JPH0768408B2 - Synthetic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a synthetic resin composition, and more specifically, by adding a specific phosphite compound, it is possible to prevent deterioration due to the action of heat and oxygen over a long period of time. The present invention relates to a stabilized synthetic resin composition.

[Prior Art and Problems] It is known that synthetic resins such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride deteriorate due to the action of heat and oxygen, become colored, and have poor mechanical strength and cannot be used. There is.

In order to prevent such deterioration of the synthetic resin, many additives have been used singly or in various combinations. Among these additives, phosphite compounds have been widely used because they have the advantages of imparting heat resistance and light resistance to synthetic resins and suppressing the coloring of synthetic resins.

For example, pentaerythritol diphosphite such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite. The compound has been proposed as a phosphite compound which is particularly effective. However, the effect of these phosphite compounds is not yet sufficient, and there has been a demand for a phosphite compound having a greater effect.

The inventors of the present invention have made extensive studies in view of the current situation,
The present inventors have found that when a specific organic phosphite compound is used as a stabilizer for a synthetic resin, it exhibits a long-term stabilizing effect on the resin, and arrived at the present invention.

That is, the present invention provides a stabilized synthetic resin composition obtained by adding an organic phosphite compound represented by the following general formula (I) to a synthetic resin.

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms) In the general formula (I), the alkyl group represented by R is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. , T-butyl, t-amyl, octyl, t-octyl and the like.

Examples of the synthetic resin stabilized by the organic phosphite compound of the present invention include polyethylene, polypropylene, polybutene, α-olefin polymers such as poly-3-methylbutene or ethylene-vinyl acetate copolymers,
Polyolefins such as ethylene-propylene copolymers and their copolymers, polyvinyl chloride, polyvinyl bromide,
Polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer Polymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-
Maleic anhydride terpolymer, vinyl chloride-styrene-
Acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid Ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resin such as internally plasticized polyvinyl chloride, petroleum resin,
Coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, polyacrylonitrile, styrene or a copolymer of α-methylstyrene and other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), ABS resin (styrene component A so-called heat-resistant ABS resin in which a part is replaced with α-methylstyrene and a so-called super heat-resistant ABS resin obtained by copolymerizing maleimides are included), acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, Methacrylic acid ester-butadiene-styrene copolymer, methacrylate resin such as polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, linear polyester such as polybutylene terephthalate, polyphenylene Lenoxide, polyamide,
Examples thereof include polycarbonate, polyacetal, polyurethane, fibrin resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Further, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber and blends of these resins may be used. Further, a cross-linked polymer such as cross-linked polyethylene cross-linked by peroxide or radiation and a foamed polymer such as expanded polystyrene foamed by a foaming agent are also included.

The amount of the organic phosphite compound in the composition of the present invention is preferably 0.01 to 10% by weight based on the synthetic resin.

The composition of the present invention may be used in combination with a phenol-based or sulfur-based antioxidant.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and stearyl- (3,5-di-
Methyl-4-hydroxybenzyl) thioglycolate,
Stearyl-β- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl-3,5-
Di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert-butyl-4'
-Hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzyl malonate, 2,2'-methylenebis (4
-Methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-
Methylenebis [6- (1-methylcyclohexyl) p-
Cresol], bis [3,5-bis (4-hydroxy-3)
-Tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-
m-cresol), 2,2'-ethylidene bis (4,6-di-
Tertiary butylphenol), 2,2'-ethylidene bis (4
-Tert-butyl-6-tert-butylphenol), 1,1,3-
Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] Terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl)
Benzyl isocyanurate, 1,3,5-tris (3,5-di-
Tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, tetrakis [methylene-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) isocyanurate, 1,3,5-
Tris [(3,5-di-tert-butyl-4hydroxyphenyl) propionyloxyethyl] isocyanurate, 2
-Octylthio-4,6-di (4-hydroxy-3,5-di-
Tert-Butyl) phenoxy-1,3,5-triazine, 4,4′-
Thiobis (6-tert-butyl-m-cresol) and the like, particularly stearyl-β- (4-hydroxy-3,5
-Di-tert-butylphenyl) propionate, 1,3,5-
Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1, 3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-
Hydroxyphenyl) propionyloxyethyl] isocyanurate is useful. The amount of the phenolic antioxidant added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the synthetic resin.

It is also possible to improve the oxidative stability of the composition of the present invention by adding a sulfur-based antioxidant. Examples of these sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl-, and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, and stearyl- (for example, Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) ester (eg pentaerythritol tetralauryl thiopropionate)
Is mentioned.

The light resistance can be further improved by adding a light stabilizer to the composition of the present invention. Examples of these light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone and 2,4-dihydroxy. Hydroxybenzophenones such as benzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'- Benzotriazoles such as di-t-amylphenyl) benzotriazole, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-
Benzoates such as t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,2'-thiobis (4- t-octylphenol) N
i salt, [2,2′-thiobis (4-t-octylphenolate)]-n-butylamine Ni, (3,5-di-t-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt, etc. Nickel compounds, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,
6,6-Pentamethyl-4-piperidyl) -n-butyl-
3,5-di-tert-butyl-4-hydroxybenzyl-malonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) bis (3,5-di-tert-butyl-
4-hydroxybenzyl) malonate, tetrakis (2,
2,6,6-tetramethyl-4-piperidyl) butane-1,2,
3,4-Tetracarboxylate, 1-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate condensate, cyanuric chloride / tertiary octylamine / 1,6-bis (2, Piperidine compounds such as 2,6,6-tetramethyl-4-piperidylamino) hexane condensate, α-
Substituted acrylonitriles such as methyl cyano-β-methyl-β- (p-methoxyphenyl) acrylate and N-2
Examples include oxalic acid dianilides such as -ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide.

In addition, if necessary, the composition of the present invention contains a heavy metal deactivator, a nucleating agent, a metallic soap, an organic tin compound, a plasticizer, an epoxy compound, a pigment, a filler, a foaming agent, an antistatic agent, a flame retardant, and a lubricant. , Processing aids and the like can be included.

When using the organic phosphite compound of the present invention, it is preferable to add a small amount of a non-aromatic amine compound in order to improve its water resistance. Examples of these amine compounds include trialkanolamines such as triethanolamine, triisopropanolamine, and tri-n-propanolamine; diethanol / aliphatic amines, diisopropanol / aliphatic amines, di-n-propanol / aliphatic amines. Dialkanol / aliphatic amines such as diethanol / dodecylamine, diethanol / octadecylamine, diethanol / beef tallow alkylamine, diethanol / soybean oil alkylamine, diethanol / oleylamine, diethanol / octylamine, diethanol / coconut oil alkyl Amine, diethanol / hardened tallow alkylamine, diethanol / hexadecylamine, etc.); diisopropanolamine, diethanolamine, tetraethanolethylenediamine Dialkanolamines such as tetraisopropanol ethylenediamine; heterocyclic amines such as hexamethylenetetramine, piperidine, pyrrolidine, piperazine, diketopiperazine, N-methylpyrrolidine, oxazolidine, isoxazolidine; lauryldimethylamine oxide, stearyldimethylamine oxide, etc. Amine oxide; N
Examples include amino acid alkanolamines such as coconut oil fatty acid acyl-L-glutamic acid monotriethanolamine and N-lauroyl-L-glutamic acid monotriethanolamine.

The mixing ratio of the phosphite compound and the organic amine compound is
Amine is 0.01 to 100 parts by weight of the phosphite compound.
The amount is preferably 5 parts by weight, more preferably 0.1 to 2 parts by weight.

〔Example〕

Next, the present invention will be specifically described with reference to examples. However, the invention is not limited to these examples.

Synthesis Example-1 Bis (2,4,6-trimethylphenyl) pentaerythritol diphosphite (phosphite No. 1)
Synthesis of pentaerythritol 6.81 g (0.05 mol), xylene 4 in a 4-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube.
0 g and triethylamine 0.05 g (0.0005 mol) were charged, and phosphorus trichloride 15.13 g (0.11 mol) was added dropwise at 60 ° C. over 20 minutes. After reacting at 70 ° C. for 3 hours, 13.6 g (0.1 mol) of 2,4,6-trimethylphenol and 6 g of triethylamine (0.
(06 mol) was charged and reacted at 90 ° C. for 5 hours. After hot filtration,
Methanol was added for crystallization, filtration and drying to obtain a white powder. The melting point was 188-189 ° C.

As a result of infrared spectroscopic analysis, P-O-C (aromatic) at 1205 cm ^-1
In based absorption, absorption based on the P-O-C (alkyl) in the of 1020 cm ^-1 is also there is absorption based on 4-substituted phenyl group in 860 cm ^-1, it was confirmed that it was the desired product.

Synthesis Example-2 Synthesis of bis (2,6-dimethyl-4-t-butylphenyl) pentaerythritol diphosphite (phosphite No. 2) 2,6-dimethyl instead of 2,4,6-trimethylphenol A white powdery product having a melting point of 245 ° C. was obtained in the same manner as in Synthesis Example 1 except that -4-t-butylphenol was used.

Results of infrared spectroscopy, P-O-C (aromatic) to ^{1190cm -1, P-O-C} ( alkyl) in 1015 cm ^-1 and 870 cm ^-1
It was confirmed that the compound was a target since it had absorption based on a 4-substituted phenyl group.

Synthesis Example-3 In the same manner, bis (2,6-dimethyl-4-t-octylphenyl) pentaerythritol diphosphite (phosphite No. 3) was obtained.

Example 1 The following formulations were blended in a mixer for 5 minutes and then compounded in an extruder (cylinder temperature 230 ° C and 2
40 ℃, head die temperature 250 ℃, rotation speed 20rpm).

Using this compound, a 95 × 40 × 1 mm test piece was prepared with an injection molding machine (cylinder temperature 240 ° C., nozzle temperature 2
50 ℃, injection pressure 475kg / cm ² ). 150 using the obtained test piece
The thermal stability was measured in a gear oven at ℃, and the yellowness (%) of the test piece after irradiation with a fluorescent lamp for 72 hours was measured using a Hunter colorimeter. The results are shown in Table-1.

<Compound> Polypropylene resin (Profax 6501) 100 parts by weight Calcium stearate 0.1 3,5-di-t-butyl-4-hydroxyphenylpropionic acid octadecyl ester 0.1 Dilauryl thiodipropionate 0.2 Phosphite compound (Table 1) 0.1 * Phosphite compound Comparative phosphite A Bis (2,6-dimethylphenyl) pentaerythritol diphosphite Comparative phosphite B Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite Example 2 Inventive composition In order to see the stabilization effect of the product during high temperature processing, the changes in its melt index (g / 10min) were measured by mixing the following compounds and using a compound with one extrusion and one extrusion at 300 ° C. did. In addition, a Nox gas contamination test (JIS-L0815) was performed, and the yellowness of the test piece after 72 hours was measured using a Hunter colorimeter. The results are shown in Table-2.

<Compound> Polypropylene resin (Profax 6501) 100 parts by weight Calcium stearate 0.05 3,5-di-t-butyl-4-hydroxyphenylpropionic acid pentaerythritol tetraester 0.1 Phosphite compound (Table-2) 0.1 Example 3 The following formulation was kneaded at 150 ° C. for 5 minutes with a mixing roll, and then compression molded for 5 minutes at 150 ° C. and 180 kg / cm ² to prepare a sheet having a thickness of 1.0 mm. This sheet 10
As a test piece of × 20 mm, a thermal stability test was performed on an aluminum foil at a temperature of 150 ° C. in a gear oven. Show progress-
3 shows.

<Compound> Polyethylene resin (HIZEX 5100E) 100 parts by weight 3-t-butyl-4-hydroxy-5-methylphenylpropionic acid-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2, 4,8,10-Tetraoxaspiro (5,5)
Undecane diester 0.05 part by weight Phosphite compound (Table 3) 0.15 Example 4 In order to examine the effect of the compound of the present invention on the ethylene-vinyl acetate copolymer, a sample having the following composition was prepared.
The thermal stability and initial colorability in a gear oven at ℃ were measured. For initial coloring, the degree of yellowness was determined using a Hunter colorimeter. The results are shown in Table-4.

<Compound> Ethylene-vinyl acetate copolymer resin 100 parts by weight Montaic acid-based lubricant 0.3 3-t-butyl-4-hydroxy-5-methylphenylpropionic acid triethylene glycol diester 0.05
Phosphite compound (Table-4) 0.1 Example 5 100 parts by weight of polybutylene terephthalate 3,5-di-t-butyl-4-hydroxyphenylpropionic acid pentaerythritol tetraester 0.2 phosphite compound (Table 5) 0.2 The above composition was injection processed at 270 ° C., A test piece was prepared. Using this test piece, the residual tensile strength after heat aging at 150 ° C. for 300 hours was measured. The results are shown in Table-5.

Example 6 Poly (2,6) having an intrinsic viscosity of 0.51 dl / g (25 ° C. in chloroform)
-Dimethyl-1,4-phenylene oxide) 50 parts by weight,
Polystyrene 47.5 parts by weight, polycarbonate 2.5 parts by weight, titanium oxide 3.0 parts by weight, phosphite compound 0.1 parts by weight and 1,1,3-tris (2-methyl-4-hydroxy-)
0.1 part by weight of 5-t-butylphenyl) butane was added, thoroughly mixed with a Henschel mixer, pelletized with an extruder, and then injection molded to prepare a test piece. This test piece was heated in a gear oven at 125 ° C. for 100 hours, and the elongation and Izod impact value retention rate were measured. The results are shown in Table-6.
Shown in.

Example 7 100 parts by weight of a polycarbonate resin and 0.15 parts by weight of a phosphite compound were mixed and pressed at 260 to prepare a test piece having a thickness of 1.0 mm. 230 this test piece in a gear oven
The degree of discoloration of the test piece after heating for 45 minutes at ℃ was observed. The results are shown in Table-7.

Example 8 ABS resin (Styrac 200: Asahi Dow) 100 parts by weight Calcium stearate 1.0 Phosphite compound 0.1 Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate 0.2 The above composition was added at 200 ° C. Was extruded to prepare pellets, and the pellets were subjected to injection processing at 230 ° C. to prepare test pieces. The degree of coloring of this test piece after heating for 30 hours in a gear oven at 135 ° C. is shown by the whiteness measured by a Hunter colorimeter. Furthermore, the test piece at 20 ℃
The Izod impact value was also measured. The results are shown in Table-8.

Claims (1)

[Claims] 1. A stabilized synthetic resin composition obtained by adding an organic phosphite compound represented by the following general formula (I) to a synthetic resin. (In the formula, R represents an alkyl group having 1 to 8 carbon atoms)