JPS625464B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to stabilized synthetic resin compositions. Specifically, heat resistance, light resistance, and
The present invention relates to a synthetic resin composition with improved processability. It is known that synthetic resins such as polyethylene, polypropylene, ABS, and polyvinyl chloride deteriorate due to the effects of heat and light, becoming discolored or having a 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 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, tetraalkylbisphenol A diphosphite, etc. have relatively large effects and are prized as stabilizers for synthetic resins. was used. However, conventionally used phosphite compounds often lose their effectiveness in a relatively short time, especially outdoors or in a humid atmosphere. Moreover, when processing synthetic resins at high temperatures, the effect is lost, and the process is still unsatisfactory in practical terms. Among these phosphite compounds, cyclic phosphite compounds are proposed to have relatively excellent light resistance and heat resistance. For example, Japanese Patent Publication No. 37-10927 proposes the use of polyalkylene glycol bisalkylene phosphite as a stabilizer for polyvinyl chloride resin, and Japanese Patent Publication No. 43-9904 proposes the use of polyalkylene glycol bisalkylene phosphite as a stabilizer for polyvinyl chloride resin. It was proposed to be used for color stabilization of cellulose resin, and was published in Japanese Patent Application Publication No. 1989-
No. 105741 proposes the use of alkylene or arylene biscyclic phosphites as light stabilizers for synthetic resins, and JP-A No. 18544/1983 proposes the use of alkylene or arylene biscyclic phosphites as light stabilizers for synthetic resins. The use of cyclic alkylene phosphite as a stabilizer for synthetic resins was proposed and
No. 81893 proposes the use of alkyl phenyl neopentylene phosphites as stabilizers for synthetic resins, and JP-A-55-136295 proposes the use of bisneopentylene phosphites such as bisphenol A. It has been proposed to be used as a stabilizer for polycarbonate. However, the effects of these compounds are still insufficient, especially when processing synthetic resins at high temperatures, their effects are rapidly lost, and their water resistance is also insufficient, so they are not satisfactory for practical use. It wasn't. As a result of intensive studies in view of the current situation, the present inventors have discovered that heat resistance, light resistance, and processability can be significantly improved by adding an organic phosphite compound having a specific group in the molecule, and the present invention has been made. This is the completed version. That is, the present invention provides a stabilized synthetic resin composition obtained by adding an organic phosphite compound represented by the following general formula () or () to a synthetic resin. (In the formula, SPG is a group , R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, a polyhydric alcohol or a polyhydric phenol residue, and the other hydroxyl group remains free or becomes a phosphite ester, X is a hydrogen atom or

[Formula] and n represents 1 to 10. R represents an alkylene group, an arylene group, an alkylidene diarylene group or a thiodiarylene group. ) Table 1 below shows specific compounds represented by the general formula (I) or () of the present invention. Furthermore, the table-
In 1, the group -SWP- is

[Formula] is shown, and the group + is

[Formula] is shown. The amount of the organic phosphite compound used is 0.001 to 5, preferably 0.001 to 5, per 100 parts by weight of the synthetic resin.
It is 0.01 to 3 parts by weight. Further, the organic phosphite compound used in the present invention can be easily synthesized by a conventionally well-known method. For example, phosphorus trichloride, glycol (3,9-bis(1,1-dimethyl-
It can be easily produced by reacting 2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane), phenols, and alcohols sequentially or in one step.
Also, using triphenyl phosphite or trimethyl phosphite instead of phosphorus trichloride,
It can also be produced by transesterification. A specific synthesis example is shown below. Synthesis Example No. 46 (Table-1) Synthesis of Compound A mixture of 75 ml of dichloroethane, 100 ml of benzene, and 5.50 g of phosphorus trichloride was cooled to 5°C, and 2,2'-methylenebis(4-methyl-6-t -butylphenol) was added, and then 14.57 g of triethylamine was added dropwise at a liquid temperature of 3 to 7°C.
After the dropwise addition was completed, the reaction was carried out at room temperature for 2 hours and then at 50°C for 2 hours. Cool to 22℃ and add 3,9-bis(1,1-dimethyl-2-hydroxyethyl)
-2,4,8,10-tetraoxaspiro [5,
5] 6.08g of undecane was added. At this time, the temperature rose to 33°C due to the heat of reaction. The mixture was refluxed and reacted for 15.5 hours, cooled, and triethylamine hydrochloride was separated. Dichloroethane was distilled off from the liquid, and an appropriate amount of benzene was added thereto for filtration. Kyowad 600 was added to this solution and left overnight. Separate the Kiyowado 600, distill off the benzene, and check the melting point.
A light brown powder with a temperature of 145-149°C was obtained. The yield was 17.4g. Examples of the synthetic resins stabilized by the present invention include α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, etc. Polyolefins and their copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyfluorinated vinylidene, 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 copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internal plasticization Halogen-containing synthetic resins such as polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers 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, polyurethane, polyphenylene oxide,
Examples include cellulose resins, phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. Furthermore, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber,
Rubbers such as styrene-butadiene copolymer rubber or 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. Phenolic antioxidants may be added to the compositions of the present invention to further improve their oxidative stability. Examples of phenolic antioxidants include 2,6-di-
Tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol)
butylphenol), 2,2′-methylenebis[6
-(1-methylcyclohexyl)p-cresol], 2,2'-methylenebis(4-ethyl-6-
tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 4,4'-
Isopropylidene bis(2,6-di-tert-butylphenol), 4,4′-butylidene bis(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-methylbenzyl)-4-methylphenol, bis[2-
tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, thiodiglycol bis(3,5-di-t-butyl-4-hydroxyphenyl) propionate), 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-
dimethylbenzyl) dithiol terephthalate,
Tetrakis [methylene-3-(3,5-di-3
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-tert-butyl)benzyl malonate, 1,3,5-tris(3,5
-di-tert-butyl-4-hydroxybenzyl) isocyanurate, stearyl (3,5-di-methyl-4-hydroxybenzyl) thioglycolate, bis[3,3-bis(4-hydroxy-3-
tertiary-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-
Examples include hydroxy-4-tert-butylbenzyl) isocyanurate. If a light stabilizer is added to the composition of the invention,
Since they can improve photostability, they can be appropriately selected and used depending on the purpose of use. These include benzophenone, benzotriazole, salicylate, substituted acrylonitrile, piperidine, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, and the like. The composition of the present invention can also contain a sulfur-based antioxidant. Examples of the sulfur-based antioxidant include distearylthiodipropionate, dilaurylthiodipropionate, pentaerythritol tetralaurylthiopropionate, and the like. Other additives as necessary, such as organic acid metal salts, epoxy compounds, pigments, fillers, foaming agents, amine antioxidants, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, lubricants, and flame retardants. , a fluorescent agent, a fungicide, a bactericidal agent, a metal deactivator, a photodegrading agent, an infrared absorbing agent, a processing aid, a mold release agent, a reinforcing agent, and the like. The following examples illustrate the effects of the composition according to the present invention, but the present invention is not limited to these examples. Example 1 After blending the following formulation in a mixer for 5 minutes,
A compound was created using an extruder (cylinder temperature 230℃ and 240℃, head die temperature 250℃,
rotation speed 20r.pm). Using this compound, test pieces of 95 x 40 x 1 mm were made using an injection molding machine (cylinder temperature: 240
℃, nozzle temperature 250℃, injection pressure 475Kg/cm ² ). Using the obtained test piece, thermal stability was measured in a gear oven at 170°C, and yellowness (%) of the test piece was measured using a Hunter colorimeter. Table of results-2
Shown below. <Composition> Polypropylene resin (Profax 6501 manufactured by Hercules) 100 parts by weight Calcium stearate 0.2 Dilaurylthiodipropionate 0.2 Pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyphenylpropionate) 0.1 Phosphite compounds (Table-2) 0.1

[Table] Example 2 In order to examine the stabilizing effect of the phosphite compound used in the present invention during high-temperature processing, the following formulation was mixed and then extruded at 300°C. Compounds that had been extruded 1, 3, and 5 times were used to measure changes in melt index. The results are shown in Table-3. <Composition> 100 parts by weight of polypropylene resin (Profax 6501) Calcium stearate 0.2 Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyphenylpropionate) 0.1 Phosphite compound (Table 3) 0.1

[Table] Example 3 The following formulation was kneaded with a mixing roll at 150°C for 5 minutes, and then compression molded at 150°C and 180 kg/cm ² for 5 minutes to produce a sheet with a thickness of 1.0 mm. This sheet was used as a 10 x 20 mm test piece, and a thermal stability test was conducted on aluminum foil in a gear oven at a temperature of 150°C. The results are shown in Table-4. <Composition> Polyethylene resin (Hizex 5100E manufactured by Mitsui Petrochemicals) 100 parts by weight Distearyl thiodipropionate 0.3 Stearyl-3,5-di-t-butyl-4-hydroxyphenylpropionate 0.1 Phosphite compound (Table -4) 0.1

[Table] Example 4 ABS resin (Styrac 200: Asahi Dow)
100 parts by weight Calcium stearate 1.0 Phosphite compound (Table 5) 0.3 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate
0.1 The above formulation was extruded at 200°C to form pellets, and the pellets were then subjected to injection processing at 230°C to form test pieces. 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 Izod impact value of the test piece at 20°C was also measured. In addition, after being immersed in 100℃ hot water for 24 hours,
The Izod impact value of specimens heated at 135°C for 30 hours was also measured. The results are shown in Table-5.

[Table] Example 5 Styrene-acrylonitrile copolymer resin
100 parts by weight Phosphite compound (Table 6) 0.1 The above formulation was extruded at 230°C to prepare pellets, and a retention test in an in-die extrusion was conducted at 230°C. Test pieces with a thickness of 2 mm were injection molded without retention, after 10 minutes of residence, and after 20 minutes of residence, and the degree of coloration of the test pieces was expressed as yellowness measured with a Hunter colorimeter. The results are shown in Table-6.

【table】

[Table] Example 6 50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) with an intrinsic viscosity of 0.56 dl/g (in chloroform at 25°C), 47.5 parts by weight of polystyrene,
Add 2.5 parts by weight of polycarbonate, 3.0 parts by weight of titanium oxide, and 0.3 parts by weight of a phosphite compound,
The mixture was thoroughly mixed using a Henschel mixer, pelletized using an extruder, and then injection molded to prepare test pieces. This test piece was placed in a gear oven at 125℃ and 100℃.
After heating for a period of time, elongation and Izod impact value retention were measured. The results are shown in Table-7.

[Table] Example 7 Polycarbonate resin 100 parts by weight Phosphite compound (Table 8) 0.1 The above mixture was pressed at 260°C to prepare a colorless test piece with a thickness of 1.0 mm. 230 using this sheet
The degree of discoloration of the test piece after heating in a gear oven at ℃ for 30 minutes was observed. The results are shown in Table-8.

【table】

[Table] Example 8 The following formulation was processed with a kneading roll to a thickness of 1 mm.
A sheet was created. Using this sheet, 190℃
Thermal stability and initial coloring properties were tested. We also conducted a weather resistance test using a weatherometer. The results are shown in Table 9. <Composition> Polyvinyl chloride (Vinica 37H) 100 parts by weight Di-2-ethylhexyl phthalate 45 Tricresyl phosphate 3.0 Bisphenol A diglycidyl ether 2.0 Zinc stearate 0.8 Barium stearate 0.4 Barium nonyl phenate 0.5 Sorbitan mono Palmitate 3.0 Methylenebisstearylamide 0.3 Phosphite compounds (Table 9) 0.3

【table】

【table】

【table】

Claims (1)

[Claims] 1. A stabilized synthetic resin composition obtained by adding an organic phosphite compound represented by the following general formula () or () to a synthetic resin. (In the formula, SPG is a group , R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, a polyhydric alcohol or a polyhydric phenol residue, and the other hydroxyl group remains free or becomes a phosphite ester, X represents a hydrogen atom or [Formula], and n represents 1 to 10. R represents an alkylene group, an arylene group, an alkylidene diarylene group or a thiodiarylene group. )