JPS5815550A - Stabilized halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. useful for heat forming, prepared by adding a hydrotalcite and a trihydric or higher alcohol compd. to a halogen- contg. resin. CONSTITUTION:Hydrotalcite of the formula (where 0<X<=0.5; A is CO3, SO4; m is a real number) which is a hydrous double salt. consisting of Mg and Al, and a trihydric or higher alcohol compd. (e.g. glycerol) are added to a halogen-contg. resin (e.g. polyvinyl chloride). The hydrotalcite and alcohol compd. are added in amounts of 0.01-10, pref. 0.05-5pts.wt. each to 100pts.wt. resin. An organic or inorganic acid salt of metal may also be added to the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a stabilized...
The present invention relates to a stabilized norogen-containing resin composition containing a polyhydric alcohol compound having a higher valence or higher.

Halogen-containing resins tend to undergo thermal decomposition mainly due to removal of hydrogen and halogenation during heat molding.
This causes deterioration of the mechanical properties and color tone of processed products, resulting in significant disadvantages. In order to avoid such disadvantages, it is necessary to add one or more kinds of heat stabilizers to the synthetic resin to suppress deterioration during processing steps.

Conventionally, various fatty acid metal salts or phenol metal salts have been used for this purpose. As a result, almost satisfactory results were obtained in terms of thermal stability. However, [7] In recent years, these metal salts, especially cadmium salts, have had serious toxicity problems;
Its use is severely restricted. For this purpose, various combinations of metal salts other than cadmium salts are used, such as Ba/Zn series, Cd/Zn series, Ba/Ca/Z.
N series etc. have been proposed. However, its performance is not sufficient, and various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, and β
-The use of diketone compounds, ultraviolet absorbers, etc. has been proposed.

In recent years, the use of hydrotalcites having a specific crystal structure as a stabilizer for halogen-containing resins has been proposed (Japanese Unexamined Patent Publication No. 80445/1983).

However, hydrotalcites have a neutralizing effect as a stabilizing effect and also have a deoxidizing effect and promote the dehydrochlorination reaction, so their use is severely limited. It also has the disadvantage of imparting color to the resin.

In view of the current situation, the present inventors have conducted various studies on P.
The inventors have now completed the present invention by discovering that a significant stabilizing effect can be obtained when hydrotalcites and a polyhydric alcohol compound having a valence of 3 or more are used in combination.

That is, the present invention provides a stabilized halogen-containing resin composition comprising a halogen-containing resin blended with hydrotalcites and a trihydric or higher polyhydric alcohol compound.

The composition of the present invention will be explained in detail below.

The hydrotalcites used in the present invention are hydrous double salt compounds consisting of magnesium and aluminum represented by the following general formula [I].

Mg1-, Alx(OH)2 Ax72・mH20(1
) (-In the above formula, X is 0 (a real number in the range of x≦0.5, A represents CO3 or SO4, and m represents a real number.

) The above hydrotalcites may be natural products,
It may be a synthetic product. Examples of the synthesis method include known methods such as those disclosed in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 5-300!19, and Japanese Patent Publication No. 51-29129. Further, in the present invention, it can be used without being restricted by its crystal structure or crystal particle size. Also,
The surface was coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acid ester, or a wax. You can also use things.

Therefore, the amount of the hydrotalcites used is o, o1 to 10 parts by weight, based on 100 parts by weight of the halogen-containing resin.
Preferably it is 5 to 5 parts by weight of O.

Furthermore, as the trihydric or higher polyhydric alcohol compound in the present invention, various compounds can be used without limitation, such as trimethylolethane, trimethylolpropane, glycerin, 2-hydroxymethyl-3-methylbutane-1,S-
diol, 3-methylpentane-1,5,5-)diol, tris-(2-hydroxyethyl)in cyanurate, hexane-1,2,6-)diol, 2-hydroxymethyl-2-methylbutane-1, 3-diol, 2.
4-dimethyl-5-hydroxymethylpentane-2,a
-Diol, pentaerythritol, diglycerin, ditrimethylolethane, citrimethylolpropane, 2
12.6.6-titramethylolcyclohexanol,
Cichentaerythritol, inositol, mannitol,
Examples include sorbitol.

Therefore, the amount of the polyhydric alcohol compound used is o, oi to 10 parts by weight, based on 100 parts by weight of the halogen-containing resin.
Preferably it is 0.05 to 3 parts by weight.

It goes without saying that metal organic acid salts (ordinary metal soaps) may be used in combination with the composition of the present invention. Examples of metal components in this case are Ll, Na, K,
Examples include Mg, CaXBa, Zn, Sn, Sr, etc., and organic acid residues include the following carboxylic acid and phenol residues.

Examples of carboxylic acids include acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, dinandoic acid, caprylic acid, neodeca/acid, 2-ethylhexylic acid, be2urgonic acid, capric acid, undecanoic acid, diuric acid, tridecanoic acid, myristic acid, valmitic acid, isostearic acid, stearin. acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-tar
t-Butylbenzoic acid, dimethylhydroxybenzoic acid, 3
, 5-ditart-butyl-4-hydroxybenzoic acid,
Toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N
-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, P-tart-octylsalicylic acid, oleic acid,
Monocarboxylic acids such as elaidic acid, linoleic acid, linuric acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sepatic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid , monoesters or monoamide compounds of divalent carboxylic acids such as itaconic acid, aconitic acid, thiodipropionic acid, etc., and monoesters or monoamide compounds of divalent carboxylic acids such as itaconic acid, aconitic acid, thiodipropionic acid, etc.; Examples include di- or triester compounds.

Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, inoctylphenol, and 2-ethylhexylphenol. ,tert
-nonylphenol, tert-
Examples include octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, cyamylphenol, methylisohexylphenol, and methyl-t-octylphenol.

In addition, the above metals (Li, Na, K% Mg, Ca
, Ba, Zn, Sn, Sr, etc.) can also be suitably used in combination, and examples of the inorganic salts of these metals include MgO.
, ZnO etc., Ca(,0H)2, Mg(O
Examples include hydroxides such as H)2, Ba(OH)2, phosphates, phosphites, nitrates, and sulfates.

An excellent synergistic effect is exhibited by further using an organic phosphite compound and/or an epoxy compound in the composition of the present invention.

The organic phosphite compounds that can be used in the present invention include:
Diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, l-lis (
dinonylphenyl) bosphite, l-lilauryl trithiophosphite, trilauryl phosphite, bis(
(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisotecylben erythritol diphosphite, diphenyl acid phosphite, tris(lauryl-2-thioethyl) phosphite, tetratridecyl -1,1,5-)lis(2-methyl-5-tert-butyl-4-oxyphenyl)buta/diphosphite, tetra(C12-C1,a combined alkyl)4,4-inpropylidene diphenyl diphosphite , Tris(4-
oxy-2,5-di-5-tert-butyrunenyl) phosphite, tris(4-oxy-5,5-di-5-t-ruphenyl)phospha-f), 2-ethylhexyldiphenyl phosphite, tris(mono- , dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isoglopylidene diphenol polyphosphite, diphenyl bis[
:4.4-n-butylidene bis(2-tert-butyl-5-
methylphenol)] Thiogetanol diphosphite, bis(octylphenyl) bis[4,4'-n-butylidenebis(2-5-butyl-5-methylphenol))-1,6-hexanediol diphosphite , phenyl-4,4-isopropylidenediphenol pentaerythritol diphosphite, phenyldiisodecylbosphite, tetratridecyl-4,4-n-butylidenebis(2-5th-butyl-5-methylphenol) diphosphite, tris( Examples include 2゜4-di-6-butylphenyl) phosphite.

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 polybutadiene, epoxy methyl stearate, -butyl , -2 ethylhexyl, -stearyl, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid butyl, 5-(2-xenoxy)-1,2-epoxypropane, bisphenol -A diglycidyl ether, vinylcyclohexene dieboxide, dicyclopentadiene dieboxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate, and the like.

The amount of these epoxy compounds added is 0.01 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the resin.

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 appropriately select and use these depending on the purpose of use. These include benzophenone series, benzotriazole series, salicylate series, substituted acrylonitrile series, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine series, piperidine series, and the like.

Furthermore, in order to obtain a non-toxic polymer containing No-Ritin, it is possible to select and use a non-toxic one from the above-mentioned commonly used metal soaps. A combined composition is obtained.

Others may be added as necessary, such as crosslinking agents, normal phases, fillers, foaming agents, anti-banding agents, antifogging agents, pre-fouling prevention agents, etc.
Surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, bactericidal agents,
Metal deactivators, photodegradants, processing aids, mold release agents, reinforcing agents, and the like can be included.

Examples of halogen-containing heavy compounds used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride,
Chlorinated polyethylene, chlorinated polypropylene, odorized polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, chlorinated Vinyl-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride- Isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinyritine chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, thickened vinyl-malein dispersion ester copolymer, Halogen-containing synthetic resins such as vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acryloni copolymer, internally plasticized polyvinyl chloride, and the above halogen-containing resins with polyethylene, polypropylene, polybutene, poly-3- α-olefin polymers such as methyl butene or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, 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 blended products with styrene copolymers and methacrylic acid ester-butadiene-styrene copolymers.

The following examples demonstrate the effectiveness of the halogen violet-containing binding agent composition according to the present invention.

The present invention is limited by these examples-C
Vj, no.

Example 1 The following composition was mixed in 11 mm, and then pressed to produce a sheet with a JV diameter of 1 mm. Using this Sea 1-, initial colorability, transparency, and thermal stability at 190°C were examined. The results obtained are shown in Table 1.

<Blend> Polyvinyl chloride 1 fat 100 Parts by weight Di-sealed chilluntalate 50 Epoxidized linseed oil 1.0 Zinc stearate
0.5 Pariuno Stearic Acid 0.
7 Hydrotalcite compound 90.1 Polyhydric alcohol compound (Table 1) 0.2*
(abbreviated as T'DIET-4A) 1st
Table Example 2 A sheet with a thickness of 1 m was prepared in the same manner as in Example 1 using the following formulation, and the heat stability at 190°C, initial colorability,
The elongation and tensile strength after deterioration at 120° C. for 280 hours were measured. The results obtained are shown in Table 2.

Blend> Polyvinyl chloride resin 50 parts by weight A
BS resin 5゜NBR1゜Epoxidized soybean oil 1゜Calcium stearate 1.0 Zinc stearate 0.5DHT-4A
O,2 polyhydric alcohol compound (Table 2) 0.2 Table 2 Example 3 Using the following formulation, a sheet with a thickness of 1 cup was prepared in the same manner as in Example 1, and heated at 190°C. Thermal stability and initial coloration were investigated. The results obtained are shown in Table 5.

<Formulation> Polyvinyl chloride resin 100 parts by weight Zinc stearate 0.5 Barium stearate 0.5 Dibutyltin malate polymer 0.2 Dibeni/taerythritol Skin 590 Example 4 Organic phosphite compound added to the composition of the present invention When used in combination, an even greater stabilization effect was obtained. The effects were investigated in the same manner as in Example 1 using the following formulations. The results obtained are shown in Table 4.

<Blend> Polyvinyl chloride resin 100 Parts by weight Dioctyl ntalate (DOP) 50
Epoxidized soybean oil 2.0 Zinc octylate 0.5 Calcium stearate 0.5 Di (T-4
A O,5 Sorbitol 0.1 Organophosphite Compounds Table 01) 0.1 Table 4 Example 5 In order to investigate the effect of using other stabilizing aids in combination with the composition of the present invention, the following formulation was prepared. A sheet with a thickness of 1 mm was prepared in the same manner as in Example 1 using the same material, and a thermal stability test at 180°C was conducted. The results of the survey are shown in Table 5.

<hself combination> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 5 Magnesium stearate 0,2 Calcium stearate 0.5 Zinc stearate 0.5 Mgo, 75A1o,
25(OH)2(C05)o, t25・o, 6! +H2
00-1 Jibe/Taerythritol
0.1 Other stabilization aids (Table 5)
Table) Table 5

Claims (1)

[Claims] A stabilized halogen-containing resin composition comprising a halogen-containing resin mixed with 21-hydrotalcites and a trivalent or higher polyhydric alcohol compound.