JP2674209B2 - Stabilized thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a stabilized thermoplastic resin composition.
More specifically, it relates to a thermoplastic resin composition which is excellent in heat-resistant processing stability during hot molding and heat discoloration resistance.

<Prior Art> Among thermoplastic resins, particularly butadiene-based polymers are
The present inventors have previously found a compound effective as a stabilizer for such a butadiene-based polymer, although it is susceptible to thermal deterioration during molding (Japanese Patent Application No. 62-327731).

On the other hand, thermoplastic resins other than butadiene-based polymers are
Although not as good as a butadiene-based polymer, it suffers from problems such as gelation due to thermal deterioration during molding and discoloration, which significantly reduces the commercial value. Especially recently,
With the aim of improving productivity, there is a tendency for molding at higher temperatures, and prevention of thermal deterioration during high temperature molding is becoming more necessary than ever.

Conventionally, pentaerythrityl tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] or octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, either alone or in combination with other antioxidants. It has been used in various combinations.

<Problems to be Solved by the Invention> However, by adding various antioxidants, although the thermal deterioration during molding is considerably improved, the effect in the case of molding at a higher temperature is still insufficient, There has been a demand for a further excellent heat-resistant processing stabilizer.

<Means for Solving the Problems> Therefore, the inventors of the present invention have made extensive studies in order to further improve these insufficient points, and have arrived at the present invention.

That is, the present invention provides a thermoplastic resin other than a butadiene-based polymer with the addition of 2-t-amyl-6- [1- (3,5-di-t-amyl-
2-Hydroxyphenyl) ethyl] -4-t-amylphenyl acrylate is provided to provide a thermoplastic resin composition having excellent heat-resistant processing stability during hot molding and heat discoloration resistance.

The above 2-t-amyl-6- [1- (3,5-di-t-
Amyl-2-hydroxyphenyl) ethyl] -4-t-
Amylphenyl acrylate is preferably used in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the thermoplastic resin. If the compounding amount is less than 0.01 part by weight, the above effect is not sufficient, and if it exceeds 1 part by weight, bleeding is increased. Cause

The thermoplastic resins that can be stabilized by the present invention are generally various polymers showing thermoplasticity (excluding butadiene-based polymers), and include, for example, the following.

(1) Polyethylene, such as high density polyethylene (HD
-PE), low-density polyethylene (LD-PE), linear low-density polyethylene (L-LDPE).

(2) Polypropylene.

(3) Methylpentene polymer.

(4) EEA (ethylene-ethyl acrylate copolymer) resin.

(5) Ethylene-vinyl acetate copolymer.

(6) Ionomer resin.

(7) Polystyrene, poly (p-methylstyrene),
Poly (α-methylstyrene).

(8) AS (acrylonitrile-styrene copolymer) resin.

(9) ABS (acrylonitrile-butadiene-styrene copolymer) resin.

(10) AAS (Special Acrylic Rubber-Acrylonitrile-
Styrene copolymer) resin.

(11) ACS (acrylonitrile-chlorinated polyethylene-styrene copolymer) resin.

(12) Chlorinated polyethylene, polychloroprene, chlorinated rubber.

(13) Polyvinyl chloride, polyvinylidene chloride.

(14) Methacrylic resin.

(15) Ethylene-vinyl alcohol copolymer resin.

(16) Fluorine 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, polyether ether ketone,
Polyether sulfone.

(25) Aromatic polyester resin.

In the composition of the present invention, if necessary, other additives such as other phenolic antioxidants, sulfur antioxidants, ultraviolet absorbers, hindered amine light stabilizers, lubricants, plasticizers, flame retardants. , An antistatic agent, a pigment and an inorganic filler may be added. 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'-thio-diethylene bis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate and the like.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (β-lauryl). Thiopropionate) 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
Condensate 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 1,6,6-Pentamethyl-4-piperidinol and 1-tridecanol mixed esterified product, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1- Mixed esterification product with tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2
-Hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed esterified product, 1,2,3,4-butanetetracarboxylic acid and 2,2 , 6,6-Tetramethyl-4-piperidinol and 3,9-bis (2-
Hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed esterified product, N, N'-bis (2,2,6,6-tetramethyl -4-Piperidyl) hexamethylenediamine and 1,2-dibromoethane polycondensate, 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> Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 An ethylene-vinyl acetate copolymer "Evatate CVX-006" [Sumitomo Chemical Co., Ltd.] was used as a thermoplastic resin, and the following phenol compounds were used.

AO-1: 2-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] -4-t-amylphenyl acrylate AO-2: 2-t-butyl -6- (3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate AO-3: pentaerythrityl tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate These compounds were dry blended with the above-mentioned ethylene-vinyl acetate copolymer in the amounts shown in Table 1, and then 200 with a single screw extruder having a diameter of 30 mm. Melt kneading at ℃,
Pelletized. The following physical properties were measured using the obtained pellets, and the results are shown in Table 1.

Heat-resistant processing stability (MI retention): Melt indexer [Takara Kogyo Co., Ltd.]
It evaluated by the fluidity (g / 10min) after making it hold | maintain for 0 minute. Since the ethylene-vinyl acetate copolymer is crosslinked by heat and its fluidity is lowered, it means that the higher the melt flow rate is, the more excellent the high temperature processing stability is.

Heat discoloration degree: Using a single-screw extruder with a diameter of 30 mm, repeatedly extruding 5 times at 280 ° C, the pellets obtained at the 1st and 5th times are further molded at 240 ° C by a 1 ounce injection molding machine, 1
A flat plate having a thickness of mm was used. The YI value of each flat plate obtained from the pellets of the first and fifth times of repeated extrusion was measured,
The thermal discoloration degree was evaluated by the difference ΔYI between the two. The smaller the value of ΔYI, the better the heat discoloration resistance.

Example 2 Acrylonitrile-styrene copolymer was used as the thermoplastic resin, and the following phenol compounds were used.

AO-1: 2-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] -4-t-amylphenyl acrylate AO-4: triethylene glycol bis [ 3- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionate] AO-5: octadecyl 3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate These compounds were dry-blended to the acrylonitrile-styrene copolymer resin in the amounts shown in Table 2, and then melt-kneaded at 200 ° C with a single-screw extruder having a diameter of 30 mm, Pelletized. The following physical properties were measured using the obtained pellets, and the results are shown in Table-2.

Processing Stability (Residual Monomer Concentration): The above pellets were run on a 5.5 oz injection molding machine at 300 ° C.
After staying for 15 minutes, a sheet having a thickness of 1 mm was formed. This sheet was dissolved in toluene and the residual monomer concentration was measured by GC analysis using GC-9A [Shimadzu Corporation]. The lower the residual monomer concentration, the smaller the decomposition due to heat during molding and the better the processing stability.

<Effects of the Invention> The thermoplastic resin composition of the present invention is excellent in heat-resistant processing stability and heat discoloration resistance during high-temperature molding.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kikumitsu Inoue 3-1,98 Kasugadenaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (56) Reference JP-A-59-71341 (JP, 59-71341) A) JP-A-58-84835 (JP, A) JP-A-56-77241 (JP, A) JP-A-56-61323 (JP, A) JP-A-63-146947 (JP, A) JP-A-1 -168643 (JP, A)

Claims (1)

(57) [Claims] 1. A thermoplastic resin other than a butadiene-based polymer is prepared by adding 2-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] -4-t-amyl. A stabilized thermoplastic resin composition comprising a phenyl acrylate.