JP2998121B2 - 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, in particular, 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 having excellent mechanical properties and flame retardancy. However, polyphenylene ether-based resins have a disadvantage that they are easily discolored by light, particularly yellow. For applications used indoors, the solar rays rarely reach directly, and are exposed to light through windows and energetically weakened lights such as indoor lighting. Therefore, the polyphenylene ether-based resin undergoes severe discoloration, particularly yellowing, and the ΔYI value representing the 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. 62-6042
No. 0 and JP-B-4-33305 disclose that when a specific hydroxybenzophenone-based compound is combined with a specific hindered amine-based compound, a polyphenylene ether-based resin having very good stability to ultraviolet light can be obtained. Have been. 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 order to stabilize plastics.

[0004] Ethylene vinyl alcohol copolymer is
JP-A-4-53855 discloses a composition with polyphenylene ether. However, in this publication, an ethylene / vinyl alcohol copolymer is used to increase the oil resistance and molding processability of a polyphenylene ether-based resin, and nothing is taught about improving light resistance.

[0005]

The above-mentioned benzophenone-based compound has a maximum absorption wavelength of ultraviolet light at 280 to 300 nm and does not absorb a large amount of ultraviolet light of about 300 to 330 nm which deteriorates plastics. The suppression effect is often low. Also, when a large amount of organic low molecular weight compounds such as hindered amine, benzotriazole, benzophenone, and salicylate are added to polyphenylene ether resin, the organic low molecular weight compounds adhere to the surface of the molded article during injection molding, resulting in poor appearance. In addition, the gas vent of the mold is closed, and the organic low molecular weight compound adheres to the protruding pins and the like, which makes it difficult to continuously form good products.

An object of the present invention is to solve the above-mentioned problems and to improve the light resistance of polyphenylene ether-based resin, particularly the light resistance against light through glass.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the polyphenylene ether-based resin, and as a result, have found that a mixture of polyphenylene ether and a styrene-based polymer has a hindered amine compound and a hydroxy group. By adding a benzotriazole-based compound and an ethylene / vinyl alcohol copolymer, it was found that the light resistance was remarkably improved, and the present invention was reached.

That is, the present invention relates to (a) 10 to 90 parts by weight of polyphenylene ether and (b) styrene-based polymer 90
(C) 0.05 to 5 parts by weight, (d) hydroxybenzotriazole-based compound 0.05 with respect to 100 parts by weight of a resin component composed of components (a) and (b) To 5 parts by weight, and (e) an ethylene / vinyl alcohol copolymer 0.5 to 2
It is a polyphenylene ether-based resin composition comprising 0 parts by weight.

The polyphenylene ether (a) used in the resin composition of the present invention is described in, for example,
It can be produced according to the method described in Japanese Patent No. 286464. In particular, poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethyl-1,4-phenol / 2,3,6-trimethyl-1,4-phenol copolymer and the former A graft copolymer obtained by graft-polymerizing styrene is preferred as the polyphenylene ether used in the present invention. The intrinsic viscosity of the polyphenylene ether suitable for the present invention is preferably in the range of 0.35 to 0.60 dl / g as measured with a chloroform solution at 25 ° C. If the intrinsic viscosity is higher than 0.60 dl / g, the melt viscosity of the composition will be high, and the bar flow length will be reduced, making it particularly difficult to form a large thin molded product. Conversely, the limiting viscosity is 0.3
If it is lower than 5 dl / g, the mechanical strength is greatly reduced and the value as a practical molded product is impaired.

In the resin composition of the present invention, polystyrene, rubber-modified polystyrene (impact polystyrene), MS, MBS, AS,
AAS, AES, AMBS, styrene / maleic acid copolymer resin (for example, trade name: Dailark, manufactured by Arco Chemical Co., USA), SBR, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, hydrogenated SEBS elastomer (for example, Clayton G, manufactured by Shell Chemical Co., Ltd.); core-shell type elastomer in which the core layer is made of rubber and the shell layer is made of hard resin (for example, manufactured by Takeda Pharmaceutical Co., Ltd .; Lloyd), MBS-based elastomer, Kureha BTA elastomer, diblock or triblock copolymer in which the polystyrene phase is a hydrogenated polyisoprene phase (for example, Kuraray Co., Ltd., trade name: Septon).

In the resin composition of the present invention, when a mixture of polyphenylene ether and styrene-based polymer is used, the ratio of the two is generally 90/10 to 10 /.
90, preferably 80/20 to 20/80.

As the hindered amine compound (c) used in the resin composition of the present invention, 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, Bis (1-ethyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane Tetracarboxylate, 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.

The hydroxybenzotriazole compound (d) used in the resin composition of the present invention is 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-chlorobenzotriazole, 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.

The amount of the hindered amine compound (c) to be added is in the range of 0.05 to 5 parts by weight based on 100 parts by weight of the resin component comprising the components (a) and (b). The amount of the hydroxybenzotriazole-based compound is selected in the range of 0.05 to 5 parts by weight. If the amount of the hindered amine-based compound or hydroxybenzotriazole-based compound is larger than this range, the moldability and workability will be reduced, and if the added amount is smaller than this range, the effect of light resistance will be small.

The (e) ethylene-vinyl alcohol copolymer used in the resin composition of the present invention is obtained by random copolymerization of ethylene and vinyl alcohol, and the copolymer ratio of ethylene is 20 to 60 mol%. Are preferred. The ethylene / vinyl alcohol copolymer is commercially available from Kuraray Co., Ltd. under the trade name "EVAL". The amount of the ethylene / vinyl alcohol copolymer to be added is generally 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the resin component comprising the components (a) and (b). It is in the range of parts by weight. If the addition amount is too large, the strength and thermal stability are impaired, and if the addition amount is too small, the effect of light resistance is small.

The resin composition of the present invention contains other thermoplastic resins such as PC, PBT, PET, PA, PE, P
P, maleic acid-modified PP, POM, PMMA, polyphenylene sulfide, polyether ether ketone, polysulfone, and the like can be blended.

Various elastomers can be blended with 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 a hydrogenated product thereof, styrene-
Examples include an isoprene-styrene tereblock copolymer, a hydrogenated product thereof, a methyl methacrylate-butadiene copolymer, and a butyl methacrylate-butadiene copolymer.

Further, the resin composition of the present invention may contain, if desired, reinforcing agents, fillers, known heat stabilizers, antioxidants, flame retardants, flame retardant auxiliaries, pigments, lubricants, plasticizers and the like. Various additives 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.

Examples of the above-mentioned reinforcing material and filler include 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 metal 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, etc. No.

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.

[0021]

Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these. In addition, the part of each component in an Example shows a weight part.

Comparative Example 1 50 parts of poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity [η] of 0.44 dl / g, impact-resistant polystyrene (manufactured by Denki Kagaku Kogyo KK, product Name HI-UM-301
50), 3 parts of titanium oxide and 0.2 parts of zinc oxide were uniformly mixed using a super mixer. The obtained mixture is extruded with a 30 mmφ biaxial extruder (PCM-30, manufactured by Ikegai Iron & Steel Corp.)
The mixture was melt-kneaded under the conditions of a cylinder set temperature of 270 ° C. and a screw rotation speed of 50 rpm, and then pelletized. The pellets obtained here were dried for 2 hours using a hot air dryer at a temperature of 120 ° C., and then a cylinder set temperature of 290 ° C. using an injection molding machine (J100SA-II type, manufactured by Nippon Steel Works, Ltd.). A strip test piece (for light resistance test, size 3.2 × 12.7 × 63.6 ml) was prepared under the condition of a mold temperature of 90 ° C. Next, the strip-shaped test piece obtained here was used as a 6.5 kW xenon arc type fade meter (manufactured by Atlas, Ci-65).
And a filter (Pyrex glass (inner), clear glass (outer)), a black panel temperature of 63 ° C., and no rain spray. The strip-shaped test piece was taken out of the testing machine with 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 Hindered amine compounds (hereinafter abbreviated as HALS) and hydroxybenzotriazole compounds (hereinafter abbreviated as BTA) of the type shown in Table 2 were used with respect to 100 parts of the resin composition shown in Comparative Example 1. The same operation as in Comparative Example 1 was performed using any one of the ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) in the proportion shown in Table 1. Table 1 shows the results.

Comparative Examples 5 to 7 With respect to 100 parts of the resin composition shown in Comparative Example 1, two kinds of HALS, BTA and EVOH of the kind shown in Table 2 were used in proportion amounts shown in Table 1, The same operation as in Comparative Example 1 was performed. Table 1 shows the results.

Examples 1 to 6 In the same manner as in Comparative Example 1 except that HALS, BTA and EVOH 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. The operation was performed. Table 1 shows the results.

[0026]

As is clear from the above examples, the polyphenylene ether-based resin composition of the present invention has an excellent feature that light resistance to light through glass and indoor illumination light is greatly improved.

[0027]

[Table 1] HALS BTA EVOH Type Blended amount (parts) Type Blended amount (parts) Type Blended amount (parts) △ YI Actual-1 1-1 2.0 2-1 1.0 3-1 5.0 16.5 Actual-2 1- 1 2.0 2-2 1.0 3-1 5.0 16.9 Actual-3 1-2 2.0 2-1 1.0 3-1 5.0 16.6 Actual-4 1-1 2.0 2-1 1.0 3-2 5.0 15.5 Actual -5 1-1 2.0 2-2 1.0 3-2 5.0 15.8 Actual-6 1-2 2.0 2-1 1.0 3-2 5.0 15.8 Ratio-1 50.3 Ratio-2 1-1 2.0 36. 5 Ratio-3 2-1 1.0 40.0 Ratio-4 3-2 5.0 43.0 Ratio-5 1-1 2.0 2-1 1.0 22.3 Ratio-6 1-1 2.0 3-1 5.0 25.3 Ratio -7 2-1 1.0 3-1 5.0 29.2

[0028]

[Table 2] Type of compound No. Manufacturer Brand name HALS1-1 Sankyo LS-765 1-2 Asahi Denka LA-52 BTA 2-1 Sumitomo Chemical Sumisorb 300 2-2 Asahi Denka LA-34 EVOH 3- 1 Kuraray EVAL EP-F101 3-2 Kuraray EVAL EP-E105

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 23:26 29:04 25:04) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 1/00-101/14

Claims (1)

(57) [Claims] (A) polyphenylene ethers 10 to 9
0 parts by weight, (b) 90 to 10 parts by weight of a styrene-based polymer, resin component 10 comprising components (a) and (b)
With respect to 0 parts by weight, (c) 0.05 to 5 parts by weight of a hindered amine compound, (d) 0.05 to 5 parts by weight of a hydroxybenzotriazole compound, and (e) an ethylene / vinyl alcohol copolymer. A polyphenylene ether-based resin composition comprising 5 to 20 parts by weight.