JPH06329854A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition improved in light resistance against light passing through glass and the light of room illumination by adding zinc oxide and two kinds of specific light-resistant stabilizers to a polyphenylene ether resin and a vinylic aromatic hydrocarbon resin. CONSTITUTION:The objective composition comprising (A) a polyphenylene ether resin [preferably poly(2,6-dimethyl-1,4-phenylene)ether], (B) a vinyl aromatic hydrocarbon resin (preferably a rubber-modified polystyrene), (C) a hindered amine compound selected from compounds of formulas I and II [e.g. bis(1,2,2,6,6- pentamethyl-4-piperidyl)sebacate], (D) a hydroxy benzotriazole compound of formula III (Z<1> is halogen; R<4> is H, alkyl, etc.) [e.g. 2-(2'-hydroxy-3'-tert-butyl-5'- methylphenyl)-5-chlorobenzotriazolel, and (E) zinc oxide having an average particle diameter of <=0.6mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin composition having improved light resistance, particularly light resistance against light through glass and indoor lighting.

[0002]

2. Description of the Related Art Polyphenylene ether resins have been put to practical use as engineering plastics for various purposes because they are excellent in heat resistance, mechanical properties, electrical properties and various other properties. For example, due to its excellent mechanical properties and flame retardancy, the demand for housings for computers and office equipment has been particularly increasing in recent years. However, the polyphenylene ether resin has a drawback that it is easily discolored by light, particularly yellowing. It is rare for sunlight to reach indoor use directly, and it is exposed to light passing through window glass and energetically weakened light such as indoor lighting. Thus, the polyphenylene ether-based resin undergoes severe discoloration, particularly yellowing, and the ΔYI value representing the change in yellowness increases early.

In order to improve this drawback, it is generally known that a compound such as a hindered amine type, a benzotriazole type, a benzophenone type or a salicylic acid ester type is blended with a polyphenylene ether type resin as a light resistance stabilizer. There is. For example, Japanese Patent Publication 62-604
No. 20 and Japanese Patent Publication No. 4-33305 disclose that when a specific hydroxybenzophenone compound is combined with a specific hindered amine compound, a polyphenylene ether resin having very good stability against ultraviolet rays is obtained. It is disclosed. Generally, in the light stabilization of plastics, it is known to combine a light stabilizer such as a hindered amine compound having a different action mechanism with an ultraviolet absorber.

However, the benzophenone-based compound has a maximum absorption wavelength of ultraviolet rays in the range of 280 to 300 nm and does not absorb a large amount of ultraviolet rays in the range of 300 to 330 nm, which deteriorates the plastic, so that the effect of suppressing yellowing may be low. . Also, if a large amount of these organic low molecular weight compounds are added to the polyphenylene ether resin, the organic low molecular weight compounds will adhere to the surface of the molded product during injection molding, resulting in poor appearance, or the gas vent of the mold will be clogged, and it will also stick out. The organic low molecular weight compound adheres to the pins and the like, which makes it difficult to continuously mold good products.

It is also known to add an inorganic compound having an ultraviolet blocking property such as zinc oxide to a polyphenylene ether resin. For example, Japanese Patent Laid-Open No. 61-62545
The report proposes a method of adding zinc oxide and a nickel-based complex. However, even with this method, the degree of improvement in light resistance was low.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and improve the light resistance of polyphenylene ether resins, especially the light resistance against light through glass.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a mixture of a polyphenylene ether resin and a vinyl aromatic hydrocarbon resin has a specific hindered amine system. The inventors have found that the light resistance is remarkably improved by adding a compound, a specific hydroxybenzotriazole compound, and zinc oxide to the present invention.

That is, the present invention provides (a) a polyphenylene ether resin, (b) a vinyl aromatic hydrocarbon resin,
(C) at least one selected from the group of hindered amine compounds represented by general formula 4 and hindered amine compounds represented by general formula 5, and (d) hydroxybenzo represented by general formula 6. The present invention relates to a polyphenylene ether resin composition comprising a triazole compound and (e) zinc oxide having an average particle size of 0.6 μm or less.

[0008]

[Chemical 4] (R ¹ represents an alkylene group, an arylene group or the absence of any, R ² represents an alkyl group)

[0009]

[Chemical 5] (R ³ represents an alkyl group)

[0010]

[Chemical 6] (Z ¹ represents a halogen atom, R ⁴ represents hydrogen, an alkyl group or an arylene group, and two R ⁴ may be the same or different from each other.)

The polyphenylene ether resin (a) used in the resin composition of the present invention is a monocyclic phenol represented by the following general formula 7.

[Chemical 7] (In the formula, R ⁵ is a lower alkyl group having 1 to 3 carbon atoms, R ⁶ and R ⁷ are hydrogen atoms or a lower alkyl group having 1 to 3 carbon atoms.) Polyphenylene obtained by polycondensation It includes an ether, and a graft copolymer having a polyphenylene ether as a backbone, which is obtained by graft-polymerizing a vinyl aromatic compound to the polyphenylene ether. This polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula 7 include 2,6-dimethylphenol,
2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, o-cresol, 2,3- Dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol,
2-methyl-3-propylphenol, 2-ethyl-3
-Methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol, 2 ，
3,6-Tripropylphenol, 2,6-dimethyl-
3-ethylphenol, 2,6-dimethyl-3-propylphenol and the like can be mentioned. And as polyphenylene ether obtained by polycondensation of one or more of these phenols, for example, poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,
6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,
Styrene was grafted onto 3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene) ether. A graft copolymer may be mentioned. In particular, poly (2,6-dimethyl-1,
4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, and graft copolymer obtained by graft-polymerizing styrene to the former two are preferable as the polyphenylene ether resin used in the present invention. Is.

Next, in the resin composition of the present invention, the (b) vinyl aromatic hydrocarbon resin, which is used as a mixture with the polyphenylene ether resin, means the monomer structural unit shown in Chemical formula 8 as a polymer thereof. A resin having at least 25% by weight or more, such as polystyrene, rubber modified polystyrene (impact polystyrene), styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-acrylic acid rubber-acrylonitrile copolymer, styrene- Examples thereof include α-methylstyrene copolymer and styrene / butadiene / block copolymer, and these may be used as a mixture of two or more kinds. Among them, rubber modified polystyrene is preferably used.

[0014]

[Chemical 8] (In the formula, R ⁸ represents a hydrogen atom or a lower alkyl group, Z ² represents a halogen atom or a lower alkyl group, and p is 0 or a positive integer of 1 to ^3. )

In the resin composition of the present invention, when the polyphenylene ether resin and the vinyl aromatic hydrocarbon resin are mixed and used, the ratio (part by weight) of both is generally 90/10 to 10 /. 90, preferably 80 / 20-
It is 20/80. The (c) hindered amine compound used in the resin composition of the present invention is a compound represented by the general formula 4 or 5. Specific examples of the compound represented by Chemical formula 4 include bis (1,
2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) malonate, bis (1,2,2,6)
6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, Examples thereof include bis (1-ethyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. In particular, screws (1, 2,
2,6,6-Pentamethyl-4-piperidyl) sebacate is sold by Sankyo Co., Ltd. under the trade name of SANOL LS-765.

Specific examples of the compound represented by Chemical formula 5 are:
Tetrakis (1,2,2,6,6-pentamethyl-4-
Piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1-ethyl-2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1-propyl-
2,2,6,6-tetramethyl-4-piperidyl) 1,
2,3,4-butane tetracarboxylate and the like can be mentioned. In particular, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate is sold under the trade name LA-52 by Asahi Denka Co., Ltd. There is.

The hydroxybenzotriazole compound (d) used in the resin composition of the present invention is a compound represented by the above chemical formula 6. Specific examples of the (d) hydroxybenzotriazole-based compound include 2- (2'-hydroxy-3'-methylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-5'-methylphenyl)-. 5-fluorobenzotriazole, 2-
(2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5)
′ -Methylphenyl) -5-bromobenzotriazole, 2- (2′-hydroxy-3′-ethylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-5'-ethylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5-chlorobenzo Triazole, 2-
(2'-hydroxy-3 ', 5'-diethylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-dipropylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3',
5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-methyl-5'-ethylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy -3'-ethyl-5'-
Methylphenyl) -5-chlorobenzotriazole, 2
-(2'-hydroxy-3'-methyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2
′ -Hydroxy-3′-propyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-methyl-5′-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and the like can be mentioned.
In particular, 2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-chlorobenzotriazole is a product name of Sumisorb 300 manufactured by Sumitomo Chemical Co., Ltd., and is 2- (2'-hydroxy-3 ', 5'-di-tert-
Butylphenyl) -5-chlorobenzotriazole is
It is sold by Asahi Denka Co., Ltd. under the trade name of LA-34.

The amount of the above-mentioned (c) hindered amine compound added is generally 0.05 to 1 with respect to 100 parts by weight of the resin component comprising the above-mentioned components (a) and (b).
0 parts by weight, preferably in the range of 0.1 to 5 parts by weight,
The addition amount of the (d) hydroxybenzotriazole compound is generally 0.05 to 10 parts by weight, preferably 0.1.
Is selected in the range of up to 5 parts by weight. If the addition amount of each is more than this range, the moldability and workability are deteriorated, and if the addition amount is less than this range, the action and effect are small.

The zinc oxide (e) having an average particle size of 0.6 μm or less used in the resin composition of the present invention may be any zinc oxide as long as it is commercially available as a white pigment for resin addition. Good. Although the average particle size of commercially available zinc oxide varies, for the purpose of the present invention,
Those having a diameter of around 25 μm are particularly preferable. The amount of zinc oxide added is generally selected in the range of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts of the resin component comprising the components (a) and (b). If the amount added is more than this range, the moldability and processability will deteriorate, and if the amount added is less than this range, the action and effect will be small.

The resin composition of the present invention includes other thermoplastic resins such as PC, PBT, PET, PE, PP, maleic acid-modified PP, POM, PMMA, MS, MBS, A.
S, AAS, AES, AMBS, styrene / maleic acid copolymer resin (Dylark manufactured by Arco Chemical Co., USA), polyphenylene sulfide, polyether ether ketone, polysulfone and the like can be added.

Various elastomers can be added to the resin composition of the present invention as an impact resistance imparting agent. Specifically, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene-diene terpolymer, isobutylene-butadiene copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-acrylonitrile copolymer, styrene-butadiene- Styrene tereblock copolymer, or hydrogenated product thereof, styrene-isoprene-styrene tereblock copolymer, or hydrogenated product thereof, methylmethacrylate-butadiene copolymer, butylmethacrylate-butadiene copolymer and the like. To be

If desired, the resin composition of the present invention contains a reinforcing material, a filler, a known heat stabilizer, an antioxidant, a flame retardant,
One or more kinds of various additives such as flame retardant aid, pigment, lubricant, plasticizer and the like can be added. These may be used alone or as a mixture, and are used in an amount within a range that does not impair the characteristics of the resin composition of the present invention.

Examples of the above-mentioned reinforcing material and filler are glass fiber, glass beads, glass flake, glass fiber cloth, glass fiber mat, graphite, carbon fiber, carbon fiber cloth, carbon fiber mat, carbon black, carbon flake. , Metal fibers and flakes made from aluminum, stainless steel, brass and copper, metal powder, organic fibers, acicular potassium titanate, mica, talc, clay, (acicular) titanium oxide, wollastonite, calcium carbonate. To be

In preparing the polyphenylene ether-based resin composition of the present invention, a conventionally known method may be adopted. For example, after mixing the respective components in a blender such as a turnbull mixer or a Henschel mixer, an extruder is used. The method of kneading with a Banbury mixer, a roll or the like is appropriately selected. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, the part of each component in an Example shows a weight part.

[0025]

【Example】

Comparative Example 1 50 parts of poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity [η] = 0.44 dl / g, impact-resistant polystyrene (manufactured by Denki Kagaku Kogyo KK, trade name HI-UM-30)
1) 50 parts, 3 parts of titanium oxide and 0.2 parts of zinc oxide were uniformly mixed using a tumbler. 30 mm of the resulting mixture
Using a φ2-screw extruder (PCM-30, manufactured by Ikegai Iron and Steel Co., Ltd.)
Cylinder set temperature 270 ℃, screw rotation speed 50rp
After melt-kneading under the condition of m, it was pelletized. The pellets obtained here were dried for 2 hours using a hot air dryer at a temperature of 120 ° C., and then an injection molding machine (Japan Steel Works, Ltd.)
Manufactured by J100SA-II type)
Strip-shaped test pieces (for light resistance test, size 3.2 × 12.7 × 63.6 ml) were prepared under the conditions of 0 ° C. and mold temperature of 90 ° C. Next, a strip-shaped test piece obtained here was used to measure a 6.5 kW xenon arc type fade meter (Ci-65 manufactured by Atlas Co., Ltd.).
It was attached to a predetermined position of the mold), Pyrex glass was used as the inner filter and clear glass was used as the outer filter, and the treatment was performed under the conditions of a black panel temperature of 63 ° C. and no rain spray. The strip-shaped test piece was taken out of the tester at a processing time of 300 hours and the change in color tone was measured.
Colorimetry was performed by using a color difference meter (Σ-80, manufactured by Nippon Denshoku Industries Co., Ltd.) and comparing by ΔYI. The results are shown in Table 1.

Comparative Examples 2 to 4 With respect to 100 parts of the resin composition shown in Comparative Example 1, a hindered amine compound of the type shown in Table 2 (hereinafter abbreviated as HALS) and a hydroxybenzotriazole compound (hereinafter abbreviated as BTA) were used. Table 1 for any one of zinc oxide and zinc oxide
The operation of Comparative Example 1 was repeated using the ratio amount shown in. The results are shown in Table 1.

Comparative Examples 5 to 7 With respect to 100 parts of the resin composition shown in Comparative Example 1, any two kinds of HALS, BTA, and zinc oxide shown in Table 2 were used in proportion amounts shown in Table 1. The operation of Comparative Example 1 was repeated. The results are shown in Table 1.

Examples 1 to 6 The procedure of Comparative Example 1 was repeated by using 100 parts of the resin composition shown in Comparative Example 1 with HALS, BTA and zinc oxide of the types shown in Table 2 in the proportions shown in Table 1. Was repeated. The results are shown in Table 1.

[0029]

The polyphenylene ether resin composition of the present invention has an excellent feature that the light resistance to light through glass and indoor illumination light is significantly improved.

[0030]

[Table 1] HALS BTA Zinc oxide (discoloration) Type Compound amount part Type Compound amount part Type Compound amount part △ YI Example 1 1-1 2.0 2-1 1.0 3-1 5.0 17.0 Example 2 1-1 2.0 2-2 1.0 3-1 5.0 17.5 Example 3 1 -2 2.0 2-1 1.0 3-1 5.0 17.2 Example 4 1-1 2.0 2-1 1.0 3-2 5.0 15.0 Example 5 1-1 2.0 2-2 1.0 3-2 5.0 15.4 Example 6 1-2 2.0 2-1 1.0 3-2 5.0 15.3 Comparative Example 1 50.3 Comparative Example 2 1-1 2.0 36.5 Comparative Example 3 2-1 1.0 40.0 Comparative Example 4 3-2 5.0 42.0 Comparative Example 5 1-1 2.0 2-1 1.0 22.3 Comparative Example 6 1-1 2.0 3-1 5.0 24.7 Comparative Example 7 2-1 1.0 3-1 5.0 28.5

[0031]

[Table 2] No. Type of compound Manufacturer Trade name 1-1 HALS Sankyo Co., Ltd. SANOL LS-765 1-2 HALS Asahi Denka Co., Ltd. LA-52 2-1 BTA Sumitomo Chemical Co., Ltd. Sumisorb 300 2 -2 BTA Asahi Denka Co., Ltd. LA-34 3-1 Zinc oxide Sakai Chemical Co., Ltd. Zinhua No. 1 (particle size 0.52 μm) 3-2 Zinc oxide 〃 Fine zinc oxide (particle size 0.26 μm )

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 71/12 LQN LQP

Claims (2)

[Claims] 1. (a) Polyphenylene ether resin,
(B) vinyl aromatic hydrocarbon resin, (c) at least one selected from the group of hindered amine compounds represented by general formula 1 and hindered amine compounds represented by general formula 2, (d) general A resin composition comprising a hydroxybenzotriazole compound represented by Formula 3 and (e) zinc oxide having an average particle size of 0.6 μm or less. [Chemical 1] (R ¹ represents an alkylene group, an arylene group or the absence of any, and R ² represents an alkyl group) (R ³ represents an alkyl group) (Z ¹ represents a halogen atom, R ⁴ represents hydrogen, an alkyl group or an arylene group, and two R ⁴ may be the same or different from each other.) 2. (a) Polyphenylene ether resin 90
-10 parts by weight, (b) vinyl aromatic hydrocarbon resin 10
90 parts by weight, (c) hindered amine compound 0.05 to 10 parts by weight, and (d) hydroxybenzotriazole compound 0.05 to 100 parts by weight of the resin component consisting of the components (a) and (b). The resin composition according to claim 1, which comprises 10 parts by weight and (e) 1 to 20 parts by weight of zinc oxide having an average particle size of 0.6 μm or less.