JPH01121368A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a synthetic resin composition stabilized against deterioration with heat and light over a long period, by adding a specific phosphite compound. CONSTITUTION:The objective stabilized synthetic resin composition is produced by compounding (A) 100pts.wt. of a synthetic resin (e.g., polyethylene, isoprene rubber, crosslinked polyethylene or foamed polystyrene) with (B) 0.001-5pts.wt. of a phosphite compound of formula III (A is S or group of formula IV; B is H or group of formula V) produced by reacting a dihydric phenol of formula I (R is alkyl; R1 is H or alkyl) with phosphorus trichloride (or triphenyl phos phite or trimethyl phosphite) and reacting the reaction product with a dihydric phenol of formula II (R2 is alkyl; R3 is H or alkyl) and, preferably further (C) a phenolic antioxidant, a sulfur-containing antioxidant, a photostabilizer, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a synthetic resin composition, and more specifically, the present invention relates to a synthetic resin composition that can be stabilized for a long period of time against deterioration due to the effects of heat and light by adding a specific phosphite compound. The present invention relates to a synthetic resin composition.

[Conventional technology and problems]

Synthetic resins such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride deteriorate due to the action of heat and light.
It is known that it becomes discolored and its mechanical strength decreases, making it 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.

Among these phosphite compounds, tris(nonylphenyl) phosphite, diphenylisodecyl phosphite, distearylpentaerythritol diphosphite, tetraalkyl bisphenol A diphosphite, tetratridecyl 4,4'-butylidene bis(3-methyl- 6-tert-butylphenol) diphosphite, hexatridecyl 1.1.3-tris(2-methyl-4
-Hydroxy-5-t-butylaenyl)butane triphosphite and the like have relatively large effects and are prized as stabilizers for synthetic resins.

In addition, Japanese Patent Publication No. 40-8833 describes isooctyl phenyl 4,4'-thiobis(2-t-butyl-5-methylphenol) as a stabilizer for olefin polymers.
Phosphite, tri(4,4''-thiobis(2-t-butyl-5-methylphenol) phosphite, etc.) have been proposed, and Japanese Patent Publication No. 40-9743 describes them as stabilizers for polyvinyl chloride and olefin polymers. Tetraphenyl [4゜4゛-thiobis(2-t-butyl-5-methylphenyl)] diphosphite, tetraisooctyl (4,
4'-thiobis(2-L-butyl-5-methylphenyl)]diphosphite and the like have been proposed. However, the effects of these phosphite compounds are still not sufficient, and a phosphite compound with even greater effects has been sought.

[Means for solving problems]

As a result of extensive studies in view of the current situation, the present inventors have found that when a phosphite compound represented by the following general formula (I) is added to a synthetic resin, a resin composition with excellent heat resistance and light resistance can be obtained. This discovery led to the present invention.

That is, in the present invention, 0.001 to 5 phosphite compounds represented by the following general formula (I) are added to 100 parts by weight of the synthetic resin.
The object of the present invention is to provide a stabilized synthetic resin composition in which parts by weight are added.

(In the formula, A represents a sulfur atom or -CHzSCHt-,
and R2 each independently represent an alkyl group, R8 and R2
each independently represents a hydrogen atom or an alkyl group. ) The compound represented by the above general formula (I) according to the present invention will be explained in more detail.

Examples of the alkyl group include methyl, ethyl, isopropyl, t-butyl, 5ec-butyl, amyl, octyl, isooctyl, t-octyl, nonyl, t-nonyl, decyl, lauryl, cetyl, stearyl, cyclohexyl, benzyl, Examples include α-methylbenzyl, α, α-dimethylbenzyl, α-methylcyclohexyl, and the like.

Typical examples of the phosphite compound represented by the formula (I) are shown in Table 1 below.

Table-1 The phosph R5 represented by the general formula (I) according to the present invention is of the formula (
Dihydric phenol, phosphorus trichloride (or triphenyl phosphite or trimethyl phosphite) and R3R3 (in which Rt and R1 have the same meaning as in formula (I)), )
It can be easily produced by reacting the dihydric phenol represented by

Next, a specific synthesis example of the compound of the present invention will be shown.

Synthesis Example-1 (Synthesis of Nal compound) 286.9 g (0
, 8 mol), 400 g of toluene and triethylamine Ig, and without stirring, 120.9 g of phosphorus trichloride (
0.88 mol) was added dropwise at 80°C. After the dropwise addition was completed, the temperature was gradually raised under a nitrogen stream, and the reaction was carried out at a reflux temperature of 120°C for 4 hours. After removing excess phosphorus trichloride under reduced pressure, the mixture was cooled to room temperature. The precipitated crystals were filtered and dried under reduced pressure at 80"C to give 2,2"-thiobis(4-methyl-6-t-
butylphenylmonochloro)phosphite (compound A)
I got it.

84.6 g of compound A (0,
2 mol"), 4,4°-thiobis(3-methyl-6-
-butylphenol) 35.8g (0.1 mol)
, 100 g of toluene and 0.5 g of triethylamine were charged, and the mixture was reacted at 120°C for 6 hours. After cooling, the precipitated crystals were filtered and dried under reduced pressure to obtain a white powder with a melting point of 26B''C.

IR: Characteristic absorption (I600, 1180, 990, 890
,840cn+-') Old-NMR (60MHz)
(7MS standard CDCl 3 solvent) δ 1.3-1.
4 54Hs, t-CaH+2.2~2
．． 3 18Hs, s, -CH,17,0~?
, 3 12Hd, d, Aromatic C11 Synthesis Example-2
(Synthesis of Na3 compound) 84.6 g of the above compound A was placed in a 500 d fourth flask.
(0,2 mol), 2,2'-thiobis(4-methyl-6-t-butylphenol) 71.7 g (0,
2 mol), 100 g of toluene and 25 g of triethylamine
g (0.24 mol) and heated at 90-100"C for 6
Time reacted.

Triethylamine hydrochloride was removed by filtration through Celite, and the filtrate was subjected to solvent removal under reduced pressure to obtain a white solid with a melting point of 140 to 150°C.

■R: Characteristic absorption (3450, 1600, 1180, 86
0cm-')H+-NMR (60MHz) (7M
S standard CDCl3 solvent) 61.3 to 1.5 36
Hs, s+ t-CJ*2.1~2.3 12
Hs, s, -CI, 16.7~? , 3 9H
s, d, d, d, d, aromatic CH, -OH The present invention stabilizes a synthetic resin by adding a phosphite compound represented by the above formula (I) to the synthetic resin. The amount added is 0.001 to 5 parts by weight per 100 parts by weight of the synthetic resin.

Examples of the synthetic resins stabilized by the present invention include polyethylene, polypropylene, polybutene, poly-3
- α-olefin polymers such as methyl butene or polyolefins such as ethylene-vinyl acetate copolymers, 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, vinyl chloride-styrene copolymer Polymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinyritine chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, chloride and nyl-butadiene copolymer Polymer, 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 copolymers, chloride and nyl-acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resins, styrene and other monomers (e.g. maleic anhydride) , butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer (ABS resin), α-methylstyrene-modified ABS resin,
Yareimide modified ^BS resin, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer, methacrylate resin such as polymethyl methacrylate, polyvinyl alcohol,
Polyvinyl formal, polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfonic acid, polyurecne, cellulose resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicone resin, etc. be able to.

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 synthetic resins such as crosslinked polyethylene crosslinked with peroxide or radiation, and foamed synthetic resins such as foamed polystyrene foamed with a foaming agent.

By further adding a phenolic antioxidant to the composition of the present invention, the oxidative stability can be improved by acting synergistically.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-di-tert-butyl-4-hydroxyphenyl). Propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis(
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 4.4°-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4°6-di(3,5- dihydroxyphenoxy)-8-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), bis[3, 3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid coglycol ester, 4.4''-butylidenebis(6-tert-butyl-m-cresol), 2.2
°-ethylidene bis(4,6-di-tert-butylphenol), 2.2”-ethylidene bis(4-tert-butyl-6
-tertiary 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-butylbenzyl) isocyanurate, 1°3.5'-tris(3,5
-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3.5-tris(3,5-di-tert-butyl-
4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris((3,5-di-tert-butyl-4-hydroxydiphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3 −(
3゜5-ditert-butyl-4-hydroxyphenyl)propionate comethane, 2-tert-butyl-4-methyl-6
-(2'-acryloyloxy-3'-tert-butyl-
5'-Methylbenzyl)phenol, 3,9-bis(l
"1+-dimethyl-2"-hydroxyethyl) -2,
4,8,10-tetraoxaspiro(5,5)undecanebis[β-(3-tert-butyl-4-hydroxy-5-
Examples include methylphenyl)propionate.

The amount of these phenolic antioxidants added is 100% of the resin.
The amount is 0.001 to 5 parts by weight.

The composition of the present invention may also contain a sulfur-based antioxidant. Examples of sulfur-based antioxidants include distearyl thiodipropionate, dilauryl thiodipropionate, pentaerythritol tetra (β-lauryl thiolopionate), 1.3.5-) lis-β-stearylthio Examples include propionyloxyethyl isocyanurate.

By adding light stabilizers to the compositions of the invention, their light resistance can be further improved.

Examples of these light stabilizers include 2-dihydroxy-
4-methoxybenzophenone, 2-hydroxy-4-n
- 2-hydroxybenzophenones such as octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone;
2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-
Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'.

5'-'; -t-di-t-butylphenylchlorobenzotriazole, 2-(2°-hydroxy-3'.

Benzotriazoles such as 5'-di-t-amylphenyl)benzotriazole; phenyl salicylate, p-
t-phenyl salicylate, 2゜4-di-t-butylphenyl-3,5-di-L-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4
-benzoate a, 2,2 such as hydroxybenzoate
'-thiobis(4-t-octylphenol) Ni salt,
(2,2'-thiobis(4-t-octylphenol)
]-] Nickel compounds such as n-butylamine Ni salt (3,5-di-t-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) sebacate, bis(I,2,2,6,6-bentamethyl-4-piperidyl)-2 -n-butyl-2-(3,
5-di-tert-butyl-4-hydroxybenzyl) malonate, bis(I-acryloyl-2,2,6,6-tetramethyl-4-piperidyl)-2,2-bis(3,5-di-tert-butyl) -4-hydroxybenzyl)malonate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(I,2,2,6,6 -bentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1-hydroxyethyl-2,2,6,6
-Tetramethyl-4-piperiditul/diethyl succinate condensate, 2,4-dichloro-6-tert-octylamino-1,3,5-)riazine/1,6-bis(2,2,6
, 6-tetramethyl-4-piperidylamino)hexane condensates; substituted acrylonitrines such as α-cyano-β-methyl-β-(p-methoxyphenyl)methyl acrylate) -2-Ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide, and other oxalic acid diazurides.

In addition, heavy metal deactivators, nucleating agents, metal soaps, organic tin compounds, plasticizers, epoxy compounds, foaming agents, antistatic agents, flame retardants, lubricants, processing aids, etc. may be included as necessary. Can be done.

[Example] Next, the present invention will be specifically explained using Examples. However, the present invention is not limited to these examples.

Example 1 The following formulation was kneaded at 180°C for 5 minutes using a mixing roll, and then kneaded with a mixing roll for 5 minutes at 180°C.
Compression molding was performed for 5 minutes to create a test piece with a thickness of III+. A thermal stability test was conducted using this test piece in a gear oven at 160°C. Further, the yellowness of the test piece after 72 hours of fluorescent lamp irradiation was measured using a Hunter colorimeter. The results are shown in Table-2.

Blended unstabilized polypropylene 100 parts by weight Calcium stearate 0.05 Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyphenylpropionate) 0.1 Phosphite compound (Table 2) 0.1 Table - 2 Example 2 The following formulation was kneaded on a mixing roll for 5 minutes at a temperature of 150'C, then at a temperature of 150'C, 180 kg/c
Compression molding was performed for 5 minutes under mz conditions, and the thickness was 1.2 mra.
A sheet was created. This sheet is 10 x 20mm
A gear open heating deterioration test was conducted on aluminum foil as a test piece in air at a temperature of 150°C. Incidentally, 10 specimens were used for the same sample, and the time when 5 or more specimens changed color and became waxy was defined as the deterioration time. Table 3 shows the results.
Shown below.

combination Polyethylene resin (HIZEX 5100B).

Mitsui Oil Co., Ltd.) 100 parts by weight Stearyl-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.1 Phosphite compound (Table 3) 0.05 Table -
3 Example 3 Intrinsic viscosity 0.56 dl/g (25°C in chloroform
) 50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide), 50 parts by weight of polystyrene, 3. Add part OIiii and 0.5 part by weight of stabilizer,
The mixture was 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 4.

Table-4 Example 4 ABS resin (Blendex 111) 10
0 parts by weight Zinc stearate 0.5 Stearyl-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.1 Phosphite compound (Table 5) 0.3 After rolling the above mixture A sheet with a thickness of 0.5 mm was produced by pressing. This sheet was heated in a gear oven at 135° C. for 20 hours, and the degree of coloration of the sheet was measured using a Hunter colorimeter to indicate the degree of whiteness. The results are shown in Table-5.

Table-5 Example 5 100 parts by weight of polyvinyl chloride resin (Geon 103 HP, product of Nippon Zeon Co., Ltd.), dioctyl phthalate 4
2 parts by weight, 3 parts by weight of epoxidized soybean oil, 0.3 parts by weight of zinc stearate, 0.5 parts by weight of barium stearate,
0.3 parts by weight of stearic acid, and a phosphite compound (
Table-6) 0.2 parts by weight was rolled at 175° with a mixing roll.
After kneading at a temperature of C for 5 minutes, compression molding was performed at a temperature of 175°C to create a transparent sheet. A thermal deterioration test was then conducted in an air atmosphere in a gear oven at a temperature of 190°C.

Incidentally, the deterioration start time was determined based on the degree of coloring. A test was also conducted in a constant humidity chamber maintained at a relative humidity of 100% and a temperature of 175°C. The results are shown in Table-6.

Table 6 Example 6 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 property in open gear at °C were measured. Regarding the initial coloration, the degree of yellowness was determined using a Hunter colorimeter. The results are shown in Table-7.

100 parts by weight of blended ethylene-vinyl acetate copolymer resin Moncinic acid lubricant 0.3 2.6-Ditert-butyl-4-methylphenol 0.1 Distearylthiodipropionate 0.1 Phosphite compound (Table 7) 0.1 Table-7 Example 7 Polybutylene terephthalate 100 parts by weight Pentaerythritol tetrakis (3,5-di-tert-butyl-4
-Hydroxyphenylpropionate) 0.1 parts by weight Phosphite compound 0.2 The above-mentioned support was injection-processed at 270"C to prepare a test piece. Using this test piece, after heat aging at 150°C for 1240 hours, The residual tensile strength was measured.

The results are shown in Table-8.

Table-8

Claims (1)

[Scope of Claims] A stabilized synthetic resin composition obtained by adding 0.001 to 5 parts by weight of a phosphite compound represented by the following general formula (I) to 100 parts by weight of a synthetic resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, A represents a sulfur atom or -CH_2SCH_2-, B represents a hydrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R and R_2 Each independently represents an alkyl group, and R_1 and R_3 each independently represent a hydrogen atom or an alkyl group.)