JPS63186768A - Synthetic resin composition - Google Patents

Abstract

PURPOSE:To stabilize a synthetic resin and to prevent effectively it from being deteriorated by heat and oxygen over a long period of time, by adding a specified org. phosphite compd. to a synthetic resin. CONSTITUTION:An org. phosphite compd. of the formula (wherein R is a 1-8C alkyl) is added to a synthetic resin (e.g., polyethylene, polyvinyl chloride) to stabilize the resin. Examples of the org. phosphite compd. are bis(2,4,6- trimethylphenyl)pentaerythritol diphosphite, bis(2,6-dimethyl-4-t-butylphenyl) pentaerythritol diphosphite, etc. The phosphite is used in an amount of 0.01-10wt.% based on that of the resin. The resin can be prevented from being discolored by the action of heat and oxygen or its mechanical strength is prevented from being lowered over a long period of time.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a synthetic resin composition, and more specifically, by adding a specific phosphite compound, the composition can be resistant to 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.

[Conventional technology 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, becoming discolored and having reduced mechanical strength, making them unusable.

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

For example, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-dimethylphenyl)pentaerythritol diphosphite,
Pentaerythritol diphosphite compounds such as distearyl pentaerythritol diphosphite have been proposed as particularly effective phosphite compounds. However, the effects of these phosphite compounds are still not sufficient, and phosphite compounds with even greater effects have been sought.

In view of the current situation, the inventors of the present invention have conducted extensive studies, and have found that
The inventors have discovered that when a specific organic phosphite compound is used as a stabilizer for synthetic resins, it exerts a long-term stabilizing effect on the resins, and has thus 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 above general formula (I), examples of the alkyl group represented by R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and 5ec-butyl. , t-butyl, mu-
Included are amyl, octyl, t-octyl, and the like.

Examples of the synthetic resins stabilized by the organic phosphite compound of the present invention include α-olefin polymers such as polyethylene, polypropylene, polybutene, and 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, B→J vinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride- Propylene copolymer, 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 copolymers, chloride and nyl-maleic acid ester copolymers, hinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, petroleum resins, Coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, polyacrylonitrile, copolymer of styrene or α-methylstyrene with other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), ABS resin (styrene component (including so-called heat-resistant ABS resins in which a portion of the resin is replaced with α-methylstyrene and so-called ultra-heat-resistant ABS resins in which maleimides are copolymerized), acrylonitrile-butadiene-styrene copolymers, acrylic acid ester-butadiene-styrene copolymers, Methacrylate resins such as methacrylic acid ester-butadiene-styrene copolymer and polymethyl methacrylate, linear polyesters such as polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane , cellulose resin, phenolic resin, urea resin,
Examples include melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Furthermore, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used.

Also included are crosslinked polymers such as crosslinked polyethylene crosslinked with peroxide or radiation, and foamed polymers such as expanded polystyrene foamed with a foaming agent.

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

Phenol-based, sulfur-based antioxidants, etc. can be used in combination with the composition of the present invention.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 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, 2,4.6-1-lis(3',5''-di-tert-butyl-4'-hydroxybenzylthio) -1,3
, 5-) riazine, 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
-(I-methylcyclohexyl)p-cresol], bis[3,5-bis(4-hydroxy-3-tert-butylphenyl)butyric acidocoglycol ester, 4.
4'-butylidene bis(6-tert-butyl-m-cresol), 2.2'-ethylidene bis(4,6-di-tert-butylphenol), 2.2'-ethylidene bis(4-
2-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
-1-Lis(2,6-dimethyl-3-hydroxy-4-
tertiary 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 comethane, 1,3
．． 5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanate, 1.3.5-)lis((3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl)isocyanate Nurate, 2-
Octylthio-4,6-di(4-hydroxy-3,5-
(di-tert-butyl)phenoxy-1,3,5-1-riazine, 4,4'-thiobis(6-tert-butyl-m-cresol), and in particular 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-tert-butylbenzyl)isocyanurate,
Butyl-4-hydroxyphenyl)propionate comethane, 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 these phenolic antioxidants added is 0.00 parts by weight per 100 parts by weight of the synthetic resin. 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

It is also possible to further add a sulfur-based antioxidant to the composition of the present invention to improve its oxidative stability. Examples of these sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, similystyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl. esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate (e.g. pentaerythritol tetralauryl thiopropionate)
can be mentioned.

By adding light stabilizers to the compositions of the invention, their light resistance can be further improved. Examples of these light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. 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'
benzotriazoles such as -hydroxy-3°,5''-di-amylphenyl) benzotriazole, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di -t
Benzoates such as -butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2.2°-thiobis(4-t-
octylphenol) Ni salt, [2,2°-thiobis(
4-t-octylphenolate)]-]n-butylamine Ni, nickel compounds such as (3,5-di-1-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, bis(2,2, 6,6-tetramethyl-4-piperidyl) sebacate, bis(I,2,2,6
゜6-bentamethyl-4-piperidyl)-n-7'thyl-3,5-cy 1143 Butyl-4-hydroxybenzyl-malonate, bis(I-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-piperiditul/diethyl succinate condensate, cyanuric chloride/tertiary octylamine/1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)bexane Piperidine compounds such as condensates, substituted acrylonitriles such as methyl α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate, and N-2-ethylphenyl-N′-2-ethoxy-5-tertiary Butylphenyloxalic acid diamide, N-2-ethylphenyl-No.
Examples thereof include oxalic dianilides such as -2-ethoxyphenyl oxalic diamide.

If necessary, the composition of the present invention may also contain heavy metal deactivators, nucleating agents, metal soaps, organic tin compounds, plasticizers, epoxy compounds, pigments, fillers, blowing agents, antistatic agents, flame retardants, and lubricants. It is possible to incorporate processing aids, etc.

When using the organophosphite compound of the present invention, it is preferred to add a small amount of a non-aromatic amine compound to improve its water resistance.

These amine compounds include, for example, trialkanol/amines such as triethanolamine, triisopropanolamine, tri-n-propanolamine; jetanol/aliphatic amine, diisopropanol/aliphatic amine, di-n-propanol Dialkanols and aliphatic amines such as tools and aliphatic amines (specifically jetanol/dodecylamine, jetanol/octadecylamine, jetanol/tallow alkylamine, jetanol/soybean oil alkylamine, jetanol/oleylamine, jetanol/octylamine, Jetanol/coconut oil alkylamine, Jetanol/hardened beef tallow alkylamine,
Dialkanolamines such as diisopropanolamine, jetanolamine, tetraethanolethylenediamine, and tetraisopropanolethylenediamine; hexamethylenetetramine, piperidine, pyrrolidine, piperazine, diketopiperazine, N-methylpyrrolidine, oxazolidine,
Heterocyclic amines such as isoxazolidine; amine oxides such as lauryl dimethylamine oxide and stearyl dimethylamine oxide; N-coco fatty acid acyl-di-glutamate monotonaethanolamine, N-lauroyl-L-glutamate monotriethanolamine, etc. Examples include amino acid alkanolamines.

The mixing ratio of phosphite compound and organic amine compound is
The amount of amine per 100 parts by weight of the phosphite compound is 0.
01 to 5 parts by weight is preferable, more preferably 0.1 to 2 parts by weight.
Parts by weight.

〔Example〕

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

6.81 g (0.05 mol) of pentaerythritol in a 4-tube flask equipped with a thermometer, stirrer and nitrogen inlet tube
, 40 g of xylene and 0.05 g of triethylamine (
0,0005 mol) of phosphorus trichloride at 60°C.
13 g (0.11 mol) were added dropwise over 20 minutes. 70
After reacting at 90°C for 3 hours, 13.6 g (0.1 mol) of 2,4.6-drimethylphenol and 6 g (0.06 mol) of triethylamine were charged, followed by reaction at 90°C for 5 hours.

After hot filtration, methanol was added to cause crystallization, followed by filtration and drying to obtain a white powder. The melting point was 188-189°C.

As a result of infrared spectroscopy, P-0-C (
The absorption based on aromatic) is caused by P-0-
Absorption based on C (alkyl) is also 860 c+w-
' had an absorption based on a 4-substituted phenyl group, confirming that it was the desired product.

2.4.6-) 2,6 instead of trimethylphenol
A white powder product with a melting point of 245°C was obtained in the same manner as in Synthesis Example 1 except that -dimethyl-4-t-butylphenol was used.

As a result of infrared spectroscopy, 1190ca+-' po~C
(aromatic), P-0-C (alkyl) at 1015ca+-' and absorption based on a 4-substituted phenyl group at 870cm-', confirming that it was the desired product.

Synthesis Example 3 In the same manner, bis(2,6-dimethyl-4-octylphenyl)pentaerythritol diphosphite (phosphite diphosphite 3) was obtained.

Example 1 The following formulation was mixed in a mixer for 5 minutes, and then a compound was made in an extruder (cylinder temperature 230°C).
and 240°C, head die temperature 250°C, rotation speed 2
0rpa+).

Using this compound, a 95 x 40 x 1 mm test piece was made with an injection molding machine (cylinder temperature 240°
C, nozzle temperature 250°C1 injection pressure 475kg/c1a
).

Thermal stability was measured using the obtained test piece in an open gear at 150"C, and 7" using a Hunter colorimeter.
The yellowness (%) of the test piece was measured after being irradiated with a fluorescent lamp for 2 hours. The results are shown in Table 1.

<Composition> Calcium stearate 0.1 dilauryl thiodipropionate 0.2 phosphite compound (Table -
1) 0.1 Table-1 * Phosphite Compound Comparison Phosphite A Comparative Phosphite B Example 2 In order to examine the stabilizing effect of the composition of the present invention during high temperature processing, after mixing the following formulations, Compounds extruded once and five times at 300'C were used to measure changes in melt index (g/10a+tn). Further, a NOx gas contamination test (JIS-L0815) was conducted, and the yellowness of the test piece after 72 hours was measured using a Hunter colorimeter. The results are shown in Table-2.

Calcium stearate 0.05 Table-2 Example 3 The following formulation was kneaded at 150°C for 5 minutes using a mixing roll, and then kneaded at 150°C and 180 kg/cd for 5 minutes.
Compression molded for 1 minute to a thickness of 1. A sheet of Omm was created. This sheet was used as a 10×20111m test piece.
A thermal stability test was carried out on aluminum foil in a gear oven at a temperature of 150°C. The results are shown in Table-3.

<Formulation> Phosphite compound (Table 3) 0.15Table 3 Example 4 In order to examine the effect of the compound according to the present invention on ethylene-vinyl acetate copolymer, samples were prepared with the following formulation.
Thermal stability and initial coloring properties were measured at 0°C with the gear open. In addition, initial coloring was determined by determining yellowness using a Hunter colorimeter. The results are shown in Table-4.

Blend> Ethylene-vinyl acetate copolymer resin 100 parts by weight Montanic acid lubricant 0.3 phosphite compound (Table-4) 0.1 Table-4 Example 5 Polybutylene terephthalate 100 parts by weight phosphite compound (Table-4) 5) 0.2 The above formulation at 270°C
A test piece was created by injection processing. Using this test piece, the residual tensile strength after heat aging at 150°C for 1300 hours was measured.

The results are shown in Table-5.

Table 5 Example 6 50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) with an intrinsic viscosity of 0.51 g/g (in chloroform at 25°C), 47.5 parts by weight of polystyrene, 2. 5 parts by weight, 3.0 parts by weight of titanium oxide, 0.1 part by weight of a phosphite compound, and 0.1 part by weight of 1°1.3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane. was added, thoroughly mixed using a Henschel mixer, pelletized using an extruder, and then injection molded to prepare a test piece. This test piece was heated in a gear oven at 125°C for 1100 hours, and the elongation and Izot impact value retention were measured. The results are shown in Table-6.

Table 6 Example 7 100 parts by weight of polycarbonate resin and 0.15 parts by weight of phosphite compound were mixed and pressed at 260°C to prepare a test piece with a thickness of 1.0 mm. This test piece was heated in a gear oven at 230°C for 45 minutes, and the degree of discoloration of the test piece was observed. The results are shown in Table-7.

Table 7 Example 8 Calcium stearate 1.0 Phosphite compound 0.1 The above formulation was extruded at 200°C to create a pellet, and this pellet was used for 23
A test piece was prepared by injection processing at 0°C. The degree of coloration of this test piece after heating in a gear oven at 135°C for 30 hours was expressed as whiteness measured with a Hunter colorimeter. Furthermore, the rzod impact value of the test piece at 20°C was also measured. The results are shown in Table-8.

Table-8

Claims (1)

[Scope of Claims] A stabilized synthetic resin composition obtained by adding an organic phosphite compound represented by the following general formula (I) to a synthetic resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group having 1 to 8 carbon atoms)