JP3528208B2 - Resin composition and molded article - Google Patents

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.
The above characteristics obtained by melt-kneading 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 PS resin and a polyphenylene oxide resin (hereinafter abbreviated as PPO resin) The present invention relates to a resin composition and a molded product having the same.

[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-3-2).
08201), P for the purpose of improving surface smoothness and strength.
A lamp reflector (for example, Japanese Patent Laid-Open No. 4-334801) obtained by injection molding a composition in which PS and a fibrous reinforcing material having a specific diameter are combined has been proposed.

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. On the other hand, a technique of blending with a PPS resin for the purpose of improving the molding processability (fluidity) of a PPO resin having extremely good dimensional stability is disclosed (for example, Japanese Patent Publication No. 56-34032), but the reflector of this technique is disclosed. No application to the application is shown.

[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 a PPO resin satisfy the above-mentioned required characteristics. The present invention has been achieved by finding out that it is a thing.

[0006]

That is, the present invention is as follows.
(A) Polyphenylene sulfide resin (however, amino group
Excluding polyphenylene sulfide-based resin containing 2 )
0 to 45% by weight, (B) polyphenylene oxide (molecule
Contains ethylenically unsaturated double bond and carboxyl group, no acid
Selected from organic compounds having aquatic groups or glycidyl
Modified modifier (a) in the presence or absence of a radical initiator
Modified polyphenylene ether resin
Except) 5 to 30 wt%, (C) 0 to 15 wt% or less of the small diameter glass fibers with a fiber diameter 7μm and (D) calcium carbonate
From aluminum, wollastonite, alumina silicate, silica
At least one non-fibrous inorganic filler 25 to 7 selected
A resin composition characterized by being obtained by melt-kneading a mixture of 5% by weight (however, a lamp reflector)
Resin composition and polyphenylene sulfide and other heat
Resin deposited by mixing plastic resin in high temperature organic solvent
Oily substances, polyphenylene sulfide and (also
A) except for a resin composition composed of other thermoplastic resin) and a molded article having excellent surface smoothness obtained by injection molding the resin composition (however, the lamp reflector is
Except) .

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 (B) PPO resin used in the present invention basically comprises a structural unit represented by the following structural formula (II),

[Chemical 3] (Here, R1, R2, R3, and R4 are each a hydrogen atom, a halogen atom, an aliphatic group having 1 to 10 carbon atoms, an alicyclic group,
It represents an aromatic hydrocarbon group, and R1 to R4 may be the same or different from each other. ) Reduced viscosity (0.5 g / dl
Chloroform solution, measured at 30 ° C) is 0.15 to 0.70
Is a homopolymer and / or a copolymer within the range. Specific examples of such PPO include poly (2,6-dimethyl-1,4-phenylene oxide), poly (2-methyl-6-ethyl-1,4-phenylene oxide), poly (2,6-diphenyl-). 1,4-phenylene oxide), poly (2-methyl-6-phenyl-1,4-phenylene oxide), poly (2,6-dichloro-1,4-)
Phenylene oxide) and the like, and further, a copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol). Among them, poly (2,6
-Dimethyl-1,4-phenylene oxide), 2,6-
A copolymer of dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene oxide) is particularly preferable.

The method for producing such PPO is not particularly limited, and those obtained by known methods can be used. For example, it can be easily produced by oxidative polymerization using a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 as a catalyst. In the present invention, the PPO obtained as described above
It is, of course, possible to use the above after undergoing various treatments such as modification or activation with a compound containing a functional group such as an acid anhydride group, an epoxy group, an amino group or an isocyanate group.

[0012] Non-fibrous fillers for use in the present invention is a component necessary for dimensional stability improving material, coal
Calcium acid, wollastonite, alumina silicate,
It is at least one selected from silica , which may be hollow, and it is also possible to use two or more kinds of these fillers in combination. 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.

[0013] As the fibrous reinforcing material in the present invention, heat resistance by further compounding the following small diameter glass fibers Tan'ito径7 [mu] m, increase strength. Single yarn diameter of the glass fibers to be good Mashiku used 6μm or less, more preferably 3μm
It is the following.

The compounding ratio of each component in the resin composition of the present invention is 20 to 45% by weight of PPS resin and 5 to 3 of PPO resin.
0% by weight, 25 to 75% by weight of non-fibrous inorganic filler, and 0 to 15% by weight of fine glass fibers having a single yarn diameter of 7 μm or less, PPS resin 25 to 40% by weight, PPO resin 1
0-25% by weight, non-fibrous inorganic filler 30-70% by weight
Also, the range of 3 to 10% by weight of fine glass fiber having a single yarn diameter of 7 μm or less is preferable. Look heat resistance of <br/> in the above mix ratio, strength, rigidity, dimensional stability, moldability and surface smoothness, the resin composition satisfying all the characteristics of the metallized film adhesion and a molded body is obtained Be done.
For example, if the blending amount of the PPO resin 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 be lowered and the melt molding process will be difficult.
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, polyamideimide, polyimide, polycarbonate, polyether sulfone, polyether ketone, polyether ether ketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin,
Resins such as polyester, polyamide elastomer, and polyester elastomer) can be added to impart predetermined characteristics.

The PPS resin composition of the present invention contains γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-, 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 of dry-blending PPS resin, PPO resin and fibrous and / or non-fibrous filler, and then melt-kneading by the above-mentioned method, or PPS resin, It is also possible to use a method in which two of the fibrous and / or non-fibrous filler and the PPO resin are dry-blended, melt-kneaded, and then the remaining one is melt-kneaded.

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.
Electrical equipment, as possible out to be a component, such as an automobile.

[0019]

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 distortion temperature: ASTM D648 (5) Surface smoothness: 80 × 80 × 3 mm square plate surface gloss was measured with a portable sharpness gloss meter 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 deposited film: Aluminum is deposited on the surface of a molded substrate obtained by injection molding by a vacuum 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 poly (2,6-dimethyl-1,4-phenylene oxide) (reduced viscosity 0.45) as PPO resin, single yarn diameter of 6 μm After dry blending 3% by weight of glass fiber and 57% by weight of calcium carbonate with a Henschel mixer,
After melt-kneading and pelletizing with a screw type twin-screw extruder set to the cylinder temperature of. 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 had excellent strength and heat resistance, and also had extremely excellent surface smoothness, and was suitable for use as a lamp reflector for automobiles. Further, the molded product of the lamp reflector substrate was subjected to direct vapor deposition of aluminum after degreasing, and its adhesion was evaluated. The results are shown in Table 1, and the lamp reflector obtained here had good surface properties and adhesion, and was of high practical value.

[0027]

[Table 1] Comparative Example 1 Melt kneading, injection molding and property evaluation were performed in exactly the same manner as in Example 1 except that the PPO resin was not compounded and the PPS resin compounded amount 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 mixed 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 As in Example 1, melt kneading, injection molding and predetermined characteristics were carried out by changing the types and compounding ratios of PPS resin, PPO resin, glass fiber and inorganic filler as shown in Table 2. An evaluation was carried out. 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. .

[0030]

[Table 2]

[0031]

EFFECTS OF THE INVENTION The PPS resin composition of the present invention and the molded article thereof satisfy characteristics such as heat resistance, strength, rigidity, dimensional stability, moldability and surface smoothness, and adhesion of metal vapor deposition film. It

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-320506 (JP, A) JP-A-2-222452 (JP, A) JP-A-5-179133 (JP, A) JP-A-5- 59280 (JP, A) JP 5-1711043 (JP, A) JP 4-202364 (JP, A) JP 2-281788 (JP, A) JP 50-156561 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 81/02 C08K 3/00-3/40 C08K 7/14 C08L 71/12

Claims (2)

(57) [Claims] 1. (A) 20 to 45% by weight of polyphenylene sulfide resin (excluding amino group-containing polyphenylene sulfide resin), (B) polyphenylene oxide (ethylenically unsaturated double bond and carboxyl group in the molecule) , A modified polyphenylene ether resin obtained by modifying with a modifier (a) selected from organic compounds having an acid anhydride group or glycidyl in the presence or absence of a radical initiator) 5 to 30% by weight, (C) Fiber diameter 7μ
0 to 15% by weight of fine glass fibers of m or less and (D) calcium carbonate, wollastenite, alumina silicate,
A resin composition obtained by melt-kneading a mixture of 25 to 75% by weight of at least one non-fibrous inorganic filler selected from silica (however, a resin composition for a lamp reflector and polyphenylene sulfide and others Except for a resin composition comprising a resinous substance prepared by mixing the thermoplastic resin of 1. in a high temperature organic solvent and then depositing it, and polyphenylene sulfide and / or another thermoplastic resin). 2. A molded article having excellent surface smoothness obtained by injection molding the resin composition according to claim 1 (excluding a lamp reflector).