JPH064764B2 - Stabilized synthetic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a stabilized synthetic resin composition. More specifically, it relates to a synthetic resin composition having improved heat resistance, light resistance, processability and the like, which is formed by adding an organic phosphite compound having a specific group in the molecule.

[Conventional technology and problems]

It is known that synthetic resins such as polyethylene, polypropylene, ABS, and polyvinyl chloride deteriorate due to the action of heat and light, become colored, and have low mechanical strength, and cannot be used. 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. Among these phosphite compounds, tris (nonylphenyl) phosphite, diphenylisodecyl phosphite, distearyl pentaerythritol diphosphite, tetraalkylbisphenol A diphosphite, etc. have relatively large effects and are used as stabilizers for synthetic resins. It was prized.

However, the conventionally used phosphite compound often loses its effect in a relatively short period of time, and the effect is often rapidly lost especially in the outdoors or in a humid atmosphere. Further, even when the synthetic resin is processed at a high temperature, its effect is lost, which is still unsatisfactory in practical use.

Of these phosphite compounds, cyclic phosphite compounds have been proposed to be relatively excellent in light resistance and heat resistance.

For example, JP-B-37-10927 proposes to use polyalkylene glycol bis-alkylene phosphite as a stabilizer for polyvinyl chloride resin, and JP-B-43-
In 9904, it is proposed to use neon pentyl phenyl phosphite or the like for color stabilization of a cellulosic resin, and in JP-A-50-105741, alkylene or arylene bis cyclic phosphite is used as a light stabilizer for synthetic resins. It has been proposed to use it as disclosed in JP-A-53-18544,
It has been proposed to use a cyclic alkylene phosphite of -di-tertiary butyl-4-substituted phenol as a stabilizer for synthetic resins. JP-A-55-81893 discloses alkyl phenyl neopentylene phosphite as a synthetic resin. It has been proposed to use it as a stabilizer, and JP-A-55-136295 proposes to use bis neopentylene phosphite such as bisphenol A as a stabilizer for polycarbonate. However, the effects of these compounds are still insufficient, especially when the synthetic resin is processed at a high temperature, the effect is rapidly lost, and the water resistance is also insufficient, which is not practically satisfactory. There wasn't.

[Means for solving problems]

The inventors of the present invention have made extensive studies in view of the current situation,
It was found that the heat resistance, light resistance and processability can be remarkably improved by adding an organic phosphite compound having a specific group in the molecule, and the present invention has been completed.

That is, the present invention provides a stabilized synthetic resin composition obtained by adding at least one selected from the organic phosphite compounds represented by the following general formulas (I) and (II) to a synthetic resin. It is a thing.

(In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group, and R represents an alkylene group, an arylene group, an alkylidene diarylene group, or a thiodiarylene group.) Of these phosphite compounds, a general formula The compound represented by (II) is preferable because of its large effect.

The above general formula (I) or (II) used in the present invention
The compound represented by will be described in more detail.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, Examples thereof include linear or branched alkyl groups such as tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, and triacontyl, and alkyl groups having an ether bond such as cellosolve and carbitol residue.

Examples of the aryl group are phenyl, methylphenyl, dimethylphenyl, tert-butylphenyl, di-tert-butylphenyl, octylphenyl, di-tert-octylphenyl, nonylphenyl, dinonylphenyl, cyclohexylphenyl, phenylphenyl, 3-amylphenyl, di-tertiary amylphenyl and the like can be mentioned.

Examples of the alkylene group include ethylene, propylene and 2,2-dimethylpropylene.

Examples of the arylene group, alkylidene diarylene group, and thiodiarylene group include catechol, t-butylcatechol, and 2,2′-methylenebis (4-methyl-6-t-).
Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-n- Butylidene bis (4,6-dimethylphenol), bis-1,1- (2'-hydroxy-3 ', 5'
-Dimethylphenyl) -3,5,5-trismethylhexane, 2,2'-cyclohexylidenebis (4-ethyl-6-
t-butylphenol), 2,2'-isopropylbenzylidene-bis (4-ethyl-6-t-butylphenol), 2,2'-thiobis (4-t-butyl-6-methylphenol), 2,2'- Thiobis (4-methyl-6-t-butylphenol), 2,2'-thiobis (4,6-di-t-butylphenol), 2,2'-methylenebis (4-α-methylbenzyl-6-cyclohexylphenol) , 2,2'-
Methylenebis (4-cyclohexyl-6-α-methylbenzylphenol), 2,2′-dihydroxybiphenyl,
2,2'-dihydroxy-3,3 ', 5,5'-tetra-t-butylbiphenyl, 2,2'-dihydroxy-3,3', 5,5'-tetra-t-amylbiphenyl, 2, 2'-dihydroxy-3,3 ',
Two diphenols such as 5,5′-tetra-t-octylbiphenyl, bis (2-hydroxy-3-t-butylphenyl) ether, bis (2-hydroxy-3-propylphenyl) ether or two bisphenols. A residue obtained by removing a hydroxyl group can be mentioned.

Table 1 below shows specific examples of the organic phosphite compound used in the present invention.

In addition, in the table And the group + is Indicates.

The organic phosphite compound is used as a synthetic resin 10
It is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, relative to 0 parts by weight. If the blending amount is less than 0.001 part by weight, the intended effect of the present invention cannot be obtained, and if the blending amount exceeds 5 parts by weight,
No further effect can be expected.

The organic phosphite compound used in the present invention can be easily synthesized by a conventionally known method.

For example, phosphorus trichloride, a glycol having the characteristic groups of the present invention (ie, 2,2-dimethyl-3-hydroxypropyl-
It can be easily produced by reacting 2,2-dimethyl-3-hydroxypropionate) with phenols and alcohols sequentially or in one step. Further, instead of phosphorus trichloride, triphenyl phosphite or trimethyl phosphite can be used for the transesterification reaction.

A specific synthesis example is shown below.

Synthesis Example No. 14 (Table 1) Synthesis of compound In a 4-necked flask equipped with a stir bar, thermometer, and nitrogen inlet tube, 2,2'-methylenebis (4,6-di-t-butylphenyl) chloro was added. Phosphite 107.4 g (0.22 mol), 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3
-Hydroxypropionate 20.4 (0.1 mol) and 300 g of xylene were charged, and 25.3 g (0.25 mol) of triethylamine was added dropwise at 50 ° C with stirring under a nitrogen stream. Then, the temperature was raised to 90 ° C. and the reaction was carried out for 6 hours. After hot filtration, methanol was added for crystallization. Filtration and drying gave a white solid product, mp 260 ° C. Yield 101.2g (Yield 91.4%)
Met.

The results of infrared spectroscopic analysis are as follows, and it was confirmed that the product was the target.

ν (PO-phenyl); 1225 cm ^-1 , 835 cm ^-1 ν (PO ^- alkyl); 1025 cm ^-1 ν (C = 0); 1732 cm ^-1 Examples of the synthetic resin stabilized by the present invention include polyethylene and polypropylene. , Polybutene, poly-3
Α-olefin polymers such as 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, 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-
Isobrene 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, polystyrene, polyvinyl acetate,
Acrylic resins, copolymers of styrene and other monomers (eg maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic acid ester-butadiene-styrene copolymers, methacrylic acid esters -Butadiene-styrene copolymer, methacrylate resin such as polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal,
Examples thereof include polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, polyphenylene oxide, fibrin resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Furthermore, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber,
It may be a rubber such as a styrene-butadiene copolymer rubber or a blended product of these resins.

Further, a cross-linked synthetic resin such as cross-linked polyethylene that is cross-linked with peroxide or radiation and a foamed synthetic resin such as expanded polystyrene that is foamed with a foaming agent are also included.

A phenolic antioxidant may be added to the composition of the present invention to further improve its oxidative stability. Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2, 6-the-third
Butylphenol), 2,2'-methylenebis [6- (1-
Methylcyclohexyl) p-cresol], 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
2,2'-methylenebis (4-methyl-6-nonylphenol), 4,4'-isopropylidenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (2,6-di-
Tert-Butylphenol, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,6 -Bis (2-hydroxy-3-nonyl-5-methylbenzol) -4-methylphenol, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) ) Phenyl] terephthalate, thiodiglycol bis (3,5-t-butyl-4-
Hydroxyphenylpropionate), stearyl-β
-(4-Hydroxy-3,5-di-tert-butylphenyl)
Propionate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, bis (4-tert-butyl-3-hydroxy-2,6-dimethyl) Benzyl) dithiol terephthalate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, distearyl (4-hydroxy-3-methyl-5-third Butyl) benzyl malonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, stearyl (3,5-di-methyl-4-hydroxybenzyl) thiogrecolate , Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 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), 1,3,5-tris (2,6-di-methyl-3-hydroxy-4) -Tert-butylbenzyl) isocyanurate and the like.

If a photostabilizer is added to the composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, piperidine-based, various metal salts or metal chelates, particularly nickel or chromium salts or chelates, triazine-based and the like.

The composition of the present invention may contain a sulfur antioxidant. Examples of the sulfur-based antioxidant include distearyl thiodipropionate, dilauryl thiodipropionate, pentaerythritol tetralauryl thiopropionate and the like.

In addition, if necessary, for example, an organic acid metal salt, an epoxy compound, a pigment, a filler, a foaming agent, an amine-based antioxidant, an antistatic agent, an antifogging agent, a plateout prevention agent, a surface treatment agent,
Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, photodegradants, infrared absorbers, processing aids, flame retardants, reinforcing agents and the like can be included.

〔Example〕

The following examples show the effect of the composition according to the present invention, but the present invention is not limited by these examples.

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 20r.pm).

Using this compound, a test piece of 95 × 40 × 1 mm was prepared with an injection molding machine (cylinder temperature 240 ° C, nozzle temperature 2
50 ℃, injection pressure 475kg / cm ² ). 170 using the obtained test piece
The thermal stability was measured in a Gar oven at ℃, and the yellowness (%) of the test piece was measured using a Hunter colorimeter. The results are shown in Table-2.

<Compound> Polypropylene resin (Profax 6501 100 parts by weight manufactured by Hercules) Calcium stearate 0.2 Pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyphenyl 0.1 phenylpropionate) phosphite compound (Table-2) ) 0.2 Example 2 To examine the stabilizing effect of the phosphite compound used in the present invention during high temperature processing, after mixing the following formulations,
Extruded at 300 ° C. The change in the melt index was measured using a compound which was extruded once, three times and five times. The results are shown in Table-3.

<Compound> Polypropylene resin (Profax 6501) 100 parts by weight Calcium stearate 0.2 Pentaerythritol tetrakis (3,5-di-t-tert-butyl-4-hydroxyphenyl 0.1 phenylpropionate) phosphite compound (Table 3) 0.05 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 1
A 0 × 20 mm test piece was subjected to a thermal stability test in a gear oven at a temperature of 150 ° C. on an aluminum box. Table of results
4 shows.

<Compound> Polyethylene resin 100 parts by weight (HIZEX 5100E, manufactured by Mitsui Petrochemical Co., Ltd.) Distearyl thiodipropionate 0.3 Stearyl-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.1 phosphite compound (Table -4) 0.1 Example 4 100 parts by weight of ABS resin (Styrac 200: Asahi Dow) Calcium stearate 1.0 Phosphite compound (Table-5) 0.2 1,3,5-Tris (3,5-di-t-butyl-4-) Hydroxybenzyl) iso 0.1 cyanurate The above compound was extruded at 200 ° C to form pellets, and the pellets were injection-processed 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. was shown by the whiteness measured by a Hunter colorimeter. Iz of the test piece at 20 ℃
The od impact value was also measured. Further, the Izod impact value of the test piece which was immersed in hot water at 100 ° C. for 24 hours and then heated at 135 ° C. for 30 hours was also measured. The results are shown in Table-5.

Example 5 Poly (2,6−) having an intrinsic viscosity of 0.56 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) and phosphite compound (0.3 parts by weight) were added, and they were sufficiently mixed by a Henschel mixer, pelletized by 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.

Example 6 The following formulation was processed by a kneading roll to prepare a sheet having a thickness of 1 mm. Using this sheet, the thermal stability at 190 ° C. and the initial colorability were tested. In addition, a weather resistance test was performed using a weatherometer. The results are shown in Table-7.

<Compound> Polyvinyl chloride (Vinica 37H) 100 parts by weight Di-2-ethylhexyl phthalate 45 tricresyl phosphate 3.0 Bisphenol A / diglycidyl 2.0 ether Zinc stearate 0.8 Barium stearate 0.4 Barium nonylphenate 0.5 Sorbitan monopalmitate 3.0 Methylenebisstearylamide 0.3 Phosphite compound (Table-7) 0.2

Claims (1)

[Claims] 1. A synthetic resin containing 100 parts by weight of the following general formula (I)
And a stabilized synthetic resin composition obtained by adding 0.001 to 5 parts by weight of at least one selected from the organic phosphite compounds represented by the general formula (II). (In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group, and R represents an alkylene group, an arylene group, an alkylidene diarylene group, or a thiodiarylene group).