WO2003066735A1

WO2003066735A1 - Polyarylene sulfide resin composition and molded object obtained therefrom

Info

Publication number: WO2003066735A1
Application number: PCT/JP2003/001178
Authority: WO
Inventors: Kikuo Nagatoshi; Toru Iga; Nobuyuki Kojima
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 2002-02-06
Filing date: 2003-02-05
Publication date: 2003-08-14
Also published as: JP2003226810A

Abstract

A polyarylene sulfide resin composition which comprises (A) 100 parts by weight of a polyarylene sulfide resin, (B) 20 to 250 parts by weight of a particulate inorganic filler, (C) 0 to 50 parts by weight of whiskers, and (D) 0.1 to 5 parts by weight of a polyethylene wax. A specular object comprising a molding of the polyarylene sulfide resin composition and a metallic film deposited on a surface of the molding is usable as a lamp reflector, etc.

Description

Description Polyarylene sulfide resin composition and molded article using the same

The present invention relates to a polyarylene sulfide resin composition capable of obtaining a molded article that can be used for a mirror used under severe conditions of thermal or environmental (chemical resistance, steam resistance), and using the same. Related to molded articles. More specifically, the present invention relates to a polyarylene sulfide resin composition used for a vehicular lamp reflector such as a fog lamp, a headlamp and the like, and a reflector (downlight cover) of a lighting fixture and the like, and a molded article using the same. Background art

Conventionally, thermosetting resins such as phenolic resins and unsaturated polyesters have been used as molding materials for lamp reflectors such as automotive headlamps. In recent years, attempts have been made to convert these thermosetting resins to thermoplastic resins due to environmental issues such as recycling. Furthermore, the thermosetting resin composition itself has poor surface smoothness, and a resin paint is undercoated to give a mirror surface.However, an undercoatless thermoplastic resin composition is required to simplify the process and reduce costs. ing. In order to achieve under-tress, the thermoplastic resin composition must have extremely high surface smoothness, as well as heat resistance and rigidity to withstand high temperatures (200-230 ° C) when the lamp is lit. It is required that high surface smoothness be obtained stably during injection molding. To satisfy the above requirements, polyallyl-lens sulfide, which has high heat resistance and high fluidity, is suitable. As a result of exploring the relationship between the characteristics of polyarylene sulfide and the surface smoothness and appearance of the molded product, those having the above characteristics are excellent. In order to improve the surface smoothness of the molded product, it is, of course, necessary to make the mold a mirror finish. In addition to the smoothness of the mold surface, it is more easily adhered, and peeling that tends to impair the smoothness of the molded product surface is likely to occur when releasing the mold.

Maintain surface smoothness and increase rigidity from polyarylene sulfide resin composition Many attempts have been made to give the resulting molded article. For example, Japanese Patent Application Laid-Open Nos. Hei 7-18855-55, Japanese Patent Laid-open No. Hei 8-4-1341, Japanese Patent Laid-open No. Hei 9-251806, Japanese Patent Laid-open No. Hei 10-237370 In the polyarylene sulfide resin composition described in Publication No. 2 and the like, calcium carbonate having a specific particle size is blended in order to obtain surface smoothness. Further, the above-mentioned publication describes that one kind of whisker is blended in order to increase rigidity. Calcium carbonate and whiskers are preferred components for achieving both surface smoothness and rigidity of the molded article.

Further, in the specification of JP-A-7-188555 and JP-A-10-2327332, as a releasing agent, montanic acid and its salts, esters, polyethylene resins, etc. Is described, but there is no example. In addition, Japanese Patent Application Laid-Open No. Hei 4-220364 discloses that a natural wax or the like may be added as a release agent, but there is no example. On the other hand, Japanese Patent Application Laid-Open No. Hei 4-2722168 discloses an example in which a partially modified ester wax of montanic acid is used as a release agent. However, these can be used as a mold release agent, but the release effect is recognized, but the polyarylene sulfide resin composition can be used as a mirror surface because the molding temperature is usually from 300 to 350 ° C. In order to obtain a surface, it is necessary to select a release agent that has heat resistance that does not generate a force such as a decomposition gas and does not cause whitening of the surface due to phase separation or the like. Since the partially modified ester wax of montanic acid is inferior in heat resistance, in the case of a resin composition using the same, a large amount of volatile components is generated at the above-mentioned molding temperature, and a molded article having a mirror surface is stably molded. There was a problem.

In view of the above circumstances, the present inventors have conducted intensive studies and, as a result, have found that polyethylene wax is an excellent mold release agent that does not generate decomposition gas and the like, and have completed the present invention.

Accordingly, an object of the present invention is to provide a polyarylene sulfide resin composition having excellent surface smoothness and mirror-like properties and capable of performing stable molding, and a molded article using the same. Disclosure of Invention ·

According to the first aspect of the present invention, (A) 100 parts by weight of a polyarylene sulfide resin, (B) ′. 20 to 250 parts by weight of a particulate inorganic filler, (C) whisker 0 ~ 50 fold And a polyarylene sulfide resin composition comprising 0.1 to 5 parts by weight of (D) polyethylene wax.

Preferably, the melt viscosity of the polyarylene sulfide resin (A) is from 100 to 1,500 voids.

Preferably, the volume average particle diameter of the particulate inorganic filler (B) is 4 / xm or less. Preferably, the fiber diameter of the whiskers (C) is 7 m or less.

Preferably, the particulate inorganic filler (B) is calcium carbonate.

Preferably, the whiskers (C) are aluminum borate whiskers.

Preferably, the polyethylene wax (D) is an oxidized polyethylene wax. Further, according to a second aspect of the present invention, there is provided a molded article obtained by molding the above-mentioned polyarylene sulfide resin composition.

Further, according to a third aspect of the present invention, there is provided a mirror-like body obtained by forming a metal film on a surface of the above-mentioned molded body.

According to a fourth aspect of the present invention, there is provided a lamp reflector comprising the above-mentioned mirror-like body. BEST MODE FOR CARRYING OUT THE INVENTION

1. Polyarylene sulfide resin composition

(1) Polyarylene sulfide resin (Α)

The polyarylene sulfide resin (Α) used in the present invention preferably has a melt viscosity of 100 to 1,500 voids. When the melt viscosity is less than 100 voids, the material becomes weak in strength and brittle, so that it may not be practical. On the other hand, if it exceeds 1,500 poise, the fluidity is reduced, it is difficult to obtain a mirror surface, and a flow mark or the like is liable to appear, so that the surface appearance may be deteriorated. The melt viscosity is more preferably from 300 to 1,200 voids, and particularly preferably from 500 to 1,100 voids. Incidentally, the melt viscosity, for example, a resin temperature 3 0 0 ° C, with measurement conditions shear rate 2 0 0 se ^1, can be measured by Kiyapirogurafu (manufactured by Toyo Seiki Co., Ltd.).

Polyarylene sulfide resin (A) is a polymer based on the structural formula [1-Ar-S-] (where Ar is an arylene group and S is iodo). Is preferably 70 mol% or more of the repeating unit represented by the following general formula (1). More preferably, it is a polymer containing at least 80 mol%. When the content of the repeating unit is less than 70 mol%, the original crystalline component, which is a characteristic of the crystalline polymer, is small, and the mechanical strength may be insufficient.

(In the formula, R ¹ is an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carboxyl group or a metal salt thereof, a nitro group, and a substituent selected from halogen atoms such as fluorine, chlorine, and bromine; m is an integer of 0 to 4. n indicates the average degree of polymerization, and is in the range of 20 to 100.)

As the polyarylene sulfide resin (A), not only a homopolymer but also a copolymer can be used. Its copolymerized structural units include metaphenylene sulfide units, orthophenylene sulfide units, p, p'-diphenylene gentetone sulfide units, P, P'-diphenylene sulfone sulfide units, P, p '— Biphenylene sulfide units, p, ρ' diphenylene methylene sulfide units, p, '— diphenylene cumenyl sulfide units, naphthyl sulfide units, etc.

The polyarylene sulfide resin (A) having a melt viscosity of 100 to 1,500 voids can be produced, for example, by the method described in JP-A-2000-186208. Incidentally, polyarylene sulfide resin is generally known to have a molecular structure such as a linear type, a semi-linear type, or a cross-linked type, depending on the production method. However, the polyarylene sulfide resin (A) used in the present invention is not particularly limited. The molecular structure is not particularly limited.

(2) Granular inorganic filler (B)

In the polyarylene sulfide resin composition of the present invention, the particulate inorganic filler (B) is used for expressing surface smoothness of a molded article.

The granular inorganic filler (B) used in the present invention has a volume average particle diameter of 4 m or less. Preferably. If the volume average particle diameter exceeds 4 m, it is difficult to ensure sufficient surface smoothness of the molded article, and when a metal film is formed on the molded article, the image clarity of the obtained mirror surface may be reduced. . The volume particle size is more preferably 3.8 m or less, particularly preferably 3.5 xm or less.

The volume average particle diameter can be measured, for example, by a particle size distribution analyzer CIS-1 (manufactured by GALAI) using a laser-scan analysis method.

The blending amount of the particulate inorganic filler (B) is from 20 to 250 parts by weight per 100 parts by weight of the polyarylene sulfide resin (A). If the amount is less than 20 parts by weight, the strength of the material, particularly the rigidity, is not sufficient. On the other hand, when the amount exceeds 250 parts by weight, it is difficult to sufficiently secure the surface smoothness of the molded product, and when a metal film is formed on the molded product, the image clarity of the obtained mirror is reduced. The amount of the particulate inorganic filler (B) to be blended is preferably 50 to 200 parts by weight, more preferably 60 to 150 parts by weight. The type of the particulate inorganic filler (B) is not particularly limited, and any of those commonly used for polyarylene sulfide resin compositions can be used. Examples of the particulate inorganic filler (B) include calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium oxide, magnesium phosphate, talc, myriki, silica, alumina, silica alumina, kaolin, bentonite, montmorillonite, creel , Graphite, carbon black, glass beads, titanium oxide, zirconium oxide, silicon nitride, hydrated talcite, aluminum hydroxide, and the like. Of these, calcium carbonate is particularly preferred because of its stable quality and easy availability.

(3) Whiskers (C)

In the polyarylene sulfide resin composition of the present invention, whisker (C) is used to increase the rigidity of a molded article.

The whiskers (C) used in the present invention preferably have a fiber diameter of 7 m or less. When the fiber diameter exceeds 7, it becomes difficult to sufficiently secure the surface smoothness of the molded article, and when a metal film is formed on the molded article, the image clarity of the obtained specular body may be reduced. The fiber diameter is more preferably 5 im or less, and particularly preferably 2 / x m or less.

Here, the fiber diameter means the size of the minor axis of the major axis and minor axis of the fibrous material. You.

The fiber diameter can be measured, for example, by a microscope.

Whisker (C) is blended in a mold that requires rigidity in the molded product, and the blending amount is 0 to 50 wt.% Per 100 parts by weight of polyarylene sulfide resin (A). However, if the compounding amount exceeds 50 parts by weight, it is difficult to sufficiently secure the surface smoothness of the molded product, and when a metal film is formed on the molded product, the image clarity of the obtained mirror is reduced. The compounding amount of the whiskers (C) is preferably from 0 to 40 parts by weight, and more preferably from 0 to 35 parts by weight.

The total amount of the particulate inorganic filler (B) and the whisker (C) is preferably not more than 250 parts by weight per 100 parts by weight of the polyarylene sulfide resin (A). If the amount exceeds 0 parts by weight, the image clarity is reduced for the same reason as described above.

The type of whisker (C) is not particularly limited. Examples of whiskers (C) include potassium titanate zinc, aluminum borate whiskers, calcium carbonate whiskers, calcium silicate whiskers (wollastonite), calcium silicate whiskers (zonotrite), silicon carbide whiskers, and nitriding. Examples include silicon whiskers, zinc oxide whiskers, alumina whiskers, and graphite whiskers. Among these, aluminum borate whiskers are particularly preferable.

(4) Polyethylene wax (D)

In the polyethylene sulfide resin composition of the present invention, the polyethylene wax (D) is used as a release agent for stably forming a molded article having a mirror surface.

The blending amount of the polyethylene wax (D) is 0.1 to 5 parts by weight per 100 parts by weight of the polyarylene sulfide resin (A). If the compounding amount is less than 0.1, the releasability of the molded article is deteriorated, peeling marks appear on the surface of the molded article, and whitened substances are adhered, so that the surface appearance is significantly impaired. In addition, there arises a problem that the molded article adheres to the mold and the molding cycle becomes unstable. On the other hand, if it exceeds 5 parts by weight, it bleeds on the surface and impairs the surface appearance. That is, by setting the blending amount of the polyethylene wax (D) to 0.1 to 5 parts by weight, these problems can be solved and stable continuous molding can be performed. The blending amount of the polyethylene wax (D) is preferably from 0.3 to 2 parts by weight, and more preferably from 0.5 to 1.5 parts by weight. The type of the polyethylene wax (D) is not particularly limited, but is preferably a polyethylene oxide wax. Oxidized polyethylene wax is a particularly excellent release agent because it has excellent heat resistance and hardly causes whitening due to phase separation. Among the oxidized polyethylene waxes, those having a large weight average molecular weight (Mw) of 50,000 to 8,000, as measured by gel permeation chromatography (GPC), particularly have volatile components. The haze value in a haze test under high temperature conditions (for example, 230 ° (: 24 hours)) is significantly lower than 0.5%, and the weight average molecular weight of the oxidized polyethylene wax is preferably 2,0. It is preferably from 0000 to 8,000, more preferably from 4,000 to 6000. Therefore, a molded article obtained from the resin composition using the same is used as a lamp reflector. When the lamp is turned on, the lens does not fog due to volatile components even when exposed to a high temperature condition when the lamp is turned on: (230 ° C).

Carboxyl group

The acid preferably has an acid value of 3 or more. If the acid value is less than 3, the releasability may be insufficient. The acid value of the oxidized polyethylene wax is more preferably 10 or more, and particularly preferably 15 or more. Here, the acid value means mg of potassium hydroxide required to neutralize 1 g of wax. '

(5) Other

The polyarylene sulfide resin composition of the present invention contains a silane coupling agent, an antioxidant, a heat stabilizer, a lubricant, a plasticizer, a conductivity-imparting agent, if necessary, as long as the effects of the present invention are not impaired. Various additives such as colorants and pigments may be further compounded. 2. Method for producing polyarylene sulfide resin composition

The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited. Examples of the method include melt kneading using a ripon tumbler, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, or the like. In this case, an appropriate kneading temperature is usually from 300 to 350 ° C. 3. Molded product

The polyarylene sulfide resin composition of the present invention can be molded by a molding method such as injection molding and injection compression molding. In particular, molded products obtained by injection molding are excellent in surface smoothness, and even when exposed to high temperatures for a long time (for example, 230 or 24 hours), the surface becomes white and the surface such as Z or flow mark becomes good. Haze is extremely small due to little change in appearance and small amount of volatile components. In addition, such a molded article has excellent releasability at the time of injection molding, so that there is no peeling mark on the surface. Therefore, molding can be performed stably for a long time in a state of high mirror finish.

Such a molded article can be made into a mirror-like body by forming a metal film such as aluminum on the surface, for example, a lamp reflector for automobiles such as fog lamps and headlamps, and a reflector (such as a lighting fixture). Light cover) can be used. Example

[Example 11; Comparative Examples 1 to 5]

(1) Manufacturing of molded products

After the polyarylene sulfide resin composition is uniformly mixed in the mixing ratio shown in Tables 1 to 4 using a Super-Flow mixer (vibration-type expansion mixer), a twin-screw extruder (manufactured by Toshiba Machine Co., TEM35B) ) At 300-350 ° C to produce pellets. -'.

The obtained pellets were formed into a flat plate (80 × 80 × 2 mm) using a mirror-finished flat plate (80 × 80 × 2 mm) attached to a 50-ton injection molding machine (manufactured by JSW, J50E-P).

In Tables 1 to 4, the unit of the amount of each component constituting the polyarylene sulfide resin composition is part by weight, the melt viscosity of PPS, the volume average particle size of calcium carbonate, and aluminum borate whiskers. The weight average molecular weight (Mw) of the fiber warp and the oxidized polyethylene wax was measured by the measurement method described above.

(2) Evaluation of molded products

The peelability, surface appearance, image clarity, flexural modulus and haze of the obtained flat molded product were measured and evaluated. The results are shown in Tables 1-4.

(i) Releasability: The state when the flat molded product separates from the mold (If the molded product adheres to the mold, (When pressed with a protruding pin, warped or released.) And the surface condition was visually determined according to the following criteria.

〇: The mold release is smooth and there is no abnormality such as peeling marks on the surface.

X: Mold release is not smooth and peeling marks are seen on the surface.

(ii) Surface appearance: visually determined according to the following criteria.

Good: No whitening and no flow mark on the surface of the flat molded product.

Poor: Whitening and flow mark on the surface of the flat plate.

(iii) Image clarity

Aluminum was vacuum-deposited (thickness: about 100 nm) on the surface of the flat molded product, and measured by an image clarity tester (manufactured by Suga Test Instruments Co., Ltd.). The measurement principle is that the reflected image of the light source is diffused due to the reflection performance of the reflector (an image larger than the specular reflection image), so the light received through the optical slit (created with a fixed grid pattern) is observed. Measure the relative value (C value) with respect to the mirror surface according to the amount of light (the amount of light blocked by the grating is large if the image is diffused). That is, the test piece is set so that the incident angle of the light source is 45 degrees, and the optical slit (optical comb width: 1.0 mm) is set perpendicular to the direction of the reflection angle of 45 degrees. Further, the receiver is set ahead, an image of the light source is projected on the optical slit, the slit is moved in the setting direction, and the minimum amount of light detected by the receiver via the slit is defined as the maximum reflectance M. The image clarity (C value) is expressed as (M ^ m) Z (M + m) X100 (%), with the maximum light quantity as the minimum reflectance m.

(iv) Flexural modulus: Measured according to ASTM D790.

(V) Haze: clear to one force-bi carrying the top cover of the glass plate placed flat moldings from about 1 0 cm ^3, by mounting the evening Mantoruhi, 2 3 0 ° (:, heated for 24 hours, the glass plates The haze value (%) of the haze was measured according to JISK-7105. table 1

PP S (1): Polyphenylene sulfide resin (produced by DIP Corp., K-1, melt viscosity 390 boise)

Calcium carbonate (1): Caltex 5 (manufactured by Maruo Calcium Co., Ltd.), volume average particle size 1.0 βΐΐΐ

Calcium carbonate (2): SL 2200 (manufactured by Takehara Chemical Industry Co., Ltd.), volume average particle size 3.5 urn

Oxidized polyethylene wax (1): Licowax PED 191 (made by Clariant Japan)

Mw 5,000-6,000

Acid value 15-19mgK〇H, g

Table 2

PP S (1): Polyphenylene sulfide resin (manufactured by DIC Corporation, K-1; melt viscosity 390 boise)

Calcium carbonate (2): SL 2200 (manufactured by Takehara Chemical Industry Co., Ltd.), volume average particle

(1): Licowax PED 191 (Clarian Toji)

Weight average molecular weight 5,000 to 6,000 (2): Recolbu HI 2 (manufactured by Clariant Japan), Mw 2,000 to 3,000

Acid value 15-19mgKOH / g

Calcium stearate: (manufactured by NOF Corporation)

Table 3

P P S (2): Polyphenylene sulfide resin (LDN-1G, melt viscosity 500 boise, manufactured by DIC Corporation)

Calcium carbonate (2): SL 2200 (manufactured by Takehara Chemical Industry Co., Ltd.), volume average particle diameter 3.5 m

Aluminum borate whiskers: Albolex YS 2B (Shikoku Chemicals Co., Ltd. Fiber diameter 0.5-1.0 m, L / D: 10-

60

Acid (1): Licowax PED 191 (made by Clariant Japan) ''

Mw 5,000-6,000

Acid value 15-19mgK〇HZg

Calcium stearate: (manufactured by NOF Corporation) Table 4

PP S (2): Polyphenylene sulfide resin (LN-1G, melt viscosity 500 boise, manufactured by DIC Corporation)

PP S (3): Polyphenylene sulfide resin (manufactured by DIP Corp., LN_2G, melt viscosity 1,050 boise)

PPS (4): Polyphenylene sulfide resin (Tosoichi # 160, melt viscosity 1,800 Boyes)

Oxidized polyethylene wax (1): Licowax PED 191 (made by Clariant Japan)

Mw 5,000-6,000

Acid value 15-19mgKOHZg Industrial applicability

According to the present invention, there can be provided a polyarylene sulfide resin composition having excellent surface smoothness and specularity and capable of performing stable molding, and a molded article using the same.

Claims

The scope of the claims

1. (A) 100 parts by weight of polyarylene sulfide resin,

(B) granular inorganic filler 20 to 250 parts by weight,

(C) Whiskers 0-50 parts by weight, and

(D) Polyethylene wax resin composition containing 0.1 to 5 parts by weight of polyethylene wax.

•

2. The polyarylene sulfide resin composition according to claim 1, wherein the melt viscosity of the polyarylene sulfide resin (A) is 100 to 1,500 vise.

3. The polyolefin sulfide resin composition according to claim 1, wherein the particulate inorganic filler (B) has a volume average particle size of 4 m or less.

4. The polyarylene sulfide resin composition according to claim 2, wherein the volume average particle diameter of the granular inorganic filler (B) is 4 m or less.

5. The polyarylene sulfide resin composition according to claim 1, wherein the fiber diameter of the whisker (C) is 7 im or less.

6. The polyarylene sulfide resin composition according to claim 2, wherein the whisker (C) has a fiber diameter of 7 / im or less.

7. The polyarylene sulfide resin composition according to claim 3, wherein the fiber diameter of the whisker (C) is 7 xm or less.

8. The polyarylene sulfide resin composition according to claim 4, wherein the whisker (C) has a fiber diameter of 7 m or less.

9. The method according to claim 1, wherein the granular inorganic filler (B) is calcium carbonate. Polyarylene sulfide resin composition.

10. The polyarylene sulfide resin composition according to claim 1, wherein the whiskers (C) are aluminum borate whiskers.

11. The polyarylene sulfide resin composition according to claim 1, wherein the polyethylene wax (D) is an oxidized polyethylene wax.

12. A molded article obtained by molding the polyarylene sulfide resin composition according to claim 1.

13. A mirror body formed by forming a metal film on the surface of the molded article according to claim 12.

1 4. A lamp reflector comprising the mirror body according to claim 13.