JP2841684B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having excellent heat-resistant processing stability during high-temperature molding. is there.

<Conventional technology> Thermoplastic resins are generally susceptible to deterioration due to heat or shear during molding, and are degraded or crosslinked (gelled) due to deterioration, resulting in reduced workability and markedly worsened product properties. It is known to Conventionally, pentaerythrityl tetrakis [3- (3,5-di-
phenolic antioxidants such as tert-butyl-4-hydroxyphenyl) propionate] or octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, alone or in other It has been used in combination with inhibitors.

However, recently, thermoplastic resins with high melting temperatures during molding, including various engineering plastics, have been widely used, and even conventional thermoplastic resins have been used to improve productivity. It tends to be molded at higher temperatures.

<Problems to be Solved by the Invention> Therefore, prevention of thermal degradation during high-temperature molding of a thermoplastic resin is required more than ever. Means for Solving the Problems The present inventors have conducted intensive studies on the improvement of heat-resistant processing stability when a thermoplastic resin is molded at a high temperature, and as a result, have reached the present invention.

<Means for Solving the Problems> That is, the present invention provides a thermoplastic resin having the general formula (I) (In the formula, X is a divalent chain aliphatic group, a cycloaliphatic group or an aromatic group, which may contain halogen or oxygen. R ¹ is a hydrogen atom, a chain aliphatic A group, a cyclic aliphatic group or an aromatic group, and when X and R ¹ are both chain aliphatic groups, nitrogen atoms may be further linked to each other via R ^{1. 2} and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
R ² and R ³ may combine to form a ring. The present invention provides a thermoplastic resin composition containing a dinitrodiamine compound represented by the following formula: By blending such a specific dinitrodiamine compound, the heat-resistant processing stability of the thermoplastic resin can be improved.

Specific examples of the dinitrodiamine compound used here include the following. In the following examples,
-Z is Represents

_{(1) Z-NHCH 2 2} NH-Z (2) Z-NHCH 2 3 NH-Z (3) Z-NHCH 2 4 NH-Z (4) Z-NHCH 2 6 NH-Z (5) Z-NHCH _{2 10} NH-Z (6) Z-NHCH _{2 12} NH-Z (8) NO ₂ CH _{2 2} NHCH _{2 2} NHCH _{2 2} NO ₂ (9) NO ₂ CH _{2 2} NHCH _{2 6} NHCH _{2 2} NO ₂ Thus, the substituent X in the general formula (I) is
A divalent chain aliphatic group, a cycloaliphatic group or an aromatic group, which may contain a halogen in the group as in the above-mentioned 33rd and 34th examples; As described above, oxygen can be contained in the group. Among them, those in which X is a chain aliphatic group, particularly a chain aliphatic group having 4 to 12 carbon atoms are preferably used.

R ¹ in the general formula (I) is a hydrogen atom, a chain aliphatic group, a cycloaliphatic group or an aromatic group, and X and R ¹
Are both chain aliphatic groups, the nitrogen atoms are further linked to each other via R ¹ as in the 23rd and 24th examples above, and X, R ¹ and two nitrogen atoms Those that form a ring are also included.

Further, R ² and R ³ in the general formula (I) may be the same or different from each other, and are each a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Note that, as in the twelfth, thirteenth, twenty- ^second, and thirtieth examples, R ²
Also included are those in which R ³ is bonded to form a ring.

The heat-resistant processing stabilizer composed of such a dinitrodiamine compound may be a single compound of each compound, or may be a mixture with a carrier such as clay that does not affect the physical properties of the thermoplastic resin, Further, it may be mixed with other compounding agents. Therefore, any of these forms can be blended with the thermoplastic resin.

The amount of the dinitrodiamine compound used in blending the thermoplastic resin is not particularly limited, but if the amount is too small, the intended performance is insufficient, and if the amount is too large, the effect is saturated and uneconomical. Therefore, it is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of the thermoplastic resin.

As the thermoplastic resin that can be stabilized by the present invention,
For example, high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (L-LDP)
E), polypropylene (PP), methylpentene polymer, EEA (ethylene-ethyl acrylate copolymer) resin, E
VA (ethylene-vinyl acetate copolymer) resin, polystyrene (PS), poly (α-methylstyrene), AS (acrylonitrile-styrene copolymer) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, AAS (special acrylic) Rubber-acrylonitrile-styrene copolymer) resin, ACS (acrylonitrile-chlorinated polystyrene-styrene copolymer) resin, chlorinated polyethylene, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, ethylene-vinyl alcohol copolymer resin, fluororesin, Polyacetal, polyphenylene ether resin, polyphenylene sulfide resin, polyurethane, polyamide, polyethylene terephthalate, polybutylene terephthalate,
Examples include polycarbonate, polyarylate, polysulfone, polyetheretherketone, polyethersulfone, and aromatic polyester resin.

The composition of the present invention further comprises other additives as necessary,
For example, phenolic antioxidants, sulfur antioxidants,
Phosphorus antioxidants, UV absorbers, hindered amine light stabilizers, lubricants, plasticizers, flame retardants, antistatic agents, pigments,
An inorganic filler or the like can be contained. Specific examples of these additives include the following.

Examples of phenolic antioxidants include pentaerythrityl tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], octadecyl 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-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, 2,4-bis (n-octylthio) -6- (3,5-di-t
-Butyl-4-hydroxyanilino) -1,3,5-triazine, 1,6-hexanediol bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylene bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate], tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy) -5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and the like No.

As the sulfur-based antioxidants, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (β-lari Luthiopropionate) and the like.

Examples of phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4 ′
-Biphenylene diphosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like.

Examples of ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxy). Phenyl) 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- (3,5-di-t- Butyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl)
Benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo Triazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol], poly (3-11) (ethylene glycol) and methyl 3
-[3- (2H-benzotriazol-2-yl) -5-
Condensation product with t-butyl-4-hydroxyphenyl] propionate, 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 , 2,2'-methylenebis [4-t-butyl-6- (2H-
Benzotriazol-2-yl) phenol] and the like.

Bis (2,2,6,6-tetramethyl-4-piperidyl) is a hindered amine light stabilizer.
Polycondensate of sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-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}], bis (1,2, 2,6,6-pentamethyl-4-piperidyl)
2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]- 1- [2- ｛3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxydiethyl] -2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4- Piperidyl)
Decanedioate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, poly [｛6- (1,1,3,3-tetramethyl (Butyl) 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}], 1,2,3,4-butanetetracarboxylic acid and 1,2,2 Mixed ester with 1,6,6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol A mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-
Mixed esterified product with (hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2, Mixed ester with 6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane A polycondensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, 2-methyl-2- (2,2 , 6,6-Tetomethyl-4-piperidylamino) -N- (2,2,6,6-tetramethyl-4-
Piperidyl) propionamide, N, N ', 4,7-tetrakis [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-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, bis (1-acryloyl-2,2,6,6-tetramethyl-
4-piperidyl) 2,2-bis (3,5-di-t-butyl-
4-hydroxybenzyl) malonate, 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,
2,2,6,6-pentamethyl-4-piperidyl) amino}-
(1,3,5-triazin-2-yl) -4,7-diazadecane-
1,10-diamine, 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, tetrakis (1,2,2,6,6-pentamethyl-4 -Piperidyl) 1,2,3,4-butanetetracarboxylate.

<Examples> Hereinafter, the present invention will be described with reference to examples. However, these are merely examples, and the present invention is not limited to the gist thereof.
It is not limited to these embodiments. In the following example,
All percentages and parts are by weight unless otherwise specified.

The heat-resistant processing stabilizers used in the examples are as follows, and are indicated by the respective symbols.

A: N, N'-bis (2-methyl-2-nitropropyl)-
1,4-diaminobenzene B: N, N'-bis (2-methyl-2-nitropropyl)-
4,4'-diaminodiphenylmethane) C: N, N'-bis (2-methyl-2-nitrooctyl)-
1,4-diaminobenzene D: N, N'-bis (2-methyl-2-nitropropyl)-
1,6-diaminohexane E: N, N'-bis (2-methyl-2-nitropropyl)-
1,18-diaminooctadecane F: N, N'-bis (2-methyl-2-nitropropyl) piperazine AO: octadecyl 3- (3,5-di-t-butyl-4-)
(Hydroxyphenyl) propionate The method for measuring each physical property value in the examples is as follows.

(1) Melt flow rate According to the method specified in JIS K 6758, the temperature is 260 ° C and the load is 2.1.
Measured at 6 kg.

(2) Intrinsic viscosity The solution viscosity was measured using an Ubbelohde viscometer. The intrinsic viscosity was determined by a calculation method described in Polymer Experimental Science 11, page 491 (published by Kyoritsu Shuppan Co., Ltd. in 1982).

Examples 1 to 8 and Comparative Examples 1 and 2 Polypropylene was produced by a slurry polymerization method described in JP-A-60-28405. This polypropylene has a melt flow rate of 14 g / 10 min, an intrinsic viscosity in tetralin solvent at 135 ° C of 2.45 dl / g, a content of cold xylene-soluble portion at 20 ° C of 2.9%, and a content of boiling heptane-soluble portion The amount is 6.7%
The isotactic pentad fraction of the boiling heptane-insoluble portion was 0.952.

To 100 parts of this polypropylene, heat-resistant processing stabilizers were blended in the proportions shown in Table 1, respectively, and kneaded using a Labo Plastomill (Toyo Seiki Co., Ltd.) at 240 ° C. and 70 rpm for 5 minutes. The melt flow rate of the obtained composition was measured using a melt indexer (Takara Kogyo Co., Ltd.), and the results are shown in Table 1. Since polypropylene is molecularly cut by deterioration, the lower the melt flow rate, the better the heat processing stability.

Examples 9 and 10, Comparative Examples 3 and 4 Polystyrene having a melt flow rate of 17 g / 10 minutes was used. With respect to 100 parts of this polystyrene, heat-resistant processing stabilizers shown in Table 2 were blended in respective proportions, and
The heat processing stability was evaluated in the same manner as described above. Table 2 shows the results.
Shown in

Examples 11 and 12, Comparative Examples 5 and 6 The intrinsic viscosity measured in chloroform at 25 ° C was 0.3 dl /
g, a poly-2,6-dimethylphenylene ether having a melt flow rate of 1.6 g / 10 min. To 100 parts of this polyphenylene ether, heat-resistant processing stabilizers shown in Table 2 were blended in respective proportions, and the heat-resistant processing stability was evaluated in the same manner as in Examples 1 to 8. Table 2 shows the results.

Examples 13 and 14, Comparative Examples 7 and 8 The polystyrene used in Examples 9 and 10 and the polyphenylene ether used in Examples 11 and 12 were blended in a weight ratio of 70/30, and uniformly mixed with a Henschel mixer. Thereafter, the mixture was melt-kneaded in a twin screw extruder manufactured by Nippon Steel Works, Ltd., TEX 44 SS-30BW-2V, under the conditions of 260 ° C and an average residence time of 1.5 minutes, and a polyphenylene having a melt flow rate of 3.8 g / 10 minutes. An ether composition was produced.

For 100 parts of this polyphenylene ether composition,
The heat-resistant processing stabilizers shown in Table 2 were blended in respective proportions, and the heat-resistant processing stability was evaluated in the same manner as in Examples 1 to 8. Table 2 shows the results.

<Effects of the Invention> According to the present invention, a thermoplastic resin composition having excellent heat processing stability during high-temperature molding can be obtained by blending a specific dinitrodiamine compound with a thermoplastic resin.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroomi Abe 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Industries, Ltd. (72) Inventor Takeshi Fujii 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Industries, Ltd. (72) Inventor Masashi Yamamoto 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (56) References JP-A-2-276860 (JP, A) JP-A-2-265955 (JP, A) JP-A-3-292350 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 1/00-101/14 C08K 5/00-13/08

Claims (1)

(57) [Claims] 1. A thermoplastic resin (excluding a modified polyolefin resin) having a general formula (In the formula, X is a divalent chain aliphatic group, a cycloaliphatic group or an aromatic group, which may contain halogen or oxygen. R ¹ is a hydrogen atom, a chain aliphatic A group, a cyclic aliphatic group or an aromatic group, and when X and R ¹ are both chain aliphatic groups, nitrogen atoms may be further linked to each other via R ^{1. 2} and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
R ² and R ³ may combine to form a ring. A thermoplastic resin composition comprising a dinitrodiamine compound represented by the formula: