JPS6281454A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To improve effectively the resistance to heat and weather, processability, etc., of synthetic resins, by blending an ester compd. having a specified group in the molecule with a synthetic resin. CONSTITUTION:An ester compd. of formula I (wherein R is a group of formula II or III, etc.; R2 is an alkyl, phenyl; R3, R4 are each H, an alkyl, phenyl; a, lare each 0, 1, 2; m is 1, 2; p is 1, 2, 3; q is 0, 1, 2; p+q is 3; X is -O-, -S-; R1 is a 1-18C alkyl) in a quantity of 0.001-5wt% is blended with a synthetic resin such as polyethylene, polypropylene, etc., to stabilize the resin. The compd. of formula I can be easily synthesized, e.g., by reaction a trialkanol phosphine oxide with an acid or an ester. Examples of the compd. of formula I are those of formulas IV, V, etc.

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, weather 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]

Polyethylene, polypropylene, AB8. It is known that synthetic resins such as polyvinyl chloride deteriorate due to the action of heat and light, becoming colored 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, special public Sho 3B-12312
The publication proposes the use of dialkyl e-alkyl hydroxyphenylalkyl phosphonates 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 obtained by adding an ester compound represented by the following general formula (1) to a synthetic resin.

0(X) (R-co-R, R10H)9(1) represents a phenyl group, R9 and R11 each independently represents a hydrogen atom, an alkyl group, or a phenyl group, or represents 1,! is 0,
m represents 1 or 2, p represents 1, 2 or 3, q represents 0, 1 or 2, and s p+q is 5. X represents 10- or -8-, and R1 represents an alkylene group having 1 to 18 carbon atoms. ) The present invention will be explained in more detail below.

In the above general formula (j), the alkyl groups represented by R2, R, and R1+ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, 5-butyl, 37-mil, octyl, and 5-octyl. , nonyl, decyl, cyclohexyl, 1-methylcyclohexyl, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and the like.

The alkyl group represented by R7 is methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl,
Examples include octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, tocosyl, tetradecyl, triacontyl, and the like.

Examples of the alkylene group represented by R1 include evamethylene, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-
Butylene, hexamethylene, octamethylene, decamethinone, 1,5-hexylene, 1,4-hexylene, 1-
Isopropyl-4-methylhexylene LL5-
) Dimethyl-1°7-hebutylene, 2,6-dimethyl-1,8-octylene, and the like.

Next, represented by the general formula (I) used in the present invention, -5= Specific examples of compounds are shown in Table 1.

Table-1 t-0, R3 &13 ■ (06H1, BO2H, Coo, H6%PA 15
0 ■ (012H2,SC!2H,4Coo3)I6-)7F
A 1 7 ■ (C16~18H5u~5ry5c2aIIaoa, a6
), -pA19 0
0 The amount of the above-mentioned ester compound used is 100% of the synthetic resin.
It is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.

Furthermore, 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 trialkanolphosphine or trialkanolphosphine oxyto with an acid or an ester. A specific example is shown below.

Synthesis Example 142 (Table-1) Synthesis of Compound Tris(hydroxypropyl)phosphine 20.8 t
(o, 1 mol) ts-(3,s-di-t-butyl-4
-Hydroxyphenyl)methyl propionate 102 t
(0.55 mol) and 1.2 t (1% by weight) of sodium methoxide as a catalyst were mixed and reacted at 120° C. for 1 hour under a nitrogen atmosphere.

Then, the pressure was gradually reduced to remove methanol.

After confirming the completion of the reaction using the R spectrum, unreacted raw materials were distilled off to obtain the desired product as a pale yellow grease-like substance.

The engineering R of the product is ν. H: 3650ei-”, ν.Eng.=1720cIM-1.ν(H-0-0: 1150
oIn, ν(3H: 8750131.

Synthesis Example 2 Synthesis of A4 (Table-1) Compound Tris(hydroxypropyl)phosphine oxide 22.4 t (o, 1
The desired product as a glassy solid was obtained in the same manner as in Synthesis Example 1 using mol).

:H 172017M"", ν: 121 cm-'
, c-o-c :P=O 1150 scratches, ν. -H: 8753.

Synthesis Example 3 Synthesis of Compound A15 (Table 1) 20.8 t (0.1 mol) of tris(hydroxypropyl)phosphine, 84 t (a, s mol) of laurylthiopropionic acid and 1.0 t (a, s mol) of paratoluenesulfonic acid as a catalyst. 2F was mixed and reacted at 120° C. for 1 hour under a nitrogen atmosphere. Next, the pressure was gradually reduced to perform dehydration. After confirming the completion of the reaction with the R spectrum, neutralize the catalyst with Na, Co,
Washed with water. Unreacted phosphine was distilled off under reduced pressure and a white powder with a melting point of 33 to 38°C was obtained by cooling. Engineering R
Hashi. H: 295o and 2900rs-1°ν. Engineering.

: 1735ω, ν. -0-o: It was 117 ozono.

Synthesis Example 4 Synthesis of A19 (Table 1) Compound Tris(hydroxypropyl)phosphine oxide 22.4 y (o
, 1 mol), and in the same manner as in Synthesis Example 5, a grease-like target product was obtained.

The IR of the product is ν. H=293o and 2860cIn-
1゜νO=O” 1720cm, c-0-(3
: 1130 cm.

Examples of the synthetic resins stabilized by the present invention include polyethylene, polyglobylene, polybutene, poly-5
- 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 polyglopylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-imbutylene Copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Vinyl-acrylic ester copolymer, chloride and vinyl-
Maleic acid ester 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 ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, methacrylate resins such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal , polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, polyphenylene oxide, cellulose resin, or phenol resin, area resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. . Furthermore, it may be a blend of rubbers such as isogrene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, or cholera resin.

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 well-known phenolic antioxidants to the compositions of the present invention. Examples of these phenolic antioxidants include 2
, 6-di-6-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl-(3,5-cymethyl-4-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy −
3,5-di-tert-butyl phenyl)gropionate, distearyl-5,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2.4.6-)lis(3/,
s/-di-5-butyl-4'-hydroxybenzylthio)-1,5+"-triazine, distearyl(4-
Hydroxy-6-methyl-5-37''thyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6
= tertiary butylphenol), 4,4'-methylenebis(
2,6-di-5-butylphenol)%212'-methylenehis(6-(1-methylcyclohexyl)p-cresol), bis[3,5-bis(4-hydroxy-5-
tert-butylphenyl)butylinkandcoglycol ester, 4,4'-butyryzombis (6-5-5-butyl-m-cresol), 2,2'-ethylidene bis(4,
6-di-tert-butylphenol L212'-ethylidene bis(4-tert-butyl-6-tert-butylphenol),
1,1゜3-tris(2-methyl-4-hydrochloride 5
-5-tert-butylphenyl)butane, bis[:2-tert-butyl-4-methyl-6-(2-hydroxy-5-fg'5
f-thyl-5-methylbenzyl)phenyl]terephthalate, 1,3.5-)lis(2,6-dimethyl-5-hydroxy-4-tert-butyl)benzyl isocyanurate, 1,5r5-1' lis(3, 5-tert-butyl-
4-hydroxybenzyl) -2s4+6-) listylbenzene, tetrakis[methylene-5-(5,5-di-tert-butyl-4-hydroxyphenyl)gropionate]methanes L's5- tris(6,5-di-tert. 3-butyl-4-hydroxybenzyl)incyanure)
, 1,5,5-tris((3,5-di-tert-butyl-4
-hydroxyethyl)globionyloxyethyl]isocyanurate, 2-octylthio-4,6-di(4-hydroxy-5,5-di-tert-butyl)phenoxy-1,
7-enols such as 3,5-) riazine, 4,4′-thiobis(6-tert-butyl-m-cresol), and 4,4
'-Butylidene bis(2-tert-butyl-5-methylphenol) carbonate oligoester (for example, degree of polymerization 2.3.
Examples include polyhydric phenol carbonate oligoesters such as 4, 5, 6, 7, 8, 9, 10, etc.).

It is also possible to add a well-known 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) (Example 1)
; l'pentaerythritol tetralauryl thioglopionate).

Light resistance and heat resistance can be improved by further adding a phosphite or phosphonite compound 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(
nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)
-1,1,3-tris(2-methyl-5-5-butyl-
4-Hydroxyphenyl)butane diphosphite, tetra('12~□, mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl)-4,4'-butylidene bis(3-methyl-6
-tJ5butylphenol) diphosphite, tris(
S,S-di-5-butyl-4-hydroxydiphenyl) phosphite, tris(mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-(sogropylidene diphenol polyphosphite, bis(octyl) phenyl)
・Bis(a,a'-butylidenebis(3-methyl-6-
-116-hexanethiol cyphosphite, phenyl 4.4'-477'ropylidene diphenol pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite phyto, bis(2,6-di-5-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(4,4'-isopropylidene bis(2-5-butylphenol)) phosphite,
cy(nonylphenyl)pentaerythritol diphosphite, a,, 4'-isopropylidene bis(2-37'thylphenol) 11 di(nonylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl) - Examples include 4,4'-biphenylene diphosphonite.

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
-7 types of hydroxybenzophenones such as octoxybenzophenone, 2,2'-cyhydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone%2
-(2'-hydroxy-5'-1-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(
2'-hydroxy-S/, S/-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(
2'-hydroxy-57-methylphenyl)benztriazole, 2-(2'-hydroxy-3/,5/-di-
benzotriazoles such as t-amylphenyl)benzotriazole, phenylsalicylate), pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-monobutyl-4-hydroxybenzoate, Benzoates a, 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 N1(s,5-di-t-
Nickel compounds such as butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester N1 salt, bis(2,2
, 6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-bentamethyl-4-piperidyl)-n-butyl-3, S-di-tert-butyl-4-
Hydroxybenzyl-malonate, bis(1-acryo
yl-2゜2.6.6-tetramethyl-4-piperidyl)bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, tetrakis(2,2,Is,6-tetramethyl-4- piperidyl)butane-1,2,5゜4
-tetracarboxylate, 1- and droxyethyl-2
, 2,6,6-tetramethyl-4-piperiditul/diethyl succinate condensate, cyanuric chloride/tertiary octylamine/1,6-bis(2,2゜6.6-tetramethyl-
piperidine compounds such as 4-piperidylamino)hexane condensates, substituted acrylonitriles such as methyl α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate, and UN-2-ethylphenyl-N'-2- ethoxy
Examples thereof include oxalic acid dianilides such as 5-tert-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 The following formulation was blended in a mixer for 5 minutes, and then a compound was made in an extruder (cylinder 21 temperature 230°C and 240°C, head die temperature 250°C).
, rotational speed 2 Orpm).

Using this compound 95 x 40 x I I
A test piece of I was made using an injection molding machine (cylinder temperature 2
40℃, nozzle temperature 250℃, injection pressure 475V-2)o
Thermal stability of the obtained test piece was measured in a gear oven at 160° C., and the degree of yellowness (%) of the test piece after 72 hours of headlight irradiation was measured using a Hunter colorimeter. The results are shown in Table-2.

Blend> Calcium stearate 0.20
．． 2 Ester compound (Table-2) 0゜1 Table-2 Example 2 A test piece was prepared in the same manner as in Example 1 using the following formulation, and the same test as in Example 1 was conducted. Table-3
0 <Formulation> Calcium stearate 0.2 Table -
3 1i 012H2,0002H,5o2H,0001,,H2
゜012H2,502H,000H2-0-OH200
02H, 5o12H2゜cs.

25-Example 5 The following formulation was kneaded with a mixing roll at 150°C for 5 minutes, and then compressed for 5 minutes at 150°C and 18Ob/1s20 to create a sheet with a thickness of 1.0 mm. . 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> Distearylthiodiglobionate 0.3-ester compound (Table-4) 0.05 Table-4 Example 4 A test piece was prepared in the same manner as in Example 5 with the following formulation,
A test similar to Example 3 was conducted.

The results are shown in Table-5.

Blend> Ester compound (Table 5) 0.3 1. $2
Same as Table 3 Example 5 Calcium stearate 1.0 Polyester compound (Table 6) 0.3 The above formulation was extruded at 200°C to create a pellet,
Using this pellet, injection processing was performed at 230°C to prepare a test piece. The degree of coloration of this test piece after being heated for 50 hours at 135° C. in an open gear was expressed as the degree of whiteness measured with a Hunter colorimeter. Furthermore, the impact value of the test piece at 20°C was also measured. The results are shown in Table-6.

Table 6 Example 6 The following formulation was processed using a mixed wire roll to create a sheet with a thickness of 1U. Using this sheet, thermal stability and initial colorability tests at 190°C were conducted. A weather resistance test was also conducted using a weatherometer. Table 7 shows the results.
Shown below.

<Composition> Polyvinyl chloride (Viniriki! 17H) 1oo
Parts by weight Di-2-ethylhexyl phthalate 45 Tricresyl phosphate 6.0 Zinc stearate 0.8 Varicum stearate 0.4 Barium nonyl phenate 0.5 Octyl diphenyl phosphite 0.5 Sorbitan monopalmitate 3 .0 Methylenebisstearylamide 0.3-ester compound (Table-7) o, 1Table-7

Claims (1)

[Claims] A stabilized synthetic resin composition obtained by adding an ester 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 -(CH_2)-_nS-R_5 R_2 represents an alkyl group or a phenyl group, R_3 and R_4 each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and R_5 represents an alkyl group or ▲There is a numerical formula, chemical formula, table, etc.▼.a represents 0 or 1, l represents 0, 1 or 2, m represents 1 or 2, p represents 1, 2 or 3, q represents 0, 1 or 2, and p+q is 3 x represents -O- or -S-, and R_1 has 1 to 1 carbon atom.
18 alkylene groups are shown. )