JPS59113046A - Halogen-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition having extremely improved weather resistance, heat stability, and coloring prevention properties, obtained by blending a halogen-containing resin with a specific organic phosphorous compound and a specified piperidine light stabilizer. CONSTITUTION:100pts.wt. halogen-containing resin is blended with 0.01-5pts.wt., preferably 0.05-3pts.wt. organic phosphorous compound shown by the formula I or formula II (R1 is alkyl, alkenyl, or aryl; X is H, or Me1/2; R2 is R1 or X; Me is metal of IIa group or zinc; X and R2 may be linked to form >Me, or R1 and R2 may be linked to form alkylene, arylene, or group shown by the formula III; R3 is direct valence or alkylidene; R4, R5, R6, and R7 are H or alkyl) and 0.001-5pts.wt., preferably 0.005-1pt.wt. bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate as a specific piperidine light stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a stabilized halogen-containing resin composition, specifically, a stabilized halogen-containing resin composition containing a specific organic phosphorus compound and a specific piperidine-based light stabilizer. The present invention relates to an improved halogen-containing resin composition.

In general, halogen-containing resins such as vinyl chloride resins have poor stability against heat and light, and are susceptible to thermal decomposition mainly due to dehydrochlorination during hot molding, resulting in a decrease in the mechanical properties of processed products. , resulting in deterioration of color tone and significant disadvantages. Furthermore, even when agricultural films and the like are used outdoors for long periods of time, problems such as deterioration of color tone, decrease in strength, and decrease in transparency often occur, greatly impairing their practical use.

In order to overcome these drawbacks, various stabilizers have heretofore been used singly or in combination. For example, a certain degree of effectiveness can be obtained by blending various combinations of lead, calcium, barium, magnesium, zinc, cadmium, etc., organic tin compounds, organic phosphite compounds, Epoquin compounds, ultraviolet absorbers, etc. ing.

However, the effects of the conventionally used combinations have not been fully satisfactory, and the effects have been completely insufficient especially for use in agricultural materials that require a high degree of weather resistance.

In recent years, it has been proposed to use piperidine-based light stabilizers in various synthetic resins, but even when these compounds are used, their effects are not sufficient, and there are cases where they may adversely affect the colorability. There was a need for further improvement.

In view of the current situation, the present inventors have conducted extensive studies and found that (a) the following general formula (
0.01 to 5 parts by weight of at least one type of compound represented by I) or (■) and (b) 0.001 to 5 parts by weight of at least one type of piperidine light stabilizer at a constant percentage. The present invention was achieved by discovering that a halogen-containing resin composition has excellent weather resistance, thermal stability, anti-coloration properties, and the like.

1 l (wherein, R1 represents an alkyl group, alkenyl group, or aryl group, X represents a hydrogen atom or Meλ, and R2 represents R1
or X represents a group.

Me represents [[a group metal or zinc. Also, X and R2
may be combined with each other to represent Me, and R1 and R
2 are bonded to each other to form an alkylene group, an arylene group, or an alkylene group.Hereinafter, the composition of the present invention having the above-mentioned characteristics will be described in detail.

The above general formula (I) or (■) used in the present invention
In the organic phosphorus compound represented by R1゜R,,R
The alkyl groups represented by 9, R6, and R7 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, 6-butyl, amyl, 57-mil, hexyl, nclohekynyl, 2-ethylhexynyl, octyl, nonyl,
Decyl, dodecyl, tridecyl, tetradecyl, hexadenyl, octadecyl, eicosyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, etc., and the alkenyl group represented by R include octenyl, decenyl, Dodecenyl, ophtatecenyl, etc. are opened and Rlfi:b aryl groups include phenyl, tolyl, quinryl, 6-butylphenyl, di-tert-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl, dodecylphenyl, and the like.

The alkyritene group represented by R3 is methylidene,
Ethylidene, impropylidene, butylidene, octylidene, etc. are available.

Examples of group (a) metals represented by Me include calcium, barium, and magnesium.

When R1 and R2 combine with each other to represent an alkylene group or an arylene group, ethylene, 1,2-propylene, 1,
Examples include 3-propylene, 2,2-dimethyl-1,5-propylene, phenylene, and 6-butylphenylene.

Therefore, representative examples of the organic phosphorus compounds represented by the general formula (1) or (II) include the compounds shown in Table 1 below.

Table 1 No1gi 11 1 (CIBH370) P OCa '7. .

Haruka 2 nora5 4 5 1 (C18) 1370 SeOZn 8 Boiled 6 7 (C18H570keP-OH Goose 8 c18H,o-P(OH)2 /7fi9 (Cl2H250q p o Ca 210 (Cl8H,,0)P-0-zn V2&11 wild goose 12 ,・Go15 i14 Be15 617 618 , thread 19 no1n120 Bian 21 0 ．． 4622 ぢ25 t-C4,+(.

25, 26 t-C1 horse/29 Gallo 30% 61 562 1 CI8 upper i, -0-P-OI (■ The additive amount of these organic phosphorus compounds is carved into 100 car weight parts of L/F fat and 0601 ~5 quintillion parts, preferably 0.05
~3 parts by weight.

Shisada's piperidine light stabilizers used in the present invention include (A A ) bis(2,2,6,6-tetramethyl-4=piperidyl) sebacate (&B) bis(1,2,2, 6,6-bentamethyl-4
-piperidyl) sebacate (Three C)tetrakis(2,2,6,6-titramethel-4-piperidyl) -1,2,! 1.4-butanetetracarboxylate (應D))ris(2,2,6,6-tetramethyl-4-
piperidyl) nitrilotriacetate (Gan E) bis(1
,2,2,Is,6-bentamethyl-4-piperidyl)
-2-n-butyl-2-(3,5-di-th sj-4
-Hydroquine benzyl) malonate (bad F) bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl)-2,2-bis(s, 5
-tert-butyl-4-hydroquinebenzyl)malonate (5G)1.1'-bis(9-aza-3-ethyl-8.
A -3-ethyl-8,8°10,10-tetramethyl-1,5-dioxaspiro[
5,5]-3-undenlemethyl) hentaerythritol diphosphite (boiled I) 1-(2-hydroquinethyl) -2,2゜6
．． 6-tetramethyl-4-piperiditul/dimethyl succinate condensate (ya J) 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/tertiary-octylamine/cyanuric chloride Examples include condensates, especially compounds (A A ), (boiled B), (
Boiling C), (boiling D), (boiling G) and (boiling H) are highly effective and are preferred.

The amount of these piperidine light stabilizers added is 0.001 to 5 parts by weight, preferably 0.001 to 5 parts by weight, per 100 parts by weight of the resin.
005 to 1 part by weight.

Furthermore, when using a compound in which X is a hydrogen atom in the organic phosphorus compound, it may form a salt with the piperidine-based light stabilizer, and the use of these salts is naturally included in the present invention. .

In the present invention, various stabilizers commonly used for stabilizing halogen-containing resins can be used in combination. Examples of these other stabilizers include metal salts of organic acids, organic tin compounds, organic phosphite compounds, and evoquin compounds.

Examples of the carboxylic acids constituting the metal salt of an organic acid that can be used in the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexyl acid, myristic acid, balmitic acid, undenoleic acid, linoleic acid, linoleic acid, liluic acid, neodecanoic acid, oleic acid, stearic acid,
Isotecanic acid, isostearic acid, 12-hydroquine stearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid,
erucic acid, branzic acid and similar acids and tallow fatty acids,
mixtures of the above naturally occurring acids such as coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid,
Chlorobenzoic acid, toluic acid, salicylic acid, p-1-butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid, Examples include monobutyl maleate, monobutyl maleate, and nclohexane carboxylic acid.

Phenols are also useful as organic acids.

Examples: Evaphenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, ncrohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethylphenol, poly(di-penta)isopropylphenol , diisopropyl-m-cresol, butylphenol, isoamylphenol, inoctylphenol, 2-ethylhexylphenol, -1γnonylphenol, tenlephenol, t-dodecylphenol, L-octylphenol, octylphenol, isoamylphenol, octadecylphenol, diinbutylphenol,
Examples include methylpropylphenol, methyl-t-octylphenol, di-t-nonylphenol, and di-t-dodecylphenol.

The metal components include UB group metals such as zinc and cadmium, group 1a metals such as lithium, sodium, and potassium, and group 1a metals such as barium, calcium, magnesium, and strontium.

The amount of these metal salts added is 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the resin.

Evoquin compounds that can be used in the present invention include evoquinated natural oils such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fish oil, evoquinated fatty acid esters such as butyl and -octyl stearates, and pinylsochlohexene. Diepoxide, evoquinated polybutadiene, 6,4-evoquine cyclohexylmethyl-3゜4-
Examples include bisphenol type and novolac type epoxy resins obtained by reacting epoxylated hydrocarbons such as epoxy vv chlorohexane carboxylate, polyhydric phenols, and epichlorohydrin or methylepichlorohydrin.

As a bisphenol type epoxy resin, U, for example, Araldite 502 (manufactured by Ciba Geigy), Epoquine equivalent: 26
5-250), Araldite 508 (same; 400-45
5), Epicron 850 (manufactured by Inu Nippon Ink Chemical; 184
~194), Epicron 860 (same; 170~190)
, Epicor) 828 (manufactured by Shell; 184-194),
Epicote 864 (same: 230-270), Sumiepokin ELA, 128 (manufactured by Sumitomo Chemical; 184-194),
EP-4100 (non-electrified product; 180-200) etc. are used, and as a novolak type epoxy resin, for example, DE
N431 (manufactured by Dow; Evoquine equivalent: 172-179)
, DEN438 (same; 175-182), Epiclon N-740 (Inu Nippon Ink Chemical [; 170-190)
, Epicron N-680 (same; 220-240), C
IBAEPN 1139 (manufactured by Ciba Geigy; 172~
179), CIBAECN 1273 (same; approx. 22
5) etc.

The amount of these epoxy compounds added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin.

Examples of organic phosphite compounds that can be used in the present invention include dienyl decyl phosphite, triphenyl phosphite F., tris-nonylphenyl phosphite,
Tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis (neopentyl glycol) -1,+ -cyclohexane Dimethyl phosphite, distearyl pentaerythritol diphosphite, diintenyl pentaerythritol diphosphite, tris(lauryl-2-thioethyl)
Phosphite, tetratridecyl-1,1,3-)lis(2'-methyl-5'-6th-butyl-4'-oxyphenylene/L/)butane diphosphite, tetra(C12-C
15 mixed alkyl) 4.4'-inpropyritine diphenyl diphosphite, )'Js(4-oxyv-2.5
-6-buterphenyl) phosphite, tris(4
-oxy-3,5-di6-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-impropylidene diphenol polyphosphite Diphosphite, diphenyl group bis[4,4-n-butylidenebis(2-6th-butyl-5-methylphenol)]thiogetanol diphosphite, bis(octylphenyl)bis(4,4-n-butylidenebis(2-6th-butyl-5-methylphenol)) -5-butyl-5-methylphenol)) -1,6-hexanediol diphosphite, phenyl-4,4-isopropylidene diphenol, pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4, 4-lobed thylidene bis(2-5-butyl-5-methylphenol) diphosphite, tris(2
, 4-C tert-butyl-phenyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, diphenyltritenyl phosphite, phenyl di(tridecyl) phosphite, tris(2-cyclohexylphenyl) phosphite, cytridecyl phosphite, Ji (2
-cyclohexylphenyl) hydrogenated bisphenol A.
Diphosphite, cy(2,4-cy-tert-butylphenyl)cyclohexylphosphite, 2,4-cy-tert-butylphenyl O diisotenlphosphite, tris(butquinethoxyethyl)phosphite, diphenylandphosphite, bis( Examples thereof include 2-cyclohexylphenyl)andphosphite, bis(2,4-di-1-butylphenyl)andphosphite, bis(nonylphenyl)andphosphite, and dibenzylandphosphite.

The amount of these organic phosphite compounds added is 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin.
5 parts by weight.

Various plasticizers can be added to the composition of the present invention as required.

Examples of plasticizers that can be used in the present invention include dibutyl phthalate, diisononyl phthalate, butylbenzyl phthalate, dilauryl phthalate, dibutyl phthalate, dimethyl phthalate, diisodecyl phthalate, dioctyl tucrate, and dichlorohexyl phthalate, dioctyl adipate, and diisononyl adipate. , diisononyl adipate, dibutyl diglycol adipate and other adipates, tricresyl phosphate, tris(isopropylphenyl) phosphate,
Phosphates such as tributyl phosphate, triethyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, triethyl phosphate, other polyesters, tetrahydrophthalate, acelate, sebacate, stearic acid, citric acid and trimellitate series.

If an ultraviolet absorber is added to the composition of the present invention, the photostability can be improved, so it is possible to select and use these as appropriate depending on the purpose of use. These include benzophenone thread, benzotriazole type, salicylate type, substituted acrylonitrile type, etc.

It is also possible to add stabilizing aids commonly used in the compositions of the invention. For example, 2,6-di-7-butyl-p-cresol, dilaurylthiodipropionate,
Diphenylthiourea, phenylindole, thiocidalycol bis(aminocrotonate), pentaerythritol, dipentaerythritol, tris(hydroquinethyl)isocyanurate, nlupitol, mannitol,
Anilinoditeotriazine, melamine, bis-(dipentaerythritol) adipate, pt-butylbenzoic acid, tehydroacetic acid, zinc dehydroacetate, nonylphenoxypolyethoxyphosphoric acid, benzoic acid, cinnamic acid, dibenzoylmethane, stearoylbenzoylmethane , benzoylpentanoylmethane, etc.

Others as necessary, such as pigments, fillers, plate-out prevention agents, surface treatment agents, lubricants, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodegradation abrasions, infrared absorbers, processing Auxiliary agents, mold release agents, reinforcing agents, etc. can be included.

Examples of the halogen-containing resin used in the present invention include vinyl chloride homopolymer, polyvinyritine chloride, chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene 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-maleic anhydride terpolymer , vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-imbrene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer , vinyl chloride-urethane copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic branched ester copolymer,
(Pinyl-acryloni chloride) IJ-ru copolymer and the above resins and α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, etc. polyolefins and copolymers thereof,
Polystyrene, acrylic resin, styrene/and other monomers (
(e.g., maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-
Styrene copolymer, acrylic acid ester-butadiene-
Examples include styrene copolymers, methacrylic acid ester-butadiene-styrene copolymers, and blends with polyurethane.

Examples of the present invention will be given below to clarify the results of the present invention.

Example 1 A film with a thickness of 0.1 inch was prepared using a kneading roll using the following formulation. This film was tested for thermal stability at 190°C, initial colorability, and weather resistance using a weatherometer.

The results are shown in Table-2.

Blend> Polyvinyl chloride (Vinyl 37H) 100 Parts by weight Di-2-ethylhexyl phthalate 45 Tricresyl phosphate 5 Evoquin resin (Epicor) 828) 3゜Zinc stearate
0.6 barium stearate
0. ! 1 barium nonylphenate
0.5 octyl diphenyl phosphite)
0.5 Rubitan monobalmitate 2.0 Methylene bis stearylamide 0.5 Piperidine light stabilizer AC0.05 Organic phosphorus compound (Table 2) 0.2 Table
-2 Example The same test as in Example 1 was carried out except that the amount of υpiperidine light stabilizer was changed according to the following formulation.

The results are shown in Table 6.

Blend> Polyvinyl chloride (Vinicron 4000M-3) 1
00 parts by weight di-2-ethylhexyl phthalate 45
Triquinlinyl phosphate 5 Epicote 828 5Zn-
Laurate 0.5Ca-
Stearate 0.3Mg-
Octoate (1,5 ethylene bis stearylamide 0.3 fulvitan monostearate 2.
5 Tris (nonylphenyl) phosphite 0.6 Piveridine light stabilizer (Table 3) o, 1 Organophosphorus compound &1/&2 (1:1 commercial compound) 0.6 Table
3 Example 3 A sheet with a thickness of 1 mp was prepared by kneading roll processing using the following formulation and was tested for thermal stability at 190°C and weather resistance using a weatherometer. Table 4 shows the results.
Shown below.

<Composition> Polyvinyl chloride (Geon 1o5EP) 1 o
o kfikfMI calcium stearate
1.2 Zinc stearate
0.6 dipentaerythritol
0.5 piperidine light stabilizer (Table 4)
0.05 Table 4 Example 4 A sheet with a thickness of 1vn was prepared by kneading roll processing using the following formulation, and tests for thermal stability at 190°C and weather resistance using a weatherometer were conducted. Table 5 shows the results.
Shown below.

Compound> Polyvinyl chloride (Geon 105FJP 8)
100 heavy” 31’cu dioctyltin bis(in-octylthioglycolate) 2 stearyl alcohol
0.5 polyethylene wax
0.3 piperidine-based light stable cutting AC0,1

Claims (1)

[Claims] To 100 parts by weight of the halogen-containing resin, (a) the following general formula (1
) or at least one extraction of an organic phosphorus compound represented by ([1) 0. A halogen-containing resin composition containing cz ~ 5 weight units and (b) at least one specific piperidine light stabilizer from 0.001 to 5 weight units. l R1-0-P-0-X (1')-R2 1 Rnee0-P-0-X ([1) Summer (wherein, R1 represents an alkyl group, an alkenyl group, or an aryl group, and X is Represents a hydrogen atom or Me8, R2 is R
1 or a group represented by X. Me indicates a Ua group alloy region or zinc. Furthermore, X and R2 may be bonded to each other to represent) Me, or R1 and R2
are bonded to each other to form an alkylene group, an arylene group, or