JPS6345700B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin composition, and more particularly to a synthetic resin composition that is stabilized over a long period of time against deterioration due to the effects of heat and light by adding a specific phosphonite compound. It is known that synthetic resins such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride deteriorate due to the effects of heat and light, become colored, have reduced mechanical strength, and become unusable. In order to prevent such deterioration of synthetic resins, many additives have been used singly or in various combinations. Among these additives, phosphonite compounds are known to have a relatively large effect of improving heat resistance and suppressing coloration. For example, tetra(dialkylphenyl)biphenylene diphosphonite and bis(tetraalkylbiphenyl)biphenylene diphosphonite have been proposed and used. However, these phosphonite compounds have large photochromic properties, are inferior in light resistance, and have unsatisfactory processing stability for practical purposes. As a result of extensive studies in view of the current situation, the present inventors have found that when a phosphonite compound represented by the following general formula () is added to a synthetic resin, a resin composition with excellent heat resistance, light resistance, and processing stability can be obtained. The present invention was achieved by discovering the following. (In the formula, A represents a sulfur atom, an oxygen atom, or an alkylidene group, R represents an alkyl group, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ represents a hydrogen atom or an alkyl group.

【formula】

【formula】

【formula】

[Formula] or

[Formula] is shown. ) The compound represented by the above general formula () according to the present invention will be explained in more detail. Examples of the alkylidene group include methylene, ethylidene, isopropylidene, butylidene, cyclohexylidene, and isopropylbenzylidene. Examples of alkyl groups include methyl, ethyl,
Isopropyl, butyl, 2-butyl, t-butyl, t-amyl, octyl, isooctyl, t-
Octyl, nonyl, t-nonyl, decyl, lauryl, stearyl, cyclohexyl, benzyl, α
-Methylbenzyl, α,α-dimethylbenzyl,
Examples include groups such as α-methylcyclohexyl.

The dihydric phenol represented by the formula is 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'-dimelphenyl)-3,5,5-trimethylhexane, 2,2'-cyclohexylidene bis(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-merbenzyl-6-cyclohexylphenol), 2,2′-methylenebis(4-cyclohexyl-6-α-methylbenzylphenol), 2,
2'-ethylidene bis (4,6-di-t-butylphenol), 2,2'-ethylidene bis (4-methyl-6-t-butylphenol), 2,2'-ethylidene bis (4-second butyl-6-t-butylphenol), bis(2-hydroxy-3-t-butylphenyl) ether, bis(2-hydroxy-3-propylphenyl) ether, and the like. Representative examples of the phosphonite compound represented by the formula () used in the present invention are shown in Table 1 below. In the table, x indicates a t-butyl group. Table-1 No.1 Bis(4,4'-dimethyl-6,6'-di-t
-butyl-2,2'-methylene diphenyl)
Phenylene diphosphonite No. 2 Bis(4,4'-diethyl-6,6'-di-t
-butyl-2,2'-methylene diphenyl)
Bisphenylene diphosphonite No. 3 Bis(4,4',6,6'-tetra-t-butyl-2,2'-methylene diphenyl)terphenylene diphosphonite No. 4 Bis(4,4'-di-sec- Butyl-6,6′-
Di-t-butyl-2,2'-ethylidene diphenyl)oxydiphenylene diphosphonite No. 5 Bis(4,4',6,6'-tetra-t-butyl-2,2'-ethylidene diphenyl) ) Thiodiphenylene diphosphonite No. 6 Bis(4,4'-dimethyl-6,6'-di-t)
-butyl-2,2'-methylene diphenyl)
Biphenylene diphosphonite No. 7 Bis(4,4'-dimethyl-6,6'-di-t
-Butyl-2,2'-thiodiphenyl)biphenylene diphosphonite No.8 Bis(4,4'-diethyl-6,6'-di-t
-Butyl-2,2'-thiodiphenyl)biphenylene diphosphonite No.9 Bis(4,4'-dimethyl-6,6'-dicyclohexyl-2,2'-methylenediphenyl)biphenylene diphosphonite No.10 Bis[4 ,4'-dimethyl-6,6'-bis(α-methylcyclohexyl)-2,2'-
Methylene diphenyl biphenylene diphosphonite No.11 Bis(4,4',6,6'-tetra-t-butyl-2,2'-methylene diphenyl)bisphenylene diphosphonite No.12 Bis(5,5'- Dimethyl-6,6'-di-t
-Butyl-2,2'-methylenediphenyl)biphenylene diphosphonite No.13 Bis(4,4',6,6'-tetra-t-amyl-2,2'-methylenediphenyl)biphenylene diphosphonite No.14 Bis(4,4',6,6'-tetra-t-octyl-2,2'-methylenediphenyl)biphenylene diphosphonite The phosphonite compound represented by the above formula () according to the present invention has the formula Cl ₂ -P- A phosphine compound represented by R ₂ -P-Cl ₂ and

It can be easily synthesized by reacting with a dihydric phenol represented by the formula. Next, a specific synthesis example of the compound of the present invention will be shown. Synthesis Example 1 Synthesis of bis(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-methylenediphenyl)biphenylene diphosphonite 4,4'-biphenyl-(bis dichlorophosphenyl) Dissolve 7.12g of In) in 200ml of dichloroethane,
Cooled to 5°C. Add to this 13.62 2,2'-methylenebis(4-methyl-6-t-butylphenol)
g was added. Next, add 9.72g of triethylamine to 0.
The mixture was slowly added dropwise at ~5°C and stirred under reflux conditions at 86°C for 6 hours. The reaction product was filtered to remove triethylamine hydrochloride. After removing the solvent under reduced pressure, 150 ml of benzene was added and insoluble materials were separated. The melting point was determined by distilling off benzene again under reduced pressure.
A glassy solid was obtained at 157-161°C. 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, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate co- Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-anhydrous Maleic acid 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, internally plasticized polyester Halogen-containing synthetic resins such as vinyl 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,
Examples include polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, urea resin, melamine 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 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 0.01 to 5 parts by weight of a phenolic antioxidant to the composition of the present invention, the oxidative stability can be improved by acting additively.
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 (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[3,3-bis(4-hydroxy-3-tert-butylphenyl)butylphenyl)butyric acid] glycol ester, 4,4'-
Butylidenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
1,3,5-tris(3,5-di-tert-butyl-
4-hydroxybenzyl)-2,4,6-trimethylbenzene, 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, 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-dimethyl-3-hydroxy-
Examples include 4-tert-butylbenzyl) isocyanurate, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, and the like. 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'-hydroxy-4-methoxybenzophenone,
Hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 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-
Benzotriazoles such as (2'-hydroxy-3',5'-di-t-amyl phenyl)benzotriazole, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 , 5-di-t-butyl-4-hydroxybenzoate and other benzoates, 2,2′-thiobis(4-t-octylphenol) Ni salt,
Nickel such as [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine Ni salt, (3,5-di-t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, etc. Compounds, substituted acrylonitriles and 2,2,6,
6-Tetramethyl-4-piperidinylbenzoate, bis(2,2,6,6-tetramethyl-4-
piperidinyl) sebacate, tris(2,2,
6,6-tetramethyl-4-piperidinyl)nitrilotriacetate, tetrakis(2,2,6,
Examples include piperidine compounds such as 6-tetramethyl-4-piperidinyl)butanetetracarboxylate. The composition of the present invention may also contain a sulfur-based antioxidant. Examples of sulfur-based antioxidants include distearylthiodipropionate, dilaurylthiodipropionate, pentaerythritol tetra (β-laurylthiopropionate),
Examples include 1,3,5-tris-β-stearylthiopropionyloxyethyl isocyanurate. Light resistance and heat resistance can be further improved by adding a phosphite-based compound to the composition of the present invention, if necessary. Examples of the phosphite-based compounds include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, Stearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-
Tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra( _C12-15 mixed alkyl)-
4,4′-isopropylidene diphenyl diphosphite, tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, tris(3,5-di-tert.
Butyl-4-hydroxyphenyl) phosphite, tris(mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl) bis[4,4'- Butylidene bis(3-
Methyl-6-tert-butylphenol)]・1,6-
Hexanediol diphosphite, phenyl
4,4'-Isopropylidene diphenol pentaerythritol diphosphite, Tris [4,
4'-isopropylidene bis(2-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di(nonylphenyl) pentaerythritol diphosphite, tris(1,3-
di-stearoyloxyisopropyl) phosphite, 4,4'-isopropylidene bis(2-tertiary)
butylphenol) di(nonylphenyl) phosphite, etc. In addition, heavy metal deactivators, nucleating agents, metal soaps, organic tin compounds, plasticizers, epoxy compounds, pigments, fillers, foaming agents, antistatic agents, flame retardants, lubricants, processing aids, as necessary. etc. can be included. Next, the present invention will be specifically explained using examples. However, the present invention is not limited to these examples. Example 1 After mixing the following formulation in a grinder for 5 minutes,
Extrusion processing was carried out at °C. Next, injection molding was performed at 250°C to prepare a test piece with a thickness of 1 mm. Using this test piece, a thermal stability test was conducted in a gear oven at 160°C. Also, to check the light resistance, 72
The yellowness of the test piece after being irradiated with a fluorescent lamp for a period of time was measured using a Hunter colorimeter. Furthermore, in order to examine processing stability, the change in melt index (230°C, load 2160g) was measured when extrusion was repeated 5 times at 250°C. The results are shown in Table-2. Compounded unstabilized polypropylene 100 parts by weight Calcium stearate 0.2 Dilauryl thiodipropionate 0.2 Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyphenylpropionate) 0.1 Phosphonite compound (Table 2) ) 0.1

【table】

[Table] Example 2 The following formulation was kneaded with a mixing roll at a temperature of 150°C for 5 minutes, and then at a temperature of 150°C and 180Kg/cm ²
Compression molding was performed for 5 minutes under the following conditions to create a sheet with a thickness of 1.2 mm. This sheet was used as a 10 x 20 mm test piece and subjected to a gear oven heating deterioration test in air at a temperature of 150°C on aluminum foil. Note that 10 specimens were used for the same sample, and the time when 5 or more specimens became discolored or waxy was defined as the deterioration time.
The results are shown in Table-3. Compounded polyethylene resin (HIZEX 5100E, manufactured by Mitsui Oil Co., Ltd.) 100 parts by weight Dilauryl thiodipropionate 0.3 Stearyl-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.1 Phosphonite compound (Table 3) ) 0.05

[Table] Example 3 48 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), 50 parts by weight of polystyrene, 2 parts by weight of polycarbonate, oxidation 3.0 parts by weight of titanium and 0.5 parts by weight of a phosphonite compound were 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 100 hours, and the elongation and Izot impact value retention were measured. The results are shown in Table 4.

[Table] Example 4 ABS resin (Blendex 111) 100 parts by weight Zinc stearate 0.5 Tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl) isocyanurate 0.1 Phosphonite compound (Table 5) 0.2 Roll knead the above compound and press it to a thickness of 0.5
A sheet of mm was created. 135℃ using this sheet
The degree of coloration of the sheet after heating in a gear oven for 20 hours was measured using a Hunter colorimeter and expressed as whiteness. The results are shown in Table-5.

[Table] Example 5 Polyvinyl chloride resin (Geon103EP, Nippon Zeon product) 100 parts by weight, dioctyl phthalate 42
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 0.2 parts by weight of phosphonite compound (Table 6) were mixed at a temperature of 175°C with a mixing roll. After kneading for 5 minutes, compression molding was performed at a temperature of 175°C to create a transparent sheet. then
Thermal degradation tests were conducted in a gear oven under air atmosphere at a temperature of 190°C. Incidentally, the deterioration start time was determined based on the degree of coloring. Also related humidity 100%, temperature 175
Tests were also conducted in a constant humidity chamber kept at ℃. The results are shown in Table-6.

[Table] Example 6 In order to examine the effect of the compound according to the present invention on ethylene vinyl acetate copolymer, a sample was prepared with the following formulation and the thermal stability and initial coloring property were measured in a gear oven at 175°C. did. Regarding initial coloration, yellowness was determined using a Hunter colorimeter. The results are shown in Table-7. Compounded ethylene-vinyl acetate copolymer resin
100 parts by weight Montanic acid lubricant 0.3 Stearyl-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.05 Phosphonite compound (Table 7) 0.1

【table】

[Table] Example 7 Polybutylene terephthalate 100 parts by weight Pentaerythritol tetrakis (3,5-
Di-tert-butyl-4-hydroxyphenylpropionate) 0.1 Phosphonite compound (Table 8) 0.2 The above formulation was subjected to in-die extraction processing at 270°C to prepare test pieces. 150℃ using this test piece.
The residual tensile strength was measured after heat aging for 240 hours. The results are shown in Table-8.

[Table] Example 8 After adding 0.5 g of a phosphonite compound to 100 g of cis-1,4-isoprene rubber (Ziglar catalyst, number average molecular weight 720000), 250 ml of dried isooctane was added to prepare a homogeneous solution. .
Next, this solution was transferred to an evaporator and the solvent was removed on a hot bath. The obtained rubber composition was heat aged in a constant temperature bath at 100°C for 3 hours. Coloring tests and intrinsic viscosity measurements (toluene solvent) were performed. The results are shown in Table-9.

[Table] Example 9 100 parts by weight of polycarbonate resin and 0.1 part by weight of phosphonite 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 30 minutes, and the degree of discoloration of the test piece was observed. The results are shown in Table-10.

【table】

Claims (1)

[Claims] 1. A stabilized synthetic resin composition obtained by adding a phosphonite compound represented by the following general formula () to a synthetic resin. (In the formula, A represents a sulfur atom, an oxygen atom, or an alkylidene group, R represents an alkyl group, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ represents [Formula] [Formula] [Formula] [Formula] or [formula].)