JPH0357151B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] Regarding the stabilized synthetic resin composition of the present invention,
Specifically, the present invention relates to a synthetic resin composition with improved heat resistance, weather resistance, processability, etc., which is obtained by adding a specific sulfur-containing spiroglycol ester compound to a synthetic resin. [Prior art and its problems] 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 and losing mechanical strength, making them unusable. ing. In order to prevent such deterioration of synthetic resins, many additives have been used singly or in various combinations. Among these additives, phenolic antioxidants and sulfur antioxidants have a relatively large stabilizing effect and have been widely used. However, these conventionally used antioxidants often lose their effectiveness within a relatively short period of time;
In particular, the effect is often rapidly lost outdoors or in a humid atmosphere. In addition, when processing synthetic resins at high temperatures, the effect is lost, which is unsatisfactory from a practical standpoint. [Means for Solving the Problem] In view of the current situation, the present inventors have made extensive studies and found that if a certain sulfur-containing spiroglycol ester compound is added to a synthetic resin, the heat resistance, weather resistance, and processability will be improved. They have found that this is a significant improvement and have completed the present invention. That is, the present invention provides a stabilized synthetic resin composition obtained by adding a sulfur-containing spiroglycol ester compound represented by the following general formula () or () to a synthetic resin. (In the formula, -SPG- is a group , R ₁ represents an alkyl group having 1 to 20 carbon atoms, and R ₂ represents a hydrogen atom or

[Formula], R ₃ is a hydrogen atom, an acyl group, or

[Formula], R ₄ is an alkyl group having 1 to 20 carbon atoms or -SPG
-O- _R5 , _R5 represents a hydrogen atom or an acyl group, m represents 1 or 2, and n represents 1-20. ) The present invention will be explained in more detail below. In the above general formula () or (), R ₁ and
Examples of the alkyl group having 1 to 20 carbon atoms represented by R ₄ include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl,
Examples include hexadecyl, octadecyl, and eicosyl. Next, Table 1 shows specific examples of the sulfur-containing spiroglycol ester compounds used in the present invention. In the table, -SPG- is a group. shows.

【table】

[Table] The amount of the sulfur-containing spiroglycol ester compound used is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the synthetic resin. Further, the sulfur-containing spiroglycol ester compound used in the present invention can be easily synthesized by a conventionally well-known method. for example,
Easily obtained by reacting 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane with an acid or an ester. I can do it. A specific example is shown below. Synthesis Example 1 Synthesis of No. 2 (Table-1) Compound 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane 8.78 g (0.0289 mol),
β-dodecylthiopropionic acid 17.40g (0.0635
mole), 50 ml of xylene and 0.52 g as catalyst
(2% by weight) of para-toluenesulfonic acid was added,
The reaction was carried out at 145 to 150° C. for about 6 hours under a nitrogen atmosphere.
After the reaction, an appropriate amount of toluene was added, and the mixture was washed with a 1% aqueous sodium hydroxide solution, followed by washing with water, filtering out insoluble materials, and removing the solvent. The obtained crude product was
Recrystallization was performed with hexane to obtain the desired product as a white powder. Yield was 14.6g (62.1%), melting point 77-79°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, rubber chloride, 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 copolymer 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 copolymer, 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, cellulose resin, or phenolic resin, urea resin, melamine resin, epoxy Examples include resins, unsaturated polyester resins, and silicone resins. Further, 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. Oxidative stability can be improved by further adding a phenolic antioxidant to the composition of the present invention. Examples of these phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl-(3,5-dimethyl-4-hydroxybenzyl). ) thioglycolate, stearyl-β-(4-hydroxy-3,5
-di-tert-butyl phenyl) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl) thio)-1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl)
Benzyl malonate, 2,2'-methylenebis(4
-methyl-6-tert-butylphenol), 4,
4'-methylenebis(2,6-ditertiary bunylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], bis[3,
5-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester,
4,4'-Butylidene bis(6-tert-butyl-m-
cresol), 2,2'-ethylelidene bis(4,
6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-sec-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-butyl)benzyl isocyanurate,
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-ditert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,6-di(4-hydroxy-3,5-ditert-butyl)phenoxy-1,
Phenols such as 3,5-triazine and 4,4'-thiobis(6-tert-butyl-m-cresol) and carbonic acid oligoesters of 4,4'-butylidenebis(2-tert-butyl-5-methylphenol) (For example, degree of polymerization 2, 3, 4, 5, 6, 7, 8,
Examples include oligoesters of polyhydric phenols such as (9, 10, etc.). It is also possible to further add a sulfur-based antioxidant to the composition of the present invention to improve its oxidative stability. These sulfur-based antioxidants include, for example, dialkylthiopropionates such as dilauryl, dimyristyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and sunaryl (e.g., glycerin). , trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralaurylthiopropionate). By further adding a phosphorus-containing compound such as phosphite to the composition of the present invention, weather resistance and heat resistance can be improved. Examples of the phosphorus-containing compound include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris( butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol 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-4-tertiary) butylphenol)]・1,6-hexanediol diphosphite, phenyl・4,
4'-Isopropylidene diphenol pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) hentaerythritol diphosphite tris[4,4'-isopropylidene bis(2-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di(nonylphenyl) pentaerythritol diphosphite, tris(1,3-diteataloyloxyisopropyl) ) phosphite, 4,4'-isopropylidene bis(2-tert-butylphenol) di(nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis( 2,4-di 3rd
Examples include (butylphenyl)-4,4'-biphenylene diphosphonite. 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,
Hydroxybenzophenones such as 2,2'-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5
-benzotriazoles such as chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditertiary amyl phenyl) benzotriazole, phenyl Salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-
Benzoates such as di-tert-butyl-4-hydroxybenzoate: 2,2'-thiobis(4-tert-octylphenol) Ni salt: [2,2'-thiobis(4-tert-octylphenol)]- n-Butylamine Ni salt, (3,5-di-tert-butyl-4-
Nickel compounds such as hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, bis(2,
2,6,6-tetramethyl-4-piperidine) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-
Ditert-butyl-4-hydroxybenzylmalonate, bis(1-acroyl-2,2,6,6-tetramethyl-4-piperidyl)bis(3,5-ditert-butyl-4-hydroxybenzyl)malonate , tetrakis(2,2,6,6-tetramethyl-4-pipericyl)butane-1,2,3,4-tetracarboxylate, 1-hydroxyethyl-
2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate condensate, cyanuric chloride/
Tertiary octylamine/1,6-bis(2,2,
6,6-tetramethyl-4-piperidylamino)
Piperidine compounds such as hexane condensates, α-cyano-β-methyl-β-(p-methoxyphenyl)
Substituted acrylonitriles such as methyl acrylate and N-2-ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalic acid diamide, n-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide Examples include oxalic acid dianilides such as. In addition, as necessary, the composition of the present invention may contain a heavy metal inert agent, a nucleating agent, a metal soap, an organic tin compound, a plasticizer, an epoxy compound, a pigment, a filler, a blowing agent,
Antistatic agents, flame retardants, lubricants, processing aids, and the like 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 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 20rpm). A test piece measuring 95 x 40 x 1 mm was made using an injection molding machine using this compound. (Cylinder temperature 240
℃, nozzle temperature 250℃, injection pressure 475Kg/cm ² ) Using the obtained test piece, the thermal stability was measured in a gear oven at 160℃, and the thermal stability was measured using a Hunter colorimeter at 72℃.
The yellowness (%) of the test piece was measured after being irradiated with a fluorescent lamp for an hour. The results are shown in Table-2. <Formulation> Polypropylene resin (Profax 6501) 100 parts by weight Calcium stearate 0.2 Pentaerythritol tetrakis-β-(3,5
-di-tert-butyl-4-hydroxyphenyl)propionate 0.1 Ester compound (Table-2) 0.2

【table】

[Table] Example 2 The following compound was kneaded with a mixing roll at 150 degrees for 5 minutes, and then compression molded for 5 minutes at 150 degrees Celsius and 180 kg/cm ² to form a test piece with a thickness of 1.0 mm.
Thermal stability tests were conducted on aluminum foil in a gear oven at a temperature of 150°C. The results are shown in Table-3. <Composition> Polyethylene resin (HIZEX 5100E)
100 parts by weight Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate 0.1 Ester compound (Table 3) 0.3

【table】

[Table] Example 3 Intrinsic viscosity 0.56 dl/g (in chloroform, 25°C)
50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide), 47.5 parts by weight of polystyrene, 2.5 parts by weight of polycarbonate, 3.0 parts by weight of titanium oxide.
Parts by weight and No. 2 (Table 1) of the ester 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 placed in a gear oven.
It was heated at 125°C for 100 hours, and the elongation and Izod impact value retention were measured. In addition, as a comparative example, when no ester compound is added (comparative example 3-1) and when stearyl (3,
The case in which 5-di-tert-butyl-4-hydroxyphenyl) propionate was added (Comparative Example 3-2) was tested at the same time. The results are shown in Table 4.

[Table] Example 4 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-5. <Composition> Polyvinyl chloride resin (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 Octyl diphenate Enylphosphite 0.5 Sorbitan monopalmitate 3.0 Methylene bisstearylamide 0.3 Ester compound (Table 5) 0.1

【table】

Claims (1)

[Scope of Claims] 1. A stabilized synthetic resin composition obtained by adding a sulfur-containing spiroglycol ester compound represented by the following general formula () or () to a synthetic resin. (In the formula, -SPG- is a group , R ₁ represents an alkyl group having 1 to 20 carbon atoms, R ₂ represents a hydrogen atom or [formula], R ₃ represents a hydrogen atom, an acyl group, or [formula], and R ₄ represents a carbon atom Alkyl group of number 1 to 20 or -SPG
-O- _R5 , _R5 represents a hydrogen atom or an acyl group, m represents 1 or 2, and n represents 1-20. )