JPH02289635A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized synthetic resin composition having improved heat-resistance, weather-resistance, processability. etc., by adding a specific sulfur-containing spiro-glycol ester compound to a synthetic resin. CONSTITUTION:The objective stabilized synthetic resin composition is produced by compounding (A) 100 pts. wt. of a synthetic resin with (B) 0.001-5 pts.wt. (preferably 0.01-3 pts.wt.) of a sulfur-containing spiro-glycol compound of formula I or formula II [SPG is group of formula III; R1 is 1-20C alkyl; R2 is OH or group of formula IV; R3 is R or group of formula V (R5 is 1-20C alkyl or group of formula VI); R4 is 1-20C alkyl or group of formula VII; m is 1 or 2; n is 0 to 20] (e.g. the compound of formula VIII) produced e.g. by reacting 3,9-bis(1,1- dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane with an acid or an ester and, as necessary, (C) a phenolic antioxidant, sulfur-based antioxidant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a stabilized synthetic resin composition, and more particularly, to a stabilized synthetic resin composition that has heat resistance and weather resistance obtained by adding a specific sulfur-containing spiroglycol ester compound to a synthetic resin. The present invention relates to a synthetic resin composition with improved properties such as properties and processability.

[Conventional technology and its problems]

It is known that synthetic resins such as polyethylene, polypropylene, ABS, and polyvinyl chloride deteriorate due to the action of heat and light, becoming discolored and 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, 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 in a relatively short period of time, especially outdoors or in a humid cloud atmosphere. Moreover, when processing synthetic resins at high temperatures, the effect is lost, which is unsatisfactory in practice.

[Means to solve the problem]

In view of the current situation, the inventors of the present invention have conducted extensive studies, and have found that
The inventors have completed the present invention by discovering that heat resistance, weather resistance, and processability can be significantly improved by adding a specific sulfur-containing subiloglycol ester compound to a synthetic resin.

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 (I) or (II) to a synthetic resin.

R, -S-(CH2). co-SPG-0-R2 (
I) (In the formula, -SPG1 is a group R1 represents an alkyl group having 1 to 20 carbon atoms, and R2 is a hydroxyl group or -C-([:H2).-S-(CH2).
-R. R3 represents a hydrogen atom or -C-R, R4 represents an alkyl group having 1 to 20 carbon atoms or -SPG-0-R
represents an alkyl group 1I having 1 to 20 carbon atoms or -C-R. , m represents 1 or 2, and n represents 0 to 20. ) The present invention will be explained in more detail below.

In the above general formula (1) or (II), the alkyl group having 1 to 20 carbon atoms represented by R1, R4 and R is methyl, ethyl, proyl, isobrobyl, butyl, hevicyl, octyl, 2-ethylhexyl, Examples include nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl.

Next, specific examples of the sulfur-containing spiroglycol ester compounds used in the present invention are shown in Table 1l.

In the table, -SPG- is a group k 5 C, 6H3, SCJ. [:0-SPG-OC
[:2H. SC, 6H3. Na I C. J. ,SC
2H. CD-SPG-DH The amount of the sulfur-containing spiroglycol ester compound used is 0.001 to 5 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the synthetic resin. It is 3 parts by weight.

Further, the sulfur-containing spiroglycol ester compound used in the present invention can be easily synthesized by a conventionally well-known method. For example, 3,9-bis(1,1-
dimethyl-2-hydroxyethyl)-2.4,8.10
-Tetraoxaspiro[5,5) It can be easily obtained by reacting undecane with an acid or an ester.

A specific example is shown below.

Synthesis Example INα2 (Table 1) Synthesis of Compound 3.9-bis(
1,1-dimethyl-2-hydroxyethyl)-2.
4. 8. 10-Tetraoxaspiro (5.5)
Undecane 8.78g (0.0289mol), β-
Dodecylthiopropionic acid 17. 40 g (0.
0635 mol), 50-mol of icilene and 0.0-mol as a catalyst.
52 g (2% by weight) of balatoluenesulfonic acid was added, and the mixture was reacted 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 water washing, separation of insoluble materials, and removal of solvent. The obtained crude product was recrystallized with n-hexane to obtain the desired product as a white powder. Yield: 14.6g
(62.1%), and the melting point was 77-79°C.

Synthetic resins stabilized by the present invention include, for example, polyethylene, polypropylene, polybutene, poly-
α-olefin polymers such as 3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof;
Polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, vinylidene 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 styrene chloride copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl styrene chloride-maleic anhydride terpolymer, vinyl chloride loose Thyrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated brobylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester Copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acryloni 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.)
copolymers with, acrylonitrile-butadiene-styrene copolymers, acrylic acid ester-butadiene-styrene copolymers, methacrylic acid mono-butadiene-styrene copolymers, methacrylate resins such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl Formal, polyvinyl butyral, direct-set polyester, polyamide, polycarbonate, polyacetal, polyurethane, polyphenylene oxide, cellulose resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. I can do it.

Further, rubbers such as inbrene 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 invention.

Examples of these phenolic antioxidants include 2.
6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (
3. 5-dimethyl-4-hydroxybenzyl)thioglycolate, stearyl β-(4-hydroxy-3
．． 5-di-tert-butylphenyl)probionate, distearyl-3.5-di-tert-butyl-4-hydroxybenzylphosphonate, 2.4.6-}lis(3°,5°-di-tert-butyl-4'- hydroxybenzylthio)-1.3
．． 5-}Ryazine, distearyl (4-hydroxy-3
-methyl-5-tert-butyl)benzylmalone}, 2.
2゜-methylenebis(4-methyl-6-tert-butylphenol), 4.4'-methylenebis(2,6-ditertiary-butylphenol), 2.2゜-methylenebis[
6-(1-methylcyclohexyl)-p-cresol], bis[3,5-bis(4-hydroxy-3-tertiary butylphenyl)butyric acid] glycol ester, 4,4'-butylidene bis(6-tertiary butylphenyl) 3 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(2-13butyl-4-methyl-6-(2-hydroxy-3-13butylphenyl-5-methylbenzyl)phenyl)terephthalate, 1,
3.5-}Lis(2.6-dimethyl-3-hydroxy-
4-13 butyl) pendyl isocyanurate, 1,3.
5-}lis(3,5-di-tert-butyl-4-hydroxybenzyl)-2.4.6-}limethylbenzene, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) Probionate] Methane, 1,3.5
-} Lis(3.5-di-tert-butyl-4-hydroxybenzyl)in cyanurate, 1.3.5-Tris((3.
5-ditert-butyl-4-hydroxyphenyl)propionyloxyethyl]in cyanurate, 2-octylthio-4.6-di(4-hydroxy-3.5-ditert-vinyl)phenolicy-1.3.5- Triazine, phenols such as 4.4° thiobis (6-tert-butyl-m-cresol), and carbonic acid oligoesters of 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) (
For example, the degree of polymerization is 21. 4.5, 6.7.8.9.10
Examples include oligoesters of polyhydric phenols such as

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, and trimethylol). methylolbroban, pentaerythritol,
trishydroxyethyl isocyanurate (eg, pentaerythritol tetralauryl thiobrobionate).

Weather resistance and heat resistance can be improved by further adding a phosphorus-containing compound such as phosphite to the composition of the present invention. 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 (
butoiethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1. 1.
3-}Lis(2-methyl-5-tert-butyl-4-hydrocyphenyl)butane diphosphite, tetra(C
l2~,5 mixed alkyl)-4,4''-inbropylidene diphenyl diphosphite, tetra(tridecyl)-
4.4'-butylidene bis(3-methyl-6-tertiary
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-tert-butylphenol)] ・1,6-hexanediol diphosphite, phenyl ・4,4゜-isopropylidene diphenol ・pentaerythritol diphosphite, bis(2, 4-Ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-
methylphenyl)hentaerythritol diphosphite, tris[4,4°-isopropylidene bis(2-13
butylphenol)] phosphite, phenyl diisodecyl phosphite, di(nonylphenyl) pentaerythritol diphosphite, tris(1,3-distearyloxyisobutyl) phosphite, 4,4゜-
Isopropylidene bis(2-tertiary butylphenol)・
Di(nonylphenyl)phosphite, 9.10-dihyde-9-oxer-10-phosphaphenanthrene-
Examples include 10-oxide, tetrakis(2,4-di-tertiary butylphenyl)-4.4°-biphenylene diphosphonite, 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-
Hydroxybenzophenones such as n-octoxybenzophenone, 2.2゛-dihydroxy-4-methoxybenzophenone, 2.4-dihydroxybenzophenone, 2-(2゜-hydroxy-3'-primary:3'-thi- 5゜-methylphenyl)-5-chloropenzotriazole, 2-(2゜hydroxy-3゛.5゜-di-tert-butylphenyl)-5-1 oral penzotriazole, 2-
Penzotriazoles such as (2'-hydroxy-5''-methylphenyl)penzotriazole, 2-(2'-hydroxy-3''.5゜-tertiary amyl phenyl)benzotriazole, phenyl salicylate, p- Third
Benzoates such as butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3.5-di-tert-butyl-4-hydroysibenzoate HR: 2
．． 2'thiobis(4-tertiary octylphenol)N
i salt: C2.2°-thiobis(4-tertiary octylphenolate)]-n-butylamine N1 salt, (3.5
-';-Nickel compounds such as tertiary phthyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, bis(2.2.6.6-tetramethyl-
4-piperidyl) sebacate, bis(1,2,2,6.
6-pentamethyl-4-biperidyl) n-butyl3.
5-Ditert-butyl-4-hydroxybenzylmalonate, bis(1-acroyl-2.2.6.6
-tetramethyl-4-piperidyl)bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, tetrakis(2.2.6,6-tetramethyl-4-pipericyl)butane-1. 2. 3. 4-Tetracarpoxylate, ■Hydroxyethyl-2.2.6.6-
Tetramethyl-4-biperidinol/diethyl succinate condensate, cyanuric chloride/tertiary octylamine/1,6-
Piperidine compounds such as bis(2,2.6.6-tetramethyl-4-piperidylamino)hexane condensate, α-
Substituted acrylonitriles such as cyano β-methyl-β-(p-methoxyphenyl)methyl acrylate and N
-2-ethylphenyl-N"-2-ethoxy-5-tertiary
Examples include oxalic dianilides such as butylphenyl oxalic diamide and n-2-ethylphenyl N-2-ethoxyphenyl oxalic diamide.

If necessary, the composition of the present invention may also contain heavy metal deactivators, nucleating agents, metal soaps, organic tin compounds, plasticizers, epoxy compounds, pigments, fillers, blowing agents, antistatic agents, flame retardants, and lubricants. , processing aids, and the like.

Next, the present invention will be specifically explained using examples.

However, the present invention is not limited to these examples.

Example 1 After blending the following formulations in a mixer for 5 minutes, a compound was created in an extruder (cylinder temperature 230°C and 240°C, head die temperature 250°C, rotation speed 2Or
pm).

Using this compound 9 5 x 4 0 x 1
A test piece with a diameter of mm was prepared using an injection molding machine. (Cylinder temperature 240℃, nozzle temperature 250℃, injection pressure 475kg
/ctl) The obtained test piece was used to measure the thermal stability in a 160°C gar oven, and a Hunter colorimeter was used to measure the yellowness (%) of the test piece after 72 hours of fluorescent light irradiation.
) was measured.

The results are shown in Table-2.

Contains 0.0% calcium stearate. Ester compounds (Table-2) 0. Example 2 The following composition was kneaded with a mixing roll at 150 degrees Celsius for 5 minutes, and then compression molded at 150 degrees Celsius and 180 kg/cm'' for 5 minutes. A thermal stability test was carried out on the foil in a gar oven at a temperature of 150°C.

The results are shown in Table-3.

Blend> Cyanurate ester compound (Table-3) 0.3Table-3 Example 3 Intrinsic viscosity 0.56 dl/g (in chloroform, 25°C
) poly (2. 6-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)
Parts by weight and No. The ester compounds shown in Table 2 (Table 1) were added, thoroughly mixed using a Henschel mixer, pelletized using an extruder, and then injection molded to prepare test pieces. This test piece was heated in a GAR oven at 125° C. for 100 hours, and the elongation and Izod TTR impact value retention were measured.

As a comparative example, when no ester compound is added (
Comparative Example 3-1) and the case where stearyl (3,5 di-tert-butyl-4-hydroxyphenyl) propionate was added (Comparative Example 3-2) were tested simultaneously.

The results are shown in Table 4.

Table 4 Example 4 The following formulation was processed using a kneading roll to create a sheet with a thickness of 1 mm. Using this sheet, thermal stability and initial colorability tests at 190°C were conducted. A weather resistance test was also conducted using a weatherometer.

The results are shown in Table-5.

Blend> Polyvinyl chloride resin 100 parts by weight (Vinica 37H) Di-2-ethylhexyl phthalate tricresyl phosphate bisphenol A diglycidyl ether 3.0 2,0 Zinc stearate Barium stearate Barium nonylphenate octyl diphthate Enyl phosphite sorbitan monobalmitate methylene bis stearyl amide ester compound (Table-5) Table-5 3.0 0.3 0.1

Claims (1)

[Claims] A stabilized synthetic resin composition obtained by adding a sulfur-containing spiroglycol ester compound represented by the following general formula (I) or (II) to a synthetic resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, -SPG- indicates the group ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_1 is Represents an alkyl group having 1 to 20 carbon atoms, R_
2 indicates a hydroxyl group or ▲A mathematical formula, chemical formula, table, etc. are available▼, R_3 is a hydrogen atom or ▲A numerical formula, chemical formula, table, etc. are available▼, and R_4 is an alkyl group having 1 to 20 carbon atoms or -SPG- O-R_5, R_5 is an alkyl group having 1 to 20 carbon atoms, or ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ indicates, m indicates 1 or 2, and n indicates 0 to 20. )