin can comprise less than 30 mol% of its repeating units with repeating units having the following structural formula.

[0008]

[Chemical 2] The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, but is usually 50 to 20,0.
A 00 poise (320 ° C., shear rate 10 sec ⁻¹ ) is used.

Such a PPS resin is a known method, that is, a method for obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368 or JP-B-52-1224.
It can be produced by the method of obtaining a polymer having a relatively large molecular weight described in JP-A-No. In the present invention, the PPS resin obtained as described above is subjected to crosslinking / polymerization by heating in air, washing with an organic solvent, hot water, an aqueous acid solution, an acid anhydride group, an epoxy group, an amino group, an isocyanate group, etc. Of course, it is possible to use it after various treatments such as activation with a functional group-containing compound.

The amorphous cyclic olefin copolymer (B) used in the present invention is a copolymer of an α-olefin such as ethylene, propylene, butene 1, and 4-methylpentene 1 and at least one cyclic olefin. The glass transition point thereof is 120 ° C. or higher. Specific examples of the cyclic olefin include bicyclo [2.2.1] hept-2ene derivative, tetracyclo [4.4.0.1 ^2.5 .
1 ^7.10] -3-decene derivatives, hexacyclo [6.6.
1.1 ^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene derivative, octacyclo [8.8.0.1 ^2.9 . 1
^4.7 . 1 ^11.18 . 1 ^{13.1 6} ． 0 ^3.8 . 0 ^12.17 ] -5-
Docosene derivative, pentacyclo [6.6.1.1 ^3.6 .
0 ^2.7 . 0 ^9.14 ] -4-Hexadecene derivative, heptacyclo-5-icosene derivative, heptacyclo-5-heneicosene derivative, tricyclo [4.3.0.1 ^2.5 ]-
3-decene derivative, tricyclo [4.3.0.1 ^2.5 ]
-3-Undecene derivative, pentacyclo [6.5.1.
1 ^3.6 . 0 ^2.7 . 0 ^9.14 ] -4-Pentadecene derivative,
Pentacyclopentadecadiene derivative, pentacyclo [4.7.0.1 ^2.5 . 0 ^8.13 . 1 ^9.12] -3-pentadecene derivatives and Nonashikuro [9.10.1.
1 ^4.7 . 1 ^13.20 . 1 ^15.18 . 0 ^2.10 . 0 ^12.21 . 0
^14.19 ] -5-Pentacocene derivative and the like can be mentioned.

As the method for polymerizing the above α-olefin and at least one cyclic olefin, hexane, heptane, octane, cyclohexane, benzene, toluene,
A preferable example is a method in which a catalyst such as a vanadium compound or an organoaluminum compound is used in a hydrocarbon solvent such as xylene.

Among the amorphous cyclic olefin copolymers thus obtained, those used in the present invention are required to have a glass transition point of 120 ° C. or higher.
If the glass transition point of the copolymer is less than 120 ° C., the resulting resin composition lacks dimensional stability and heat resistance, which is not preferable. A specific example of the amorphous cyclic olefin copolymer satisfying such characteristics is the amorphous cyclic olefin copolymer manufactured and sold by Mitsui Petrochemical Co., Ltd. under the trade name of "APEL". To be

The non-fibrous filler used in the present invention is a component necessary for improving the dimensional stability of the material, and specific examples thereof include wollastonite, sericite, kaolin, mica, clay, bentonite, Silicates such as asbestos, talc, alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, etc. Examples thereof include sulfates, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, and silica, which may be hollow, and two or more kinds of these fillers may be used in combination. is there. In addition, it is more preferable to use these non-fibrous fillers after pre-treating them with a coupling agent such as a silane-based, titanate-based, or aluminum-based filler from the viewpoint of mechanical strength and the like.

In the present invention, heat resistance and strength are improved by further blending a fine glass fiber having a single yarn diameter of 7 μm or less as a fibrous reinforcing material. In order to satisfy the heat resistance, strength and rigidity required for the lamp reflector, a fibrous reinforcing material may be added. At this time, a glass fiber having a single yarn diameter of more than 7 μm which is usually used as a reinforcing material for thermoplastic resin. If used, the surface smoothness of the molded product is significantly impaired. Single fiber diameter of glass fiber used preferably is 6μ
m or less, and more preferably 3 μm or less.

The proportion of each component in the resin composition of the present invention is 20 to 45% by weight of PPS resin, 5 to 30% by weight of amorphous cyclic olefin copolymer, and 25 of non-fibrous inorganic filler.
˜75% by weight and 0-15% by weight of fine glass fiber having a single yarn diameter of 7 μm or less, 25-40% by weight of PPS resin, 10-25% by weight of amorphous cyclic olefin copolymer, non-fibrous inorganic filling It is preferable that the range is 30 to 70% by weight of the material and 3 to 10% by weight of the fine glass fiber having a single yarn diameter of 7 μm or less. A resin composition and a molded product thereof satisfying all the properties of heat resistance, strength, rigidity, dimensional stability, molding processability and surface smoothness, and metal vapor deposition film adhesiveness required for a lamp reflector only in the above mixing ratio are provided. You can get it. For example, if the blending amount of the amorphous cyclic olefin copolymer is less than 5% by weight, the adhesion of the vapor-deposited metal film will be insufficient, and conversely if the blending amount exceeds 30% by weight, the fluidity will decrease and the melt molding process will be difficult. become. If the content of the non-fibrous inorganic filler is less than 25% by weight, heat resistance and dimensional stability will be insufficient, and conversely, if the content of the non-fibrous inorganic filler exceeds 75% by weight, the fluidity will be lowered, making the melt molding process difficult. And the surface smoothness is significantly reduced. Further, when the compounding amount of the fine glass fiber exceeds 15% by weight, the surface smoothness is remarkably deteriorated.

The PPS resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and their substitution products), ultraviolet rays, etc. within a range not impairing the object of the present invention. Absorbents (eg resorcinol, salicylate, benzotriazole, benzophenone etc.), lubricants and mold release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax etc.), dyes (eg nigrosine etc.) And conventional additives such as colorants, including pigments (eg, cadmium sulfide, phthalocyanine, carbon black, etc.), plasticizers, flame retardants, flame retardant aids, antistatic agents and other thermoplastic resins (eg polyamide, polysulfone, Polytetrafluoroethylene Emissions, polyetherimide, polyphenylene oxide, polyamide, polyimide,
Polycarbonate, polyethersulfone, polyetherketone, polyetheretherketone, epoxy resin, phenolic resin, polyethylene, polystyrene, polypropylene, ABS resin, polyester, polyamide elastomer, polyester elastomer, etc.) are added to obtain the desired characteristics. Can be granted.

In the PPS resin composition of the present invention, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane are used for the purpose of improving mechanical strength and moldability such as burr, etc., within a range not impairing the effects of the present invention. Glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureido Propyltrimethoxysilane and γ
-(2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ
-Isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ-aminopropyltrisilane Organosilane compounds such as methoxysilane and γ-aminopropyltriethoxysilane can be added.

The PPS resin composition of the present invention is suitable for production by melt-kneading using a melt-kneading machine having a sufficient kneading force, since the desired characteristics can be exhibited. A known method can be used for the melt kneading, and for example, a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder can be used to melt-knead at a temperature of 270 to 380 ° C. to obtain a composition. it can. The order of mixing the raw materials is not particularly limited, and a method in which the PPS resin, the amorphous cyclic olefin copolymer and the fibrous and / or non-fibrous filler are dry-blended, and then melt-kneaded by the above-mentioned method, Alternatively, a method in which two of the PPS resin, the fibrous and / or non-fibrous filler and the amorphous cyclic olefin copolymer are dry-blended and melt-kneaded, and then the remaining one is melt-kneaded may be used. It is possible.

By molding the PPS resin composition of the present invention thus obtained by injection molding, a molded article having excellent surface smoothness can be obtained. This molded product has excellent surface smoothness, adhesion to metal vapor deposition film, dimensional stability, heat resistance, strength, and molding processability.
It can be used as a component of electric equipment, automobiles, etc., and is particularly useful as a lamp reflector base, and a very practical lamp reflector can be obtained by vapor deposition of a metal such as aluminum.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to examples. The properties described in Examples and Comparative Examples were measured by the following methods.

(1) Specific gravity of molded product: underwater substitution method (2) Molding shrinkage ratio: 80 × 80 × 3 mm square plate is injection-molded, and the molding shrinkage ratio in the direction perpendicular to the flow direction is the original size of the mold. Measured.

(3) Bending strength: ASTM D790 (4) Heat deformation temperature: ASTM D648 (5) Surface smoothness: 80 × 80 × 3 mm square plate surface glossiness is measured with a portable sharpness glossmeter PGD- It was measured using IV (Japan Color Research Laboratory, Tokyo Koden Co., Ltd.). The higher this value, the smoother the surface and the clearer the reflected image.

(6) Adhesion of vapor-deposited film: Aluminum is vapor-deposited on the surface of a molded substrate obtained by injection molding by a vacuum vapor-deposition method, and the mirror surface is cut with a razor at intervals of 5 mm in a grid pattern to form 100 squares. Had made. Next, an operation of sticking cellophane on the surface and then peeling it off at once was performed. After the above operation, the number of squares of the metal coating film remaining on the surface of the molded body was counted and used as a measure of adhesion.

Reference Example 1 (Synthesis Method of Polyphenylene Sulfide) PPS-1: Sodium Sulfide 3.26 in Autoclave
Kg (25 mol, containing 40% of water of crystallization), sodium hydroxide 4 g, sodium acetate trihydrate 0.41 Kg (about 3
Mol) and NMP 7.9 Kg were charged, the temperature was gradually raised to 205 ° C. with stirring, and about 1.5 liters of distilled water containing 1.36 Kg of water was removed. 1,4-to the residual mixture
3.75 kg (25.5 mol) of dichlorobenzene and 2 kg of NMP were added, and the mixture was heated at 265 ° C for 3.7 hours.
The reaction product was washed 5 times with hot water at 70 ° C and then washed at 80 ° C for 24 hours.
After being dried under reduced pressure for about an hour, the melt viscosity is about 400 poise (310
Approximately 2 kg of powdery polyphenylene sulfide (PPS-1) at a temperature of 1000 ° C. and a shear rate of 1000 sec ⁻¹ was obtained.

PPS-2: 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization) in an autoclave,
Sodium hydroxide 4g, sodium acetate trihydrate 1.1
9 Kg (about 8.8 mol) and NMP 7.9 Kg were charged, the temperature was gradually raised to 205 ° C. with stirring, and water 1.3
About 1.5 liters of distilled water containing 6 kg was removed. To the residual mixture, 3.75 Kg of 1,4-dichlorobenzene (2
5.5 mol) and 2 Kg of NMP are added and the mixture is mixed at 265 ° C. for 3
Heated for hours. The reaction product was washed 5 times with hot water at 70 ° C and dried under reduced pressure at 80 ° C for 24 hours to obtain a melt viscosity of about 600.
About 2 kg of powdery polyphenylene sulfide (PPS-2) having a poise (310 ° C, shear rate 1000 sec ^-1 ) was obtained.

The PPS-3 is manufactured by Toray Industries, Inc.
M2900 was used.

Example 1 28% by weight of PPS resin (PPS-1), 12% by weight of "Apel" APL5018 manufactured by Mitsui Petrochemical Co., Ltd. as an amorphous cyclic olefin copolymer, 3% by weight of glass fiber having a single yarn diameter of 6 μm % And 57% by weight of calcium carbonate were dry-blended with a Henschel mixer, melt-kneaded and pelletized with a screw type twin-screw extruder set to a cylinder temperature of 320 ° C. The obtained pellets are dried and then injection-molded using an injection molding machine under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. to obtain a predetermined test piece for characteristic evaluation and a lamp reflector base molded article for a passenger car headlight. Got The measurement results of the obtained test pieces are summarized in Table 1. The resin composition obtained here was excellent in strength and heat resistance, and also had extremely excellent surface smoothness, and was suitable for automobile lamp reflectors. Further, the molded product of the lamp reflector substrate was subjected to direct vapor deposition of aluminum after degreasing, and its adhesion was evaluated. As a result, as shown in Table 1, it was found that the lamp reflector obtained here has good surface properties and adhesion, and is of high practical value.

[0028]

[Table 1] Comparative Example 1 Melt kneading, injection molding and property evaluation were carried out in exactly the same manner as in Example 1 except that "APEL" APL5018 was not compounded and the compounding amount of the PPS resin was 40% by weight. The resin composition obtained here had a large molding shrinkage and poor dimensional stability, and a lamp reflector substrate molded product obtained by injection molding this resin was also subjected to the same vacuum evaporation method as in Example 1 by the aluminum vapor deposition method. Vapor deposition was performed and the adhesiveness was evaluated, but the result was insufficient adhesiveness as shown in Table 1.

Comparative Example 2 Glass fiber and calcium carbonate were added in amounts of 20 and 20, respectively.
Melt kneading, injection molding and property evaluation were carried out in exactly the same manner as in Example 1 except that the amount was 40% by weight. The resin composition obtained here was extremely inferior in the surface smoothness of the injection-molded product, and could not be used for a lamp reflector.

Examples 2 to 8 Melt kneading and injection molding in the same manner as in Example 1 except that the types and compounding ratios of PPS resin, amorphous cyclic olefin copolymer, glass fiber and inorganic filler are variously changed as shown in Table 2. And predetermined characteristic evaluation was implemented. The results are also shown in Table 1. The resin composition and its injection-molded article obtained here all satisfied the characteristics such as heat resistance, strength, rigidity, dimensional stability, moldability and surface smoothness, and metal vapor deposition film adhesion. .

[0031]

[Table 2]

[0032]

EFFECTS OF THE INVENTION The PPS resin composition of the present invention and the molded product thereof satisfy characteristics such as heat resistance, strength, rigidity, dimensional stability, moldability and surface smoothness, and adhesion of metal vapor deposition film. , Which makes it possible to provide excellent materials for automobile lamp reflectors.

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Claims (3)

[Claims] 1. A polyphenylene sulfide resin 20 (A).
˜45% by weight, (B) 5 to 30% by weight of an amorphous cyclic olefin copolymer having a glass transition point of 120 ° C. or higher, (C) 0 to 15% by weight of thin glass fiber having a fiber diameter of 7 μm or less, and (D) non- A resin composition obtained by melt-kneading a mixture of 25 to 75% by weight of a fibrous inorganic filler. 2. A polyphenylene sulfide resin (A) 20.
˜45% by weight, (B) 5 to 30% by weight of an amorphous cyclic olefin copolymer having a glass transition point of 120 ° C. or higher, (C) 0 to 15% by weight of thin glass fiber having a fiber diameter of 7 μm or less, and (D) non- A molded article having excellent surface smoothness obtained by injection molding a resin composition obtained by melt-kneading a mixture of 25 to 75% by weight of a fibrous inorganic filler. 3. The molded product according to claim 2, wherein the molded product is for a lamp reflector.