JPH08104802A - Polyalkylene oxide resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] The compound having a specific structure is mixed with polyalkylene oxide to suppress thermal decomposition during high temperature processing. [Structure] The polyalkylene oxide has the formula (I) A phenolic compound represented by is blended. In the above formula,
R ¹ , R ² and R ³ are each independently hydrogen or methyl, and R ⁴ and R ⁵ are independently C 1 to C 1
Alkyl of 9. [Effect] The thermal decomposition of the polyalkylene oxide is suppressed even when the polyalkylene oxide is processed at a high temperature or when the thermoplastic resin containing the polyalkylene oxide as an antistatic agent is processed at a high temperature. Therefore, a sufficient antistatic effect is obtained, and the problems of thermal discoloration and mold contamination are improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyalkylene oxide resin composition having improved processability at high temperatures.

[0002]

2. Description of the Related Art Polyalkylene oxides such as polyethylene oxide exhibit thermoplasticity and are easy to mold, but generally have poor thermal stability. For example, in the case of polyethylene oxide, the weight loss onset temperature is about 165 ° C. . Due to such a problem of thermal stability, the use of polyethylene oxide itself as a molded product is not so large at present.

On the other hand, one of the uses of polyethylene oxide is polystyrene, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene /
There are antistatic agents for thermoplastic resins including styrene-based resins such as styrene copolymer (ABS resin) and rubber-reinforced polystyrene (high impact polystyrene: HIPS). Since such a thermoplastic resin is easy to mold and the molded product has excellent characteristics,
It is widely used, and in particular, because of its good electrical insulation, it is also widely used in electric parts such as office automation equipment and home appliances. However, since molded products made of thermoplastic resins such as styrene resin are easily charged,
There is a problem that dust adheres and is easily soiled. Therefore, various antistatic grades have been developed so far, and attempts to use polyalkylene oxides as antistatic agents have also been proposed.

For example, Japanese Patent Application Laid-Open No. 2-233743 describes a styrene resin composition containing a polyethylene oxide and an alkylbenzene sulfonate, which is excellent in antistatic properties. Further, JP-A-3-227357 discloses an antistatic rubber-reinforced styrene resin composition prepared by blending polyethylene oxide and a metal salt which forms a solid solution with polyethylene oxide.

[0005]

Generally, a thermoplastic resin such as a styrene resin is processed at a high temperature of about 200 ° C. or higher, but as described above, a polyalkylene oxide such as polyethylene oxide has a thermal stability. Therefore, when a polyalkylene oxide is blended with a thermoplastic resin, not only the polyalkylene oxide is thermally decomposed during processing and the antistatic effect is difficult to be exhibited, but also a low molecular weight polyalkylene glycol which is a thermal decomposition product. Due to heat discoloration due to, the low molecular weight component adheres to the mold during injection molding and causes mold contamination.
There were various problems.

The inventors of the present invention have made it possible to improve the thermal stability of polyalkylene oxide and to solve the above-mentioned problems in blending and processing the polyalkylene oxide in another thermoplastic resin. As a result, as a result of intensive studies, it was found that such an object can be achieved by blending a specific phenolic compound with polyalkylene oxide, and the present invention has been completed.

[0007]

That is, the present invention provides a polyalkylene oxide and a compound represented by the general formula (I):

[0008]

(In the formula, R ¹ , R ² and R ³ each independently represent hydrogen or methyl, and R ⁴ and R ⁵ each independently represent alkyl having 1 to 9 carbon atoms) The present invention provides a polyalkylene oxide resin composition containing:

The polyalkylene oxide used in the present invention is a polymer having an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide and epichlorohydrin as a monomer, and one or more of these monomers are used. It can be obtained by polymerizing. The polyalkylene oxide preferably has a weight average molecular weight of 1,000 to 10,000,000.
Among the polyalkylene oxides, polyethylene oxide is particularly preferably used.

The phenolic compound of the general formula (I) used in the present invention is a mono (meta) of bisphenol in which the 6-position of 2,4-dialkylphenol or 2,4,5-trialkylphenol is linked with methylene or ethylidene. ) Acrylate. Therefore, the general formula (I)
In, R ¹ is hydrogen or methyl and R ² is also hydrogen or methyl. The ester part is acrylate,
That is, it is preferable that R ¹ is hydrogen. R ³ located at the 5-position of the phenol is also hydrogen or methyl,
Usually hydrogen is preferred. R ⁴ located at the 4-position of the phenol is selected from alkyl having 1 to 9 carbon atoms, among which alkyl having 1 to 6 carbon atoms is preferable, and particularly preferable are methyl, ethyl, t-butyl and t. -Amy. R located at the 2-position of phenol
^{5 is} also selected from alkyl having 1 to 9 carbon atoms, and among them, alkyl having 4 to 8 carbon atoms is preferable, and particularly alkyl having a quaternary carbon bonded to a benzene ring, such as t-butyl and t.
-Amyl and t-octyl are more preferred.

Preferred specific examples of the phenolic compound represented by the general formula (I) are as follows.

2-t-butyl-6- (3-t-butyl-
2-Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-butyl-6-
[1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2,4-di-
t-amyl-6- [1- (3,5-di-t-amyl-2
-Hydroxyphenyl) ethyl] phenyl acrylate and the like.

The phenolic compound of the general formula (I) is used in an amount of 0.01-2 per 100 parts by weight of polyalkylene oxide.
It is preferably used in the range of parts by weight. The blending amount is 0.0
If it is less than 1 part by weight, the effect of suppressing the thermal decomposition of polyalkylene oxide is not always sufficient, and the effect of improving the thermal stability is poor. Further, even if the amount is more than 2 parts by weight, the effect corresponding to it cannot be obtained, which is not economical.

The polyalkylene oxide resin composition of the present invention can be imparted with antistatic performance by mixing it with any thermoplastic resin. Therefore, the composition of the present invention may contain other thermoplastic resin in addition to the polyalkylene oxide and the phenolic compound of the general formula (I). When the polyalkylene oxide is blended with another thermoplastic resin in this manner, the addition timing of the phenolic compound is not particularly limited, and for example, a mixture of the polyalkylene oxide and the phenolic compound in advance may be different. It may be added to the thermoplastic resin, or a phenolic compound may be added at the stage of blending the polyalkylene oxide and another thermoplastic resin. Examples of the thermoplastic resin used in this case are shown below.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-P)
E), linear low density polyethylene (L-LDPE); (2) polypropylene; (3) methylpentene polymer; (4) EEA (ethylene / ethyl acrylate copolymer) resin; (5) ethylene / vinyl acetate copolymer Resin; (6) Ionomer resin; (7) Polystyrene, poly (p-methylstyrene), rubber reinforced polystyrene; (8) AS (acrylonitrile / styrene copolymer) resin; (9) ABS (acrylonitrile / butadiene / styrene copolymer) ) Resin; (10) AAS (acrylonitrile / special acrylic rubber /
(Styrene copolymerization) resin; (11) ACS (acrylonitrile / chlorinated polyethylene /
(Styrene copolymerization) resin; (12) Chlorinated polyethylene, polychloroprene, chlorinated rubber; (13) Polyvinyl chloride, polyvinylidene chloride; (14) Methacrylate ester resin; (15) Ethylene / vinyl alcohol copolymer resin (16) Fluorinated resin; (17) Polyacetal; (18) Grafted polyphenylene ether resin and polyphenylene sulfide resin; (19) Polyurethane; (20) Polyamide; (21) Polyethylene terephthalate, Polybutylene terephthalate; (22) Polycarbonate (23) Polyarylate; (24) Polysulfone, polyetheretherketone, polyethersulfone; (25) Aromatic polyester resin and the like.

When such a thermoplastic resin is blended with a polyalkylene oxide and a phenolic compound of the general formula (I) or a polyalkylene oxide resin composition containing the phenolic compound of the general formula (I) is blended, The blending ratio is preferably such that the polyalkylene oxide is in the range of 2 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the amount of the polyalkylene oxide compounded is less than 2 parts by weight, it becomes difficult to obtain a sufficient antistatic effect, and when it exceeds 40 parts by weight, the surface quality of the molded product deteriorates and the excellent properties of the base resin are obtained. Is not preferable because it cannot be maintained.

Further, a composition containing the polyalkylene oxide according to the present invention and the phenolic compound of the general formula (I), or a composition containing still another thermoplastic resin,
If necessary, other additives such as other phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, organic sulfonic acid metal salts, compatibilizers. , Lubricants, pigments, dyes, flame retardants, foaming agents, reinforcing agents, inorganic fillers and the like. Specific examples of these additives that can be optionally used are shown below.

Examples of the phenol-based antioxidant other than the phenol-based compound represented by the general formula (I) include the following.

N-octadecyl 3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate, pentaerythrityl tetrakis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethyl Ethyl] -2,4,8,
10-Tetraoxaspiro [5.5] undecane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,2'-ethylidene bis (4,6-di-t-butylphenol) , 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-) t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

Examples of sulfur antioxidants include the following.

Dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate,
Lauryl stearyl 3,3'-thiodipropionate and the like.

Examples of phosphorus-based antioxidants include the following.

Tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl)
Phosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-6-t-butylphenyl) diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2 , 4,6-Tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-
t-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t
-Butylphenyl) 4,4'-biphenylene diphosphonate, 2,2'-methylenebis (4,6-di-t
-Butylphenyl) octyl phosphite, 2,
2'-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphonite and the like.

Examples of the ultraviolet absorber include the followings.

2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-)
Methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone,

2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3-
(3,4,5,6-tetrahydrophthalimidomethyl)
-5-Methylphenyl] benzotriazole, 2- (3
-T-butyl-2-hydroxy-5-methylphenyl)
-5-chlorobenzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole,
2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2
-(3,5-Di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo Triazole,

2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3)
-Tetramethylbutyl) phenol], 2,2'-methylenebis [4-t-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11)
(Ethylene glycol) and methyl 3- [3- (2H
-Benzotriazol-2-yl) -5-t-butyl-
4-hydroxyphenyl] propionate condensate,
2-ethylhexyl 3- [3-t-butyl-5- (5
-Chloro-2H-benzotriazol-2-yl) -4
-Hydroxyphenyl] propionate, octyl 3
-[3-t-Butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl]
Propionate, methyl 3- [3-t-butyl-5-
(5-chloro-2H-benzotriazol-2-yl)
-4-hydroxyphenyl] propionate, 3- [3
-T-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and the like.

Examples of the hindered amine light stabilizer include the following.

Bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, bis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) 2- (3,5-
Di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,
6-tetramethyl-4-piperidyl) 2,2-bis (3,
5-di-t-butyl-4-hydroxybenzyl) malonate, bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) decandioate, bis (2, 2, 6,
6-tetramethyl-4-piperidyl) succinate,
2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-
Piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- {3- (3,5-di-t-butyl-4-hydroxy) (Phenyl) propionyloxy} ethyl] -2,2,6,6-tetramethylpiperidine, 2-
Methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide,

Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1- Mixed esterified product with tridecanol, 1,2,3,4-butanetetracarboxylic acid mixed esterified product with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3, 4-butanetetracarboxylic acid and 1,
With 2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Mixed ester compound of 1, 2,
3,4-butanetetracarboxylic acid and 2,2,6,6-
Tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,
A mixed esterified product with 4,8,10-tetraoxaspiro [5.5] undecane,

Dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-
Polycondensate with tetramethylpiperidine, poly [(6-morpholino-1,3,5-triazine-2,4-diyl)
{(2,2,6,6-tetramethyl-4-piperidyl)
Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [{6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-triazine-2,4-diyl} {(2,2,
6,6-Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (2,2,6)
Polycondensation product of 6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, N,
N ', 4,7-Tetrakis [4,6-bis {N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino} -1,3,5-triazine-2- Il-
4,7-diazadecane-1,10-diamine, N,
N ', 4-tris [4,6-bis {N-butyl-N-
(2,2,6,6-Tetramethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-
Diazadecane-1,10-diamine, N, N ', 4,7
-Tetrakis [4,6-bis {N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-
Diazadecane-1,10-diamine, N, N ', 4-tris [4,6-bis {N-butyl-N- (1,2,2,2
6,6-Pentamethyl-4-piperidyl) amino}-
1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

As the organic sulfonic acid metal salt, an alkane sulfonic acid metal salt, that is, a compound represented by the general formula

(R-SO ₃ ) n-M

Wherein R is a linear or branched alkyl having 1 to 30 carbon atoms, M is a metal, and n is one or more corresponding to the valence of the metal represented by M. Those that are integers are preferred. Examples thereof include alkanesulfonic acid metal salts in which R is methyl, octyl, dodecyl, stearyl and the like. The metal represented by M can be arbitrarily selected from alkali metals such as lithium, kallium, and sodium, and alkaline earth metals such as magnesium and calcium.

There is no particular limitation on the method for producing the polyalkylene oxide resin composition of the present invention. For example, when the phenol compound of the general formula (I) is added to the polyalkylene oxide, a Henschel mixer or a V-type blender is used. Using a kneader such as these, or by mixing them by means such as dry blending, and then using a single screw extruder, twin screw extruder, kneader, twin screw kneader, injection molding machine, etc. This composition can be produced by a method of directly kneading the phenolic compound during a melt processing operation such as extrusion molding or injection molding. When other additives are added, they may be added at any stage of producing the composition. Also, a composition containing a polyalkylene oxide, a phenolic compound of the general formula (I) and another thermoplastic resin, or optionally a composition containing further other additives, is the same as described above. It can be manufactured by any method.

[0037]

EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples show preferred specific examples and do not limit the scope of the present invention. Parts in the examples are by weight unless otherwise specified. Here, the following were used as the test stabilizers.

Compound A: 2,4-di-t-amyl-6
-[1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate Compound B: 2-t-butyl-6- (3-t-butyl-
2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate AO-1: pentaerythrityl tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate]

Example 1 In a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.),
Polyethylene oxide PEO-3 [Sumitomo Seika Chemicals Ltd., weight average molecular weight 600,000-1.100,000] was added with each of the test stabilizers in the amounts shown in Table 1, and at 200 ° C under a nitrogen gas atmosphere. The mixture was kneaded under the conditions of 60 rpm and the change in torque value was traced. Since the torque decreases when polyethylene oxide is thermally decomposed, the heat resistance was evaluated by measuring the time from the start of kneading until the decrease in torque was observed, and the results are also shown in Table 1.

[0040]

[Table 1]

[0041]

EFFECT OF THE INVENTION By blending a specific phenolic compound with polyalkylene oxide according to the present invention, thermal decomposition can be suppressed even when the polyalkylene oxide is subjected to processing at high temperature. Therefore, when the polyalkylene oxide is used as an antistatic agent for another thermoplastic resin, for example, the phenol compound is blended with the other thermoplastic resin together with the polyalkylene oxide, or the phenol compound is preliminarily polyalkylene oxide. By blending the composition obtained by blending with other thermoplastic resin, the polyalkylene oxide exhibits an excellent antistatic effect even when it is processed at a high temperature. Further, by blending such a phenolic compound, the problems of thermal discoloration and mold contamination due to thermal decomposition of polyalkylene oxide can be solved. Thus, the polyalkylene oxide having improved thermal stability can be applied to various polymers that require processing at high temperature, and can be processed at high temperature without being blended with other polymers. It also leads to the expansion of applications.

Claims (6)

[Claims] 1. A polyalkylene oxide and a compound of general formula (I) (Wherein R ¹ , R ² and R ³ each independently represent hydrogen or methyl, and R ⁴ and R ⁵ each independently represent alkyl having 1 to 9 carbon atoms). A polyalkylene oxide resin composition comprising: 2. The composition according to claim 1, wherein the polyalkylene oxide is polyethylene oxide. 3. A phenolic compound is 2-t-butyl-
6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,
4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate or 2,4-di-t-amyl-6- [1-
(3,5-di-t-amyl-2-hydroxyphenyl)
The composition according to claim 1 or 2, which is ethyl] phenyl acrylate. 4. The composition according to claim 1, 2 or 3 which contains 0.01 to 2 parts by weight of a phenolic compound per 100 parts by weight of polyalkylene oxide. 5. The composition according to claim 1, which further contains another thermoplastic resin. 6. The composition according to claim 5, which contains 2 to 40 parts by weight of a polyalkylene oxide per 100 parts by weight of another thermoplastic resin.