JPS6312664A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having remarkably improved heat- resistance, light-resistance and moldability, by compounding a base resin with an ester compound having a specific group in the molecule. CONSTITUTION:100pts.(wt.) of a synthetic resin (e.g. polyethylene, polypropylene, etc.) is compounded with 0.001-5pts., preferably 0.01-3pts. of a compound of formula I [R is group of formula II, formula III [R1-R3 are H or alkyl; t is 0-2; m is 1 or 2) or formula IV (R4 is alkyl or group of formula II; n is 1 or 2)]. The compound of formula I can be easily produced e.g. by reacting 5,5-dimethylol-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane with an acid or ester.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to stabilized synthetic resin compositions. Specifically, the present invention relates to a synthetic resin composition with improved heat resistance, light resistance, processability, etc., which is obtained by adding an ester compound having a specific group in the molecule to a synthetic resin.

[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, becoming discolored and having 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-based antioxidants have a relatively large stabilizing effect and have been widely used. For example, JP-A-59-2582
No. 6 proposes the use of spirodiketal glycol esters as stabilizers for synthetic resins. However, the effects of these compounds are still insufficient, and in particular, their effects are lost when processing synthetic resins at high temperatures, making them unsatisfactory in practice.

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, light resistance, and processability can be significantly improved by adding an ester compound having a specific group in the molecule to a synthetic resin.

That is, the present invention provides a stabilized synthetic resin composition, which is obtained by adding a compound represented by the following general formula (I) to a synthetic resin.

The present invention will be described in more detail below. do.

In the above general formula (I), the alkyl groups represented by RI+ Ri and R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary-butyl, 37-mil, octyl, tertiary-octyl, Examples include nonyl, decyl, cyclohexyl, l-methylcyclohexyl, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and the like.

The alkyl group represented by R4 is methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl,
Examples include octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, tocosyl, tetradecyl, doriacontyl, and the like.

Next, specific examples of the compound represented by the general formula (I) used in the present invention are shown in Table-1.

Table-1 7 CJ+3SCHtCHz-8 C
＋! HzsSCHtCHt-Fish 9 C+*tI
ztSCHzCNt-affected 10 C0~1111!3
~ztSCIlxCH*-The amount of the ester compound used is preferably 0.001 parts by weight per 100 parts by weight of the synthetic resin.
~5 parts by weight, more preferably 0.01 to 31 parts by weight.

Further, the ester compound used in the present invention can be easily synthesized by conventionally known methods. For example, it can be easily obtained by reacting 5,5-dimethylol-2-(I+ 1-dimethyl-2-hydroxyethyl)-1,3-dioxane with an acid or an ester. A specific example is shown below.

Synthesis Example 1m1 (Table-1) Synthesis of Compound 5.5-dimethylol-2-(I,1-dimethyl-2-
11.01g of hydroxyethyl)-1,3-dioxane
(0,05 mol'), methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate 52
．． 56 g (0.18 mol) and 0.095 g (0.15% by weight) of lithium amide as a catalyst were dissolved in mineral spirit and reacted under a nitrogen atmosphere at 140 to 160° C. for 1 hour while distilling off methanol.

The mixture was further reacted for 2 hours while removing methanol under reduced pressure. After the reaction is complete, add mineral spirits, excess 3-(3,5-
Methyl di-t-butyl-4-hydroxyphenyl)propionate and the catalyst were removed to obtain the desired product as a white powder with a melting point of 65-68°C.

The IR of the product is 'o, 13650cm-','c-
o-c 1115cm-', νC5゜1735cm-'
Met.

Synthesis Example 2ml0 (Table-1) Synthesis of Compound 5.5-dimethylol-2-(I,1-dimethyl-2-hydroxyethyl)-1,3-dioxane 22.0g (0.1 mol) and β-CI6 ~+a alkylthiopropionic acid 11
3.6 g (0.33 mol) were dissolved in 200 g of toluene. 1.4 g of para-toluenesulfonic acid (I
. Then 1% Na
After adding 200 g of zCO:+ aqueous solution and washing the catalyst, and further washing with water, toluene was removed to obtain a white wax-like target product. IR is ν. ,.

It was 1720 cm-.

Examples of the synthetic resins stabilized by the present invention include polyethylene, polypropylene, polybutene, poly-3
- α-olefin polymers such as methyl butene or polyolefins such as ethylene-vinyl acetate copolymers, 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-hynylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, 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-maleate ester copolymer, vinyl chloride-methacrylate ester copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resins such as internally plasticized 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 copolymers, methacrylic esters -butadiene-styrene copolymer, methacrylate resin such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal,
Polyvinyl butyral, linear polyester, polyfumide, polycarbonate, polyacetal, polyurethane,
Examples include polyphenylene oxide, cellulose resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Furthermore, rubbers such as isoprene rubber, butadiene rubber, acrylonitriyl-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
-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl-(
3,5-di-methyl-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゛-hydroxybenzylthio)-
1,3,5-) riazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4 .4”-methylenebis(2,6-
di-tert-butylphenol), 2,2'-methylenebis[6-(I-methylcyclohexyl)p-cresol], bis[3□5-bis(4-hydroxy-3-tert-butylphenyl)butyric acid coglycol Ester, 4.4'-butylidenebis(6-tert-butyl-m-cresol), 2.2°-ethylidenebis(4,6-di-tert-butylphenol), 2.2°-ethylidenebis(4-tert-butylphenol), 2-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-) Lis(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzyl isocyanurate, 1,3
．． 5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-) listylbenzene, tetrakis[methylene-3-(3,5-di-tert-butyl-
4-Hydroxyphenyl)propionate comethane, 1
, 3.5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1.3.5- )
Lis((3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl)isocyanurate,
2-octylthio-4,6-di(4-hydroxy-3,
Phenols such as 5-di-tert-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol) and 4,4'-butylidenebis(2-tert-butyl), butyl-5-methylphenol) carbonate oligoester (for example, degree of polymerization 2, 3, 4, 5.6.7)
, 8, 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, dialkylthiodipropionates such as dilauryl, simiristyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and sterol. (e.g. glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (e.g. pentaerythritol tetralauryl thioprobionate)
can be mentioned.

Light 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( butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-)lis(2-methyl-5-tert-butyl-4-hydroxyphenyl) ) Butane diphosphite, tetra(C82-Is mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl) -4,4'
-butylidene bis(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'-isopropylidenediphenol pentaerythritol diphosphite, bis(2,4-'
;-37'-tylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris(4,4'-isopropylidene bis(2-tert) butylphenol)] phosphite, phenyl diisodecyl phosphite, di(nonylphenyl)pentaerythritol diphosphite, tris(I,3-di-stearoyloxyisopropyl) phosphite, 4,4'-isopropylidene bis(2- tert-butylphenol) di(nonylphenyl) phosphite, 9.10-di-hydro-9-oxa-10-phosphonoaphenanthrene-
10-oxide, tetrakis(2,4-di-tert-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.

These light stabilizers include, for example, 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-4-n
-Hydroxybenzophenones such as octoxybenzophenone, 2.2'-di-hydroxy-4-methoxybenzophenone, and 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'-
Benzotriazoles such as hydroxy-5゛-methylphenyl)benzotriazole, 2-(2''-hydroxy-3゜,5゛-di-t-amylphenyl)benzotriazole, phenyl salicylate, pt-butylphenyl salicylate , 2.4-di-t-butylphenyl-3
, 5-di-t-butyl-4-hydroxybenzoate,
Benzoates such as hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,2"-thiobis(4-t-octylphenol) Ni salt, (2,2'
-thiobis(4-t-octylphenolate)]-]n
-butylamine Ni, (3,5-di-t-butyl-4
Nickel compounds such as -hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, bis(2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis(I
,2,2,6,6-bentamethyl-4-piperidyl)-
n-Butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonate, bis(l-acryloyl-2,
2,6,6-tetramethyl-4-piperidyl)bis(3
, 5-C 3rd phthyl-4-hydroxybenzyl)
malonate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, l-hydroxyethyl-2,2,6
, 6-tetramethyl-4-piperiditul/diethyl succinate condensate, cyanuric chloride/tertiary octylamine/
Piperidine compounds such as 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane condensate, methyl α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate, etc. substituted acrylonitriles and N-2-ethylphenyl-N'-2-ethoxy-5-m
Examples thereof include oxalic acid dianilides such as 3-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N-2-ethoxyphenyl oxalic acid 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.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these examples.

Example 1 After blending the following composition 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 20r).
pn+).

Using this compound, a 95 x 40 x 1 w test piece was made using an injection molding machine (cylinder temperature 240°C,
Nozzle temperature 250°C, injection pressure 475kg/aJ).

Thermal stability of the obtained test piece was measured in a gear oven at 160° C., and the yellowness (%) of the test piece after 72 hours of fluorescent lamp irradiation was measured using a Hunter colorimeter. The results are shown in Table-2.

<Composition> Polypropylene resin (Profax 6501 10
0 parts by weight manufactured by Vercules) Calcium stearate, 0.2-ester compound (Table-2) 0.1 Table-2 Example 2 To examine the stabilizing effect of the ester compound used in the present invention during high-temperature processing , after mixing the following formulations: 30
Extrusion processing was carried out at 0°C. The melt index (g/10
m1n) was measured. The results are shown in Table-3.

Polypropylene resin 100 parts by weight (Pro
fax 6501) Calcium stearate 0.2-ester compound (Table-3) 0.2 Table-3 *1,2 Table-2 Reference Example 3 The following formulation was kneaded at 150°C for 5 minutes with a mixing roll, and then Compression molding was performed for 5 minutes at 150°C and 180 kg/cj to a thickness of 1. I created an OM sheet.

This sheet was used as a 1010 x 20 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.

Formulation> Distearylthiodipropionate 0.3-ester compound (Table-4) 0.05Table-4 *1.2 Same as Table-2 Example 4 Same as Example 3 with the following formulation. Create a test piece,
A test similar to Example 3 was conducted. The results are shown in Table-5.

Combination> Ester compound (Table-5) 0.3Table-5 C1ls CH' *2 C+xll*sSCtH4COCHg-C-C
Iyo0CCJnSC+2H□H3 Example 5 Calcium stearate 1.0 Polyester compound (Table 6) 0.3 The above formulation was extruded at 200°C to create pellets, and the pellets were used for injection processing at 230°C. A test piece was prepared. 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. The results are shown in Table-6.

Table-6 *1,2 Table-2 Reference Example 6 Intrinsic viscosity 0.51 dl/g (25°C in chloroform)
50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide), 5 parts by weight of polymethyl fluoride, 2.5 parts by weight of polycarbonate, 3.0 parts by weight of titanium oxide,
and 0.3 parts by weight of an ester compound were added thereto, thoroughly mixed using a Henschel mixer, pelletized using an extruder, and then injection molded to prepare a test piece. This test piece was heated at 125° C. for 100 hours in an open gear, and the elongation and Izot impact value retention were measured. The results are shown in Table-7.

Table-7 *1 See Table-2 *2 See Table-5 Example 7 The following formulation was processed with a kneading roll to create a sheet with a thickness of 1 square inch. 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-8.

Blend> Polyvinyl chloride (vinyl 378) 100 parts by weight tricresyl phosphate 3.0 bisphenol diglycidyl 2.0 ether zinc stearate 0.8 barium stearate 0.4 barium nonyl phenate 0. 5 Octyl diphenyl phosphite 0.5 sorbitan monopalmitate 3.0 methylene bisstearylamide 0.3 functional ester compound (Table 8)
0.1 table-8

Claims (1)

[Scope of Claims] A stabilized synthetic resin composition obtained by adding a compound represented by the following general formula (I) to a synthetic resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, R_1, R_2 and R_3 each independently represent a hydrogen atom or an alkyl group, R_4 represents an alkyl group or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. l represents 0, 1 or 2, m and n indicate 1 or 2.)