JPS5827735A - Stabilized halogen-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition that contains a combination of a hydrotalcite and a specific polyhydric alcohol partial ester, thus preventing deterioration and showing remarkably improved stability. CONSTITUTION:(A) 100pts.wt. of a halogen-containing resin are conmbined with (B) 0.01-5, preferably 0.1-1.0pt. of hydrotalcite, (C) 0.005-10, preferably 0.01- 5pts. of a polyhydric alcohol monocarboxylic acid partial ester that is prepared from tri- or more hydric alcohol and di- to hexacarboxylic acid or a mixture thereof with a monocarboxylic acid, thus having at least one hydroxyl. Further, a combination of an organophosphite with an epoxy compound is preferably added.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a stabilized halogen-containing resin composition, more specifically, a stabilized halogen-containing resin composition comprising a halogen-containing resin mixed with hydrotalcites and a partial ester of a polyhydric alcohol having a valence of 5 or more. The present invention relates to a halogen-containing resin composition.

Halogen-containing resins tend to undergo thermal decomposition mainly due to dehydrohalogenation reactions during heat molding.
This results in disadvantages such as deterioration of the physical properties of processed products and deterioration of color tone. In order to avoid such disadvantages, one or more heat stabilizers have conventionally been added to the resin.

Various fatty acid metal salts or phenol metal salts have been used for this purpose. However, the metal salt alone cannot satisfy the technical challenges of the industry, and in recent years, toxicity problems have been widely discussed, and its use has been severely restricted.

For this purpose, a method of using various combinations of various metal salts, and furthermore, other stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphite compounds, organic sulfur compounds, I-diketone compounds, ultraviolet rays, etc. The combined use of absorbents and the like has been proposed. However, for example, when polyhydric alcohol is used in combination, or Hatrysnonylphenyl phosphite is used in combination, although the transparency is improved, the stabilizing effect is insufficient, and when epoxidized soybean oil is used in combination, the thermal stability is only slightly improved. However, it does not fully satisfy the industry, as it has the drawback of lowering the softening point.

Furthermore, in recent years, it has been proposed to use Mg/Al composite inorganic acid salts (hydrotalcites) having a specific crystal structure as a stabilizer for halogen-containing resins (%Kokai No. 55-80445). However, scissor hydrotalcites have both a neutralizing effect as a stabilizing effect and a deoxidizing effect as a degrading effect, and therefore their use is severely limited because they promote the dehydrochlorination reaction. . In addition, it has the disadvantage 4 of imparting color to the resin.

In view of the current situation, the present inventors have conducted various studies, and as a result, have discovered that a combination of hydrotalcites and a partial ester of a polyhydric alcohol of 3 or more valences produces a remarkable stabilizing effect, and has completed the present invention. This is what I did.

That is, the present invention provides a halogen-containing resin containing (1) hydrotalcites, and (2) a polyhydric alcohol having a valence of 5 or more and a 2- to 6-valent polycarboxylic acid, or the polyhydric carboxylic acid and 1
The object of the present invention is to provide a stabilized halogen-containing resin composition containing a polyhydric alcohol partial ester compound having at least one hydroxyl group made of a mixed acid with a hydric carboxylic acid.

The present invention will be described in detail below.

The hydrotalcites in the present invention have the following general formula [1
) is a hydrous double salt compound consisting of magnesium and aluminum.

Mg1-, AIx(OH)2AX/2・mH2O(
In the above formula, X is 0 (a real number in the range of x≦0.5, and A
represents CO3 or SO4, and m represents a real number. ) The hydrotalcites may be natural products or synthetic products. As a synthesis method, for example, Japanese Patent Publication No. 46-2
No. 280, 50-! No. 50059, No. 51-2912
A known method such as No. 9 can be exemplified. Further, the hydrotalcites in the present invention can be used without any restriction on the crystal particle size, and furthermore, the surface thereof may be coated with higher fatty acids such as stearic acid, higher fatty acids, higher fatty acid esters, wax, or the like.

The amount of the above-mentioned hydrotalcites used is 0.01 to 5 parts by weight, preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the resin.

In addition, the partial ester of a polyhydric alcohol having a valence of 5 or more in the present invention can be prepared by a known method such as a polyhydric alcohol and a inferior equivalent of a divalent to hexavalent polycarboxylic acid, or a mixture of the polyhydric carboxylic acid and a monohydric carboxylic acid. It can be easily obtained by reacting with That is, the wrinkled ester contains at least one hydroxyl group in the molecule.

Examples of the polyhydric alcohol of the partial ester include trimethylolethane, trimethylolpropane, glycerin, 2-hydroxymethyl-5-methylbutane-1,
5-diol, 5-methylpentane-1,5,5-triol, tris-(2-hydroxyethyl)in cyanurate, hexano-1,2,6-)diol, 2-hydroxymethyl-2-methylbutane-1 ,3-diol,
2.4-dimethyl-3-hydroxymethylpentane-2
, 4-diol, pentaerythritol, diglycerin, ditrimethylolethane, citrimethylolpropane, 2,2゜6.6-teto2methylolcyclohexanol, cyhentaerythritol, inositol, mannitol, sorbitol, polybentae, lythritol, etc. can give.

Examples of monovalent carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enylic acid, caprylic acid, neooctanoic acid, 2,-ethylsilic acid, benzurgonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, nistic acid, palmitic acid, isostearic acid,
Stearic acid, 2-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-t
ert-butylbenzoic acid, dimethylhydroxybenzoic acid, 5,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid,
Cumic acid, n-propylbenzoic acid, aminobenzoic acid, N
, N-dimethylaminobenzoic acid, acetoxybenzoic acid,
Examples include salicylic acid, P-tert-octylsalicylic acid, oleic acid, diacidic acid, linoleic acid, lylunic acid, thioglycolic acid, mercaptoboupionic acid, and octylmercaptopropionic acid.

Examples of 2 to 6@ polyhydric carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 3-methylphthalic acid, 2-methylisophthalic acid, cyphthalic acid, dioxyphthalic acid, aminophthalic acid, aminoterephthalic acid, dioxyphthalic acid, Dihydric carmenic acids such as 5-chlorophthalic acid and chlorterephthalic acid, aromatic polyhydric carboxylic acids such as heimellitic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid, and mellitic acid, Schella acid, ironic acid,
Conolic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sepatic acid, malic acid, maleic acid, falic acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, tartaric acid ,
i-denodiacetic acid-butan-1,2,5-)ricarmenic acid,
Propane-1,2,is-tricarmenic acid, butene-1
,2,5-)licarboxylic acid, citric acid, acetyl citric acid, nitrilotriacetic acid, nitrilotripionic acid, tris(cartoxyethyl)isocyanurate, butane-
1゜2.15.4-tetracarboxylic acid, pentane-1゜5,! To 1,5-teto-2-carmenic acid, 1,1,2,2-ethannat-2-carmenic acid, 1,2,2,5-propane tetracarboxylic acid, ethylenediaminetetraacetic acid, 5-bicyclo(2,2,1) Butene-2゜5-dicarmenic acid,
5-bicyclo[”2.2.2]]octene-2,3
-7-bicyclo dicarmenic acid (2,2,211 octene-2,5,5,6-tetracarboxylic acid, 1,6,8.1
4-tetradecanetetracarboxylic acid, 1,6,7,8,
Examples include aliphatic polycarboxylic acids such as 9,14-tetradecanehexacarmenic acid.

Next, Table 1 shows typical examples of carboxylic acid partial esters of polyhydric alcohols in the present invention.

Table 1 The amount of the partial ester of the polyhydric alcohol according to the present invention added is from o, oos to 10 parts by weight, preferably from 0.01 to 5 parts by weight, based on 100 parts by weight of the resin.

When an organic phosphite compound and/or an epoxy compound are further used in the composition of the present invention, an excellent synergistic effect is exhibited.

Organic phosphite compounds that can be used in the present invention include:
Diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris (2-ethyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl 7tCX phosphite, bis(
neopentyl glycol)-1,4-cyclohexane dimethyl diphosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite, tris(2uryl-2-thioethyl) phosphite, tetratridecyl -1,1,3-)lis(l-methyl-?-
5-butyl-4'-oΦdiphenyl)butane diphosphite, tetra(C12-015 mixed alkyl)-4,4
'-isopropylidene diphenyl diphosphite, tris(4-o-2,5-di-tert-butylphenyl) phosphite, tris(4-o-5,5-di-tert-butylphenyl χ phosphite, 2- Ethylhexyl diphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4,!-isopropylidene diphenol phosphite, diphenyl bis[
4,4'-n-butylidene bis(2-5-butyl-5-
Methylphenol)] Thiogetanol diphosphite, bis(octylphenyl) bis[4,! -n-butylidene bis(2-5-butyl-5-methylphenol)
]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-a,! -n-butylidene bis(2-5-butyl-5-methylphenol) diphosphite, tris(2°a-c-5-butylphenyl) phosphite, and the like.

The amount of these organic phosphite compounds added is 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin.
It is 3 parts by weight.

Epoxy compounds that can be used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized polypucdiene, methyl distearate in Evo, -butyl, -2 ethylhexyl, -stearyl, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized Vi dibutyl fatty acid, 5-(2-7)-1, Examples include 2-epoxybutane, bisphenol-A diglycidyl ether, vinylcyclohexene dieboxide, dicyclobentadiene dieboxide, and 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecal M palm acylate.

The amount of these epoxy compounds added is 0.01 to 101 parts by weight per 100 parts by weight of the resin. Lid part, preferably 0.5~
5 parts by weight.

The polymer composition of the present invention may contain a phthalate plasticizer or other ester plasticizer, a polyester plasticizer, a phosphate plasticizer, a chlorine plasticizer, or other plasticizer depending on the purpose. Can be used as appropriate.

Adding an antioxidant to the polymer composition of the present invention can increase the oxidative deterioration prevention properties of the polymer composition, so it can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like.

If an ultraviolet absorber is added to the polymer 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 benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts, metals, chelates, especially nickel or chromium salts or chelates, triazines, piperidines, and the like.

In order to obtain a more non-toxic halogen-containing polymer, K is
If a non-toxic one is selected from among the above-mentioned commonly used metal soaps, a halogen-containing polymer composition that is non-toxic and has good thermal stability can be obtained.

Others as necessary, such as crosslinking agents, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, narrowing agents, lubricants, flame retardants, fluorescent agents, antifungal agents, and sterilization agents. agents, metal deactivators, photodegradants, processing aids, shipshapes, reinforcing agents, and the like.

Examples of the halogen-containing polymer used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl heptadide, polyvinylidene chloride,
Chlorinated polyethylene, chlorinated polypropylene, 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-vinylidene 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-maleic acid ester copolymer, chloride Halogen-containing synthetic resins such as vinyl-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polybutene, poly-
Oα-olefin polymers such as 5-methylbutylene or polyolein such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and these O copolymers, polystyrene, acrylic resin, styrene and other monomers (e.g. anhydrous (maleic acid, butadiene, acrylonitrile, etc.), acrylic axtrilubutadiene/-styrene y copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-
Examples include blended products with ethylene copolymers.

The following examples show the effects of the halogen-containing resin composition according to the present invention, but the present invention is not limited to these examples.

Example 1 The following formulation was roll-kneaded and then pressed to produce a sheet with a thickness of 1 slI. Using this sheet, initial colorability, transparency, and thermal stability at 190°C were examined. The results are shown in Table 2.

<Composition> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate (DOP) s
.

Epoxidized soybean oil 2.0 Zinc stearate 0.5 Barium stearate 0.5 Polyhydric alcohol partial ester (Table 2) 0.2 2nd
Table Example 2 A sheet was prepared in the same manner as in Example 1 using the following formulation, and then heat stability at 190c, initial colorability and
The elongation and tensile strength were measured after aging at ℃ for 280 hours. The results are shown in Table 5.

Blend> Polyvinyl chloride resin 50 parts by weight Human BS resin 5ONB
R10 Epoxidized soybean oil 10 Tetra (012-15 mixed alkyl) bis 1.0 Phenol A diphosphite calcium stearate 1.0 Zinc stearate 0.5 DHT
-4A 0.3 polyhydric alcohol partial ester S'ld 0.2
3 Table Example 3 A thickness of 1-
A sheet was prepared, and its thermal stability and initial colorability at 190°C were examined. The results are shown in Table 4.

Blend> Polyvinyl chloride resin [100 parts by weight Zinc stearate 0.5 Barium stearate 0.5 Diptyltin malate polymer 0.1 1st fIuI
i5 Compound 0.5 Hydrotalcite b--fi41 0.2 Example 4 When an organic phosphite compound was used in combination with the composition of the present invention, a further stabilizing effect was obtained. A sheet with a thickness of 1 inch was prepared in the same manner as in Example 1 using the following formulation, and its effects were investigated. The results are shown in Table 5.

<Blend> Polyvinyl chloride resin 100 parts by weight diotatylphthalate (DOP) s.

Epoxidized soybean oil 5 Zinc octylate 0.5 Nonylphenol barium 0.3 Calcium stearate 0.5 DHT - 4 people
0.3 1st shallow mu 12 compound
0.1 organic phosphite compound (ll1g510
0.1 Table 5 Example 5 In order to examine the effect of using the composition of the present invention in combination with other stabilizing aids, a sheet was prepared in the same manner as in Example 1 using the following formulation. Thermal stability at 180°C was investigated. The results are shown in Table 6.

Blend> Polyvinyl chloride resin 100 Parts by weight Evo-life treated linseed oil 5 Zinc stearate 0.5 Calcium stearate 0.5 Magnesium stearate 0.2'go,y,"o,2
5(OH)2(CO,). , 12.・0.5H200
, 15 Table 1 Compound 1 0.
1 Other stabilizing aids (Table 6) Table 6

Claims (1)

[Claims] From a halogen-containing resin, (1) hydrotalcites, and (2) a trivalent or higher polyhydric alcohol and a divalent to hexavalent polycarboxylic acid or a mixed acid of a polycarboxylic acid and a monocarboxylic acid. A stabilized halogen-containing resin composition comprising a polyhydric alcohol partial ester compound having at least one hydroxyl group.