JP3003743B2 - Polyphenylene ether resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether-based resin composition having improved light fastness, particularly improved light fastness to 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 because of their excellent heat resistance, mechanical properties, electrical properties and various other properties. For example, in recent years, there has been a particularly high demand for use in housings of computers and office equipment by taking advantage of the properties of having excellent mechanical properties and flame retardancy. However, polyphenylene ether-based resins have a disadvantage that they are easily discolored by light, particularly yellowing. For applications used indoors, sunlight rarely reaches directly, and is exposed to light through windows and energetically weakened light such as indoor lighting. Thus, the polyphenylene ether-based resin undergoes severe discoloration, particularly yellowing, and the ΔYI value representing a change in yellowness increases early.

In order to remedy 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 mixed with a polyphenylene ether type resin as a light stabilizer. I have. For example, Japanese Patent Publication No. 62-604
No. 20 and Japanese Patent Publication No. 4-33305 report that when a specific hydroxybenzophenone compound is combined with a specific hindered amine compound, a polyphenylene ether resin having very good stability to ultraviolet light can be obtained. It has been disclosed. In general, it is known to combine a light stabilizer such as a hindered amine compound having a different action mechanism with an ultraviolet absorber in light stabilization of plastics.

[0004] However, satisfactory light fastness cannot be obtained even by the improvement by these stabilizers, and the discoloration in the outdoors due to the sunlight coming through the glass as well as the discoloration in the outdoors where the sunlight is directly received by the sunshine is obtained. It was difficult to control. In addition, benzophenone compounds are 280-3
It may not be practical because it does not absorb a large amount of the ultraviolet region of about 300 to 330 nm, which has a maximum absorption wavelength of ultraviolet light at 00 nm and deteriorates plastic, and further improvement in light resistance is desired.

[0005]

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

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a mixture comprising a polyphenylene ether resin and a vinyl aromatic hydrocarbon resin has a specific hindered amine-based compound. By adding a compound and a specific hydroxybenzotriazole-based compound, it has been found that light resistance is significantly improved,
The present invention has been reached.

That is, the present invention provides (a) a polyphenylene ether resin, (b) a vinyl aromatic hydrocarbon resin,
(C) at least one member selected from the group consisting of a hindered amine compound represented by the general formula (4) and a hindered amine compound represented by the general formula (5), and (d) a hydroxybenzo compound represented by the general formula (6) The present invention relates to a polyphenylene ether-based resin composition comprising a triazole-based compound.

[0008]

Embedded image (R ¹ is an alkylene group or an arylene group, R ² represents Ri alkyl group der may R ¹ is not)

[0009]

Embedded image (R ³ is an alkyl group)

[0010]

Embedded image (R ⁴ is hydrogen, an alkyl group or an arylene group,
Z ¹ is a halogen atom, and two R ⁴ may be the same or different from each other)

[0011] 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) (wherein R ⁵ represents a carbon atom having 1 carbon atom).
And R ⁶ and R ⁷ are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms), which is obtained by condensation polymerization of at least one of the following: Includes graft copolymers having polyphenylene ether at the root obtained by graft polymerization of compounds. The polyphenylene ether may be a homopolymer or a copolymer.

Embedded image

The monocyclic phenol represented by the above general formula 7 includes, for example, 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, ,
3,6-tripropylphenol, 2,6-dimethyl-
3-ethylphenol, 2,6-dimethyl-3-propylphenol, and the like. Polyphenylene ethers obtained by polycondensation of one or more of these phenols include, 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 on 3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene) ether. A graft copolymer. In particular, poly (2,6-dimethyl-1,
4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer and a graft copolymer obtained by graft-polymerizing styrene to the former two are preferable as the polyphenylene ether resin used in the present invention. It is.

Next, in the resin composition of the present invention, the vinyl aromatic hydrocarbon resin (b) used by mixing with the polyphenylene ether resin is a monomer structural unit represented by the following formula: A resin having at least 25% by weight or more therein. α-methylstyrene copolymer, styrene / butadiene / block copolymer and the like can be mentioned, and these may be used as a mixture of two or more. Among them, rubber-modified polystyrene is preferably used.

[0014]

Embedded image (Wherein, 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 an integer of 1-3)

In the resin composition of the present invention, when a polyphenylene ether-based resin and a vinyl aromatic hydrocarbon resin are used in combination, the ratio of both is generally 90/90.
10-10 / 90, preferably 80 / 20-20 / 80
It is. (C) used in the resin composition of the present invention
The hindered amine-based compound 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 and bis (1,2,2,
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, bis (1-ethyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, and the like. In particular, bis (1,2,2,6,6-pentamethyl-
4-Piperidyl) sebacate is sold by Sankyo Co., Ltd. under the trade name SANOL LS-765, and is easily available.

Specific examples of the compound represented by the formula (5) include:
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-butanetetracarboxylate and the like can be mentioned. In particular, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate is sold by Asahi Denka Co., Ltd. under the trade name LA-52. And is readily available.

The hydroxybenzotriazole-based compound (d) used in the resin composition of the present invention is a compound represented by the formula (6). (D) Specific examples of the hydroxybenzotriazole-based compound include 2- (2'-hydroxy-3'-methylphenyl) -5-chlorobenzotriazole, 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.
In particular, 2- (2'-hydroxy-3'-tert-butyl-
5'-Methylphenyl) -5-chlorobenzotriazole is a trade name of Sumisorb 300 from Sumitomo Chemical Co., Ltd., and is 2- (2'-hydroxy-3 ', 5'-di-tert-).
(Butylphenyl) -5-chlorobenzotriazole
It is sold by Asahi Denka Co., Ltd. under the trade name LA-34 and is readily available.

The amount of the hindered amine compound (c) is generally 0.05 to 10 parts by weight, preferably 100 parts by weight, based on 100 parts of the resin component (a) and (b). In the range of 0.1 to 5 parts by weight, the amount of the hydroxybenzotriazole-based compound (d) is generally selected in the range of 0.05 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight. . If the addition amount is larger than this range, the moldability and processability will decrease, and if the addition amount is smaller than this range, the effect will be small.

The resin composition of the present invention may contain, if desired,
An ABA ′ type block copolymer elastomer can be blended as an impact resistance imparting agent. Where A-
The BA-type block copolymer elastomer is a rubbery block copolymer composed of blocks A and A 'in which a vinyl aromatic compound is polymerized and blocks B in which a conjugated diene compound is polymerized. B includes blocks in which most of the double bonds are hydrogenated. The resin composition of the present invention further includes a resin other than the above, an elastomer, a known heat stabilizer, an antioxidant, a flame retardant, a flame retardant auxiliary,
Various additives such as pigments, lubricants, plasticizers, and organic fillers can be appropriately added. These may be used alone or as a mixture, and must be used in amounts that do not impair the characteristics of the resin composition of the present invention.

In preparing the polyphenylene ether-based resin composition of the present invention, a conventionally known method may be employed. For example, after mixing each component with a blender such as a turn bull mixer or a Henschel mixer, an extruder is used. A 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.

[0021]

EXAMPLES 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) Product 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 ° C, screw rotation speed 50rp
After melt-kneading under conditions of m, the mixture 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 (Nippon Steel Works, Ltd.)
Cylinder set temperature 29 using J100SA-2
A strip test piece (for light resistance test, size 3.2 × 12.7 × 63.6 ml) was prepared under the conditions of 0 ° C. and a mold temperature of 90 ° C. Next, the strip-shaped test piece obtained here was attached to a predetermined position of a 6.5 kW xenon arc-type fade meter (manufactured by Atlas, Ci-65 type), and pyrex glass (inner) and clear glass (outer) were attached. The filter was used as a 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 from the tester for a processing time of 300 hours, and the change in color tone was measured. The colorimetry was compared by ΔYI using a color difference meter (（-80, manufactured by Nippon Denshoku Industries Co., Ltd.). Table 1 shows the results.

Comparative Examples 2 to 4 Comparative Examples 1 and 2 were prepared by using a hindered amine compound or a hydroxybenzotriazole compound of the type shown in Table 2 with respect to 100 parts of the resin composition shown in Comparative Example 1. Operation 1 was repeated. Table 1 shows the results.

COMPARATIVE EXAMPLES 5-9 Comparative examples were prepared by using a hindered amine compound of the type shown in Table 2 and a hydroxybenzotriazole compound in the proportions shown in Table 1 with respect to 100 parts of the resin composition shown in Comparative Example 1. Operation 1 was repeated. Table 1 shows the results. Here, the chemical names of the compounds used in the comparative examples are shown below. SANOL LS-770: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate LA-57: tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3 4-butanetetracarboxylate tinuvin 144: 2- (3,5-di-t-butyl-4-
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (1,2,2,6,6-pentamethyl) hydroxybenzyl) smithsorb 340: 2- (2′-hydroxy-5′-t)
-Octylphenyl) -benzotriazole

Examples 1 to 3 The hindered amine compound and the hydroxybenzotriazole compound of the type shown in Table 2 were used in the proportions shown in Table 1 with respect to 100 parts of the resin composition shown in Comparative Example 1. Operation 1 was repeated. Table 1 shows the results.

[0025]

The polyphenylene ether-based resin composition of the present invention has excellent characteristics in which the light resistance to light through glass and indoor illumination light is greatly improved.

[0026]

Table 1 Table 1 Hindered amine benzotriazole-based compound System-based compound ΔYI Type Compounding amount (parts) Type Compounding amount (parts) Example 1 1-1 2.0 2-1 1.0 22.3 2 1-1 2.0 2-2 1.0 23.7 3 1-2 2.0 2-1 1.0 23.5 Comparative Example 1 50.3 2 1-1 2.0 36.5 3 1-2 2. 0 39.7 4 2-1 1.0 40.0 5 1-3 2.0 2-1 1.0 31.7 6 1-3 2.0 2-2 1.0 33.1 7 1-4 2.0 2-1 1.0 32.0 8 1-5 2.0 2-1 1.0 31.8 9 1-1 2.0 2-3 1.0 34.1

[0027]

Table 2 Type of compound No. Manufacturer Brand name Hindered amine 1-1 Sankyo Sanol LS-765-based compound 1-2 Asahi Denka LA-52 1-3 Sankyo Sanol LS-770 1-4 Asahi Denka LA- 57 1-5 Nippon Ciba Geigy Tinuvin 144 Benzotriazole 2-1 Sumitomo Chemical Sumisorb 300 Compound 2-2 Asahi Denka LA-34 2-3 Sumitomo Chemical Sumisorb 340

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-52-120639 (JP, A) JP-A-2-300168 (JP, A) JP-A-3-229748 (JP, A) JP-A-3-230 220256 (JP, A) JP-A-4-159353 (JP, A) JP-A-4-159354 (JP, A) JP-A-63-51442 (JP, A) JP-A-6-57087 (JP, A) JP-B-4-33305 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/14 C08K 3/00-13/08

Claims (1)

(57) [Claims] 1. A (a) polyphenylene ether resin 10
90 parts by weight, (b) vinyl aromatic hydrocarbon resin 10
90 parts by weight , the total of the components (a) and (b) being 100
Relative to the weight parts, selected from the group consisting of hindered amine-based compound represented by (c) General formalized 1 or general formalized 2
A resin set consisting of 0.05 to 10 parts by weight of at least one compound obtained and 0.05 to 10 parts by weight of a hydroxybenzotriazole compound represented by the general formula (3).
Adult . Embedded image (R ¹ is an alkylene group or an arylene group, R ² represents Ri alkyl group der may R ¹ is not) ## STR2 ## (R ³ is an alkyl group) (R ⁴ is hydrogen, an alkyl group or an arylene group,
Z ¹ is a halogen atom, and two R ⁴ may be the same or different from each other)