JPH04173854A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain a chlorine-containing resin composition having excellent thermal stability and light-resistance and suitable for interior and exterior material for automobile, etc., by compounding a metal perchlorate, a hydrotalcite treated with perchloric acid or a silicate treated with perchloric acid. CONSTITUTION:The objective composition is produced by compounding 100 pts.wt. of a chlorine-containing resin (e.g. polyvinyl chloride) with (A) 0.001-5 pts.wt. (preferably 0.01-3 pts.wt.) of a perchloric acid metal salt and (B) 0.001-5 pts.wt. (preferably 0.01-3 pts.wt.) of a hydrotalcite treated with perchloric acid or a silicate (e.g. calcium silicate or magnesium silicate) treated with perchloric acid. The stabilizing effect can be remarkably improved by using the composition in combination with 0.1-5 pts.wt. of an organic acid salt of a metal such as Na, K, Ca or Mg.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a stabilized chlorine-containing resin composition, specifically, a chlorine-containing resin containing a metal salt of perchloric acid and a perchloric acid-treated hydrotal. The present invention relates to a chlorine-containing resin composition to which silicates or perchloric acid-treated silicate are added.

[Prior art and problems to be solved by the invention] Chlorine-containing resins tend to undergo thermal decomposition mainly due to dehydrochlorination when subjected to heat molding, and this causes deterioration of the mechanical properties of processed products. , resulting in deterioration of color tone and significant disadvantages.

In order to avoid such disadvantages, it is necessary to add one or more heat stabilizers to the resin to suppress deterioration during processing.

Conventionally, metal salts of various organic or inorganic acids,
Combinations of several types of organic tin compounds have been used, and almost satisfactory results have been obtained in terms of thermal stability.

However, combinations of these various metal salts, such as Cd/Ba system, Ba/Zn system, Ca/Zn system, Ba
/Ca/Zn type etc., performance such as colorability is not sufficient, and various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds,
The use of phenolic compounds, β-diketone compounds, etc. has been proposed, but it is still not sufficient, and furthermore, when lined with polyurethane or polypropylene, such as in automobile interior materials, or with steel plates, the use of phenolic compounds, β-diketone compounds, etc. The thermal coloring property when low-temperature heat is applied is not sufficient, and there is a need for further improvement.

In recent years, among inorganic acid metal salts, metal salts of halogen oxyacids have been found to be particularly effective in improving coloring properties, and can be used in combination with metal salts of the above-mentioned organic or inorganic acids, organotin compounds, etc. It is proposed to do so. For example, JP-A-5
3-13659 proposes the combination of a basic inorganic acid salt and a halogen oxyacid, and JP-A-58-122951
JP-A-61-34042 proposes the combination of hydrotalcite i and halogen oxyacid, and JP-A-61-34042 proposes the combination of aluminosilicate having a zeolite structure and halogen oxyacid. .

It has also been proposed to use perchloric acid treated hydrotalcites and perchloric acid treated silicates.

For example, in JP-A-59-140261, hydrotalcite a treated with perchloric acid was proposed;
1-78874 and JP-A-61-113636 propose silicate treated with perchloric acid, but the stabilizing effect is still insufficient and is not practically satisfactory. Ta.

[Means to solve the problem]

In view of the above-mentioned current situation, the present inventors have conducted various studies and found that (a) at least one metal salt of perchloric acid and (b) perchloric acid-treated hydrotalcite or perchloric acid are added to the chlorine-containing resin. It has been discovered that a significant stabilizing effect can be obtained by adding at least one type of chloric acid-treated silicate,
This has led to the present invention.

Hereinafter, the chlorine-containing resin composition of the present invention will be explained in detail.

Examples of metal components constituting the metal salt of perchloric acid used in the present invention include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, cadmium, lead, and aluminum. The metal salt may be anhydrous or hydrated. Further, it may be dissolved in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrated product thereof.

The amount of these metal salts of perchloric acid added is 10% of the chlorine-containing resin.
0 parts by weight, 0.001 to 5 parts by weight, especially 0.0 parts by weight
1 to 3 parts by weight is preferred.

The perchloric acid-treated hydrotalcite used in the present invention is a perchloric acid-modified product in which part and all of the carbonic acid in the hydrotalcite compound is replaced with perchloric acid. The above hydrotalcite compound is a carbonate double salt compound of magnesium and/or zinc and aluminum, and these are
Contains natural hydrotalcite and synthetic hydrotalcite.

Synthetic hydrotalcite is a compound represented by the following formula, and the ratio of magnesium and zinc to aluminum can be changed arbitrarily, and the amount of crystal water contained can also be changed arbitrarily depending on the degree of heat dehydration. be able to.

Mgy+Zn,zAlx・(OH)z・(COt)x
zz·mHzO (where x, y, and y2 each represent a number that satisfies the conditions expressed by the following formula, and m represents O or any positive number.

0<x≦0.5, y++Vz=1 x, 0.1≦y+
<1.0≦y2<0.8) The perchloric acid-treated silicates used in the present invention include silicate metal salts such as calcium silicate, magnesium silicate, barium silicate, and zinc silicate, and various silicate clay mineral acids. Examples of treated products include natural or synthetic silicates such as kaolin, bentonite, mica powder, talc, diatomaceous earth, acid clay, activated clay, and zeolite, which are treated with an aqueous perchloric acid solution. Among silicates, calcium silicate, magnesium silicate, barium silicate, kaolin, bentonite, talc,
Acid clay, activated clay, and processed products of zeolite are preferred.

These perchloric acid-treated hydrotalcites or perchloric acid-treated silicates can be produced, for example, by adding hydrotalcite or silicates to a dilute aqueous solution of perchloric acid and stirring, or by adding hydrotalcites or silicates to a dilute aqueous solution of perchloric acid and stirring. Add a concentrated aqueous solution of perchloric acid and stir, then filter, if necessary.
It can be easily produced by dehydration or drying.

The molar ratio of hydrotalcite or silicate to perchloric acid can be set arbitrarily, but in general, 0.1 to 1 mol of perchloric acid to 1 mol of hydrotalcite or silicate.
It is preferable to use a ratio of 2 moles.

The amount of the perchloric acid-treated hydrotalcite or perchloric acid-treated silicate to be added is preferably 0.001 to 5 parts by weight, particularly 0.01 to 3 parts by weight, per 100 parts by weight of the chlorine-containing resin.

In addition, the metal salt of perchloric acid, perchloric acid-treated hydrotalcite, or perchloric acid-treated silicate used as a stabilizer in the present invention can be separately blended into the chlorine-containing resin, but they can be mixed together. It can also be used as
In this case, it can also be used as a so-called composite stabilizer containing other stabilizer components as required.

Examples of chlorine-containing resins used in the present invention include the following. For example, polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, Polymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl, cycloalkyl or aryl Maleimide 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 copolymer Original copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-urethane copolymer chlorine-containing resins such as
and the above chlorine-containing resin and an α-olefin polymer such as polyethylene, polypropylene, polybutene, poly-3-methylbutene or an ethylene-vinyl acetate copolymer,
Polyolefins such as ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene Examples include copolymers, methacrylic acid ester-butadiene-styrene copolymers, and blends with polyurethane.

In addition, the composition of the present invention contains Li, K, Na, Mg,
Sr, Ca+Ba+ Zn, cd, Sn, p
By using an organic acid salt of a metal such as b in combination, the stabilizing effect is significantly improved.

This organic acid salt may be a normal salt, a basic salt, or an overbased salt.

As the organic acid residue constituting the above-mentioned organic acid salt, carboxylic acids, phenols, acid phosphates, acid phosphites, etc. are useful.

Examples of the carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid,
Stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, benzoic acid,
Monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid , m carboxylic acids such as acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sepacic acid, maleic acid, Divalent carboxylic acids such as fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, or monoester or monoamide compounds thereof, Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, pyromellitic acid, and the like.

Examples of the above phenols include phenol, cresol, xylenol, methylpropylphenol, methyl tert-octylphenol, ethylphenol, isopropylphenol, tert-butylphenol, n-butylphenol, diisobutylphenol, isoamylphenol, cyamylphenol, isohexylphenol. ,
Examples include octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, cyclohexylphenol, and phenylphenol.

Examples of the above acid phosphate i include mono/distearyl acid phosphate, mono/diphenylacinodophosphate, mono/dinonylphenyl acid phosphate, and the like.

Examples of the acid phosphites include phenyl acid phosphite, nonylphenyl acid phosphite, octyl acid phosphite, stearyl acid phosphite, and the like.

The amount of these metal salts of organic acids added is 100% of the chlorine-containing resin.
0.01 to 10 parts by weight, especially 0.1 to 10 parts by weight
5 parts by weight is preferred.

Furthermore, an alkyltin stabilizer can be used in combination with the composition of the present invention.

Examples of the above-mentioned alkyltin stabilizers include mercaptides, malates, laurates of mono/dimethyltin, mono/dibutyltin, mono/dioctyltin, singly or as a mixture.

The amount of these alkyltin stabilizers added is 1
0.00 parts by weight, 0.01 to 10 parts by weight, especially 0.00 parts by weight.
1 to 5 parts by weight is preferred.

The composition of the present invention further includes an organic phosphite compound and/or
Or, when used in combination with an epoxy compound, an excellent synergistic effect is exhibited.

Examples of the organic phosphite compounds include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono- , dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2.2゛-methylenebis(4゜6-ditert-butylphenyl)octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri- (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite,
Trilauryl trithiophosphite, bis(neopentyl glycol)/1,4-cyclohexane dimethyl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl -4,4“
-isopropylidene diphenol/pentaerythritol diphosphite, tetra(C22-15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis(4,4”-n-butylidenebis(2-tert-butyl-
5-methylphenol)] 1,6-hexanediol diphosphite, tetratridecyl 4,4゜-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl) 1.1.3
-Tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane and triphosphite.

The amount of these organic phosphite compounds added is preferably 0.01 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

In addition, the above-mentioned epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized raw brain oil, epoxidized castor oil, epoxidized safflower oil, and epoxidized linseed oil. Butyl fatty acids, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris(epoxypropyl) isocyanurate, 3-(2-xenoxy)-1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A di Examples include glycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene dieboxide, 3°4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, and the like.

The amount of these epoxy compounds added is 100% of the chlorine-containing resin.
0.01 to 20 parts by weight, especially 0.5 to 20 parts by weight
The amount is preferably 10 parts by weight.

When the composition of the present invention is further combined with a polyhydric alcohol compound, an excellent synergistic effect is exhibited.

Examples of the polyhydric alcohol compound include pentaerythritol, dipentaerythritol, sorbitol, mannitol, pentaerythritol or dipentaerythritol stearic acid half ester, bis(
Dipentaerythritol) adipate, glycerin, tris(2-hydroxyethyl)isocyanurate, and the like.

The amount of these polyhydric alcohol compounds added is preferably 0.1 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin.

When the composition of the present invention is further combined with a nonmetallic stabilizing agent, an excellent synergistic effect is exhibited.

Examples of the nonmetallic stabilizing aid include dehydroacetic acid, dihenzoylmethane, stearoylhendiylmethane, and ester-containing β-diketone compounds as β-diketone compounds.

The amount of these nonmetallic stabilizing aids is 10% of the chlorine-containing resin.
It is preferable to set it as 0.001-1 weight part with respect to 0 weight part.

The composition of the present invention may contain ester plasticizers such as phthalate plasticizers, adipate plasticizers, polyester plasticizers, phosphate plasticizers, chlorine plasticizers, and other plasticizers. It can be used as appropriate depending on the purpose.

In addition, as inorganic compounds, synthetic talcites, calcium phosphate, magnesium phosphate, etc. can be used in combination as appropriate depending on the purpose.

If a photostabilizer is added to the 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, benzotriazole,
Included are salicylates, substituted acrylonitriles, hindered amines, various metal salts or metal chelates, especially nickel or chromium salts or chelates.

Furthermore, in order to obtain a non-toxic or low-toxic chlorine-containing resin composition, it is possible to select and use a non-toxic or low-toxic one from among the above-mentioned commonly used organic acid metal salts. A chlorine-containing resin composition with good properties can be obtained.

In addition, if necessary, the composition of the present invention may include, for example, a crosslinking agent, a filler such as calcium carbonate or barium sulfate, a pigment, a foaming agent, an antistatic agent, an antifogging agent, a plate-out inhibitor, a surface treatment agent, and a lubricant. , a flame retardant, a fluorescent agent, a fungicide, a bactericide, a photodegradant, a processing aid, a mold release agent, an antioxidant, and the like.

The stabilized chlorine-containing resin composition of the present invention can be used in a variety of processing methods and applications.

Examples of this processing method include calendar processing, extrusion processing, injection processing, blow processing, powder slush processing, paste processing, casting processing, and other processing methods.

Applications include automobile interior and exterior materials, steel plate construction materials, marking films, hard sheets, plates, pipes, profile extrusion products, wrap films, agricultural films, flooring materials, leather, wallpaper,
Examples include tarpaulins and chlorine-containing resin products made by Shinkin Banks.

[Example] Next, the stabilizing effect of the composition of the present invention will be specifically shown by Examples. However, the invention is not limited to the examples listed below. Example 1 The following formulation was roll-kneaded and then press-worked to produce a sheet with a thickness of 1 m. About this sheet, 12
The colorability after heat aging at 0°C for 4 days and the thermal stability at 190°C were measured.

The results are shown in Table 1 below.

<Formulation> Weight parts Polyvinyl chloride resin 100 Di(C9-,,)alkyl phthalate 50 Epoxidized soybean oil
3Ba-Olate
0.8Zn-Metatoluate 0
．． 4 tetra(C+□-1, alkyl)・0.4
Bisphenol A diphosphite dibenzoylmethane 0.05 Barium perchlorate 0.2 1st
Table #: Compounding amount of barium perchlorate d: DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) / Perchloric acid = 110.5 mol Processed product Book 2: DHT 4A (manufactured by Kyowa Chemical Industry Co., Ltd.)
/ Perchloric acid - 1/1 mole treatment rate 3: DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) /
Perchloric acid = 1/1.5 mole treated product *4: Alkamizer-4 (manufactured by Kyowa Chemical Industry Co., Ltd.) /
Perchloric acid = 1/1 mole treated product Book 5: Magnesium silicate / perchloric acid - 1/1 mole treated product *6: Calcium silicate / perchloric acid - 1/1 mole treated product *7: Zeolite I -4A/perchloric acid = 1/1 mole treated product The coloring property after heat aging was evaluated on a scale of 10, with 1 indicating no discoloration and 10 indicating extremely significant discoloration.

Example 2 A test similar to Example 1 was conducted using the following formulations.

The results are shown in Table 2 below.

<Formulation> Weight parts Polyvinyl chloride resin 100 Di(Cq-++) alkyl phthalate 50 Epoxidized soybean oil
3Ba-Olate
0.8 Zn-metatoluate 0.4 Tetra(C+□-15 alkyl)・0.4 Bisphenol A diphosphite dibenzoylmethane 0.05 sample
20.1 Perchlorate (Table 2) (Table 2)
2 Table #: Blend amount of sample 2 Example 3 The following blend was roll-kneaded and then press-processed to produce a sheet with a thickness of 1 inch. About this sheet, 19
Thermal stability at 0°C was measured.

Further, this sheet was set in a mold, and the urethane foam polyol and polyisocyanate were stirred and quickly poured into the mold to form a urethane foam layer, thereby creating a urethane backing sheet (urethane foam layer 10 mm thick).

Using this urethane backing sheet, 110"C x 400
The coloration (heat aging resistance) after time heat aging and the coloration (light resistance) after 600 hours of light irradiation in a fade meter with a black panel temperature of 83°C were observed, ranging from 1 (no coloration) to 1.
It was displayed on a scale of 10 to 0 (severely colored).

The results are shown in Table 3 below.

<Composition> Weight parts Polyvinyl chloride resin 100 di(Ca-+□Dealle) phthalate 70 Epoxidized soybean oil
3.0 Calcium carbonate 2
0 Titanium oxide 10 Zinc octylate 0.5 Barium stearate 1.0 Barium perchlorate
0.1 Sample compound (Table 3) 0.1 Table 3 #: Blend amount of barium perchlorate 8: Silicic acid it lL't'y A / perchloric acid = 11
0.5 mol processed product *9: Barium silicate/perchloric acid = 11
0.5 mol treated product *10; Zeolite 4A/Perchloric acid-
110.5 mol processed product Example 4 A thick laminate was prepared as in Example 1 using the following formulation:
Create a + sheet and set the temperature to 120°C for this sheet.
and thermal stability at 190°C.

The results are shown in Table 4 below.

Blend> Part by weight Polyvinyl chloride resin 50ABS resin
5ONBR10 Epoxidized soybean oil 10 Barium stearate 0.8 Zinc laurate
0.4 barium perchlorate
0.1 Sample compound (Table 4) 0.1 Table 4 #: Blend amount of barium perchlorate *2 Blend amount of sample 1 or sample 7 Example 5 Obtained by uniformly dispersing the following compound. paste sol,
Apply to a thickness of 0.5cm on a stainless steel plate and heat at 200°C.
Cure for 5 minutes. The obtained sheet was set in a mold, and the polyol for urethane foam and polyisocyanate were quickly stirred and poured into the mold to form a urethane foam layer with a thickness of 10 rIm, thereby producing a urethane backing sheet.

Using this sheet, a heat aging test was conducted at 110°C.
Coloring was observed over time.

The results are shown in Table 5 below.

Formulated: Part by weight Calcium carbonate 10 Epoxidized linseed oil
4 Phenyl ditridecyl phosphite 1.0 Barium oleate 0
．． 6 Zinc tert-butylbenzoate 0.3 Barium perchlorate 0.1 Sample compound (
Table 5) 0.1 Table 5 #: Blend amount of barium perchlorate Example 6 The following formulations were mixed in a Henschel mixer to create a powder compound. This powder compound was made into a thickness of 3 circles and gelled in a gear oven at 230"C for 4 minutes to produce a sheet with a thickness of 1.8 mm. This sheet was tested for thermal stability in the same manner as in Example 3. , heat aging resistance and light resistance tests were conducted.

The results are shown in Table 6 below.

<Composition> Part by weight Polyvinyl chloride resin 90 Polyvinyl chloride resin for paste 10 Tri (C7-9 alkyl)
trimellitate 70 epoxidized soybean oil
5 Titanium dioxide 10
Zinc octylate 0.3 Barium stearate 1.0 Sample 20
．． 5 Sample 70.1 Perchlorate (Table 6) (Table 6) No.
Table 6 [Effects of the invention] When a metal salt of perchloric acid is added alone, the effect of improving thermal stability (heat aging resistance) and light resistance at relatively low temperatures is observed to some extent, but it is still insufficient. However, the effect of improving thermal stability at high temperatures is only small.

In contrast, at least one of a metal salt of perchloric acid and a perchloric acid-treated hydrotalcite or a perchloric acid-treated silicate
The composition of the present invention in which seeds are used in combination has better thermal stability at high temperatures, thermal stability at relatively low temperatures (heat aging resistance), and light resistance than would be expected from the results when these are added alone. It is clear that the effects of the present invention are extremely specific.

Patent applicant: Asahi Denka Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] Adding (a) at least one metal salt of perchloric acid and (b) at least one of perchloric acid-treated hydrotalcite or perchloric acid-treated silicate to a chlorine-containing resin. A stabilized chlorine-containing resin composition.