JPH03126745A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, capable of producing marked stabilizing effects, remarkably improved in thermal stability, heat aging resistance and light resistance by adding antimony pentoxide and a metal salt of perchloric acid to a chlorine-containing resin. CONSTITUTION:A composition obtained by blending a chlorine-containing resin with antimony pentoxide and at least one metal salt of perchloric acid. Stabilizing effects are remarkably improved by further blending a salt, such as Li, K or Na, of an organic acid (carboxylic acid or phenol) therewith. An organic phosphite compound or epoxy compound may be blended. The amounts of the components based on 100 pts.wt. chlorine-containing resin are preferably 0.1-5 pts.wt. antimony pentoxide and 0.01-3 pts.wt. metal salt of perchloric acid.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a stabilized chlorine-containing resin III or a chlorine-containing resin by adding antimony pentoxide and a metal salt of perchloric acid. The present invention relates to a chlorine-containing resin composition.

[Problems to be solved by the prior art and the invention] Chlorine-containing resins tend to undergo thermal decomposition, mainly due to dehydrochlorination, when subjected to heat molding, and as a result, the mechanical properties of processed products deteriorate. This causes deterioration and deterioration of color tone, resulting in 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 Cd1Ba 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,
Although the use of phenol compounds, β-diketone compounds, etc. has been proposed, it is still not sufficient and there is a need for further improvements.

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,
3-1.3659 proposes the combination of a basic inorganic acid salt and a halogen oxyacid, and JP-A-58-12295
Publication No. 1 proposes a combination of Hydrotalzi+1 and a halogen oxyacid, and JP-A-61-34042 proposes a combination of an argonosilicate having a zeolite structure and a halogen oxyacid. However, the stabilizing effect was still insufficient and unsatisfactory for practical use.

Measures to Solve the Problem c] In view of the above-mentioned current situation, the present inventors have conducted various studies and found that (a) antimony pentoxide and (b)
The present invention was achieved based on the discovery that a significant stabilizing effect was obtained by adding at least one metal salt of perchloric acid.

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

Antimony oxides include trioxide, tetroxide, and pentoxide, and these are used as flame retardants for synthetic resins, but antimony dioxide, which is the most widely used, is used to achieve the purpose of the present invention. is completely inadequate and only antimony pentoxide is effective.

The amount of antimony pentoxide added is preferably 0.01 to 20 parts by weight, particularly 0.1 to 5 parts by weight, per 100 parts by weight of the chlorine-containing resin.

In addition, the metal components constituting the metal salt of perchloric acid used in the present invention include lithium, sodium, potassium 1
, magnesium, calcium, strontium, barium, zinc, cadmium, lead, aluminum, etc., and these metal salts of perchloric acid may be anhydrous or hydrated. Furthermore, the metal salt of perchloric acid used in the present invention includes perchloric acid-treated hydrotalcite obtained by treating a metal salt of an inorganic weak acid such as hydrotalcite or a modified product thereof with perchloric acid. .

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.

Further, the antimony pentoxide and perchloric acid metal salts used as stabilizers in the present invention can be individually blended into the chlorine-containing resin, but they can also be used as a mixture. It can also be used as a so-called composite stabilizer containing other stabilizer components if necessary.

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 loop 1.1 Pyrene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene copolymer
Maleic anhydride terpolymer, vinyl chloride-alkyl,
Cycloalkyl or arylmaleimide 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-
Chlorine-containing resins such as maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-urethane copolymer, and the above chlorine-containing resins, polyethylene, polypropylene, polybutene , poly-3-methylbutene and α
- Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile) etc.), acrylonitrile-butadiene-styrene copolymers, methacrylic acid ester-butadiene-styrene copolymers, and blends with polyurethane.

In addition, the composition of the present invention contains Li, K, Na, Mg,
By using an organic acid salt of a metal such as 5rCa, Ba, Zn, Cd, Sn, or Pb, the stabilizing effect is significantly improved.

The organic acid residues constituting the above organic salt include carboxylic acid,
Phenols etc. are useful.

Examples of the carboxylic acids include acetic acid, propionic acid, acetic acid, valeric acid, caproic acid, enanic acid, caprylic acid, nemedecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, and tridecane acid. Acid, rhistic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, hehenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, lilunic acid, thioglycolic acid, mercapdobu [
1pionic acid, octylmercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5 di-tert-butyl-4-
1'-loki dibenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid,
Monovalent carboxylic acids such as acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, schelic acid, azelaic acid, cehatic acid, maleic acid, fumaric acid acids, divalent carboxylic acids such as citraconic acid, methaconic acid, iconic acid, aconitic acid, thiodipropionic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, or their monoesters or monoamide compounds, butane Examples include di- or l-lyester compounds of trivalent or tetravalent carboxylic acids such as tricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, and biromellitic acid.

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

The amount of these metal salts of organic acids added is 10% of the chlorine-containing 4Z resin.
0.01 to 10 parts by weight, especially 0.01 to 10 parts by weight. ]
~5 Heavy objects are dangerous.

Each time the Jl acid compound (of the present invention) is used in combination with an organic phosphite compound and/or an epoxy compound, a more excellent synergistic effect is exhibited.

Examples of organic phosphite compounds include triphenylphosphate, nibutylphenyl)phosphite, 1,1-lis(nonylphenyl)phosphite, l-lis(dinonylphenyl)phosphite, tris(mono-, di- mixed nonylphenyl) phosphite, diphenyl acid phosphite l-,
2.2'-methylenebis(46-di-tert-butylphenyl)octylphospha・fl・, diphenyldecylphosphite, phenyldiisodecylphosphite]・, tridecylphosphite, tos(2-Konichi J Shihexyl) phosphite I, tridecyl phosphite], tridecyl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl 1-lithiophosphite, bis(neopentyl glycol) 1 4-
Cyclohexanedimethyldiphosphite, bis(2.4
-ditert-butylphenyl) to penquerythritol diphosphite, distearylbentaerythritol diphosphite 1-, phenyl 4 4 -isopropylidene diphenol penquerythritol diphosphite 2-15 mixed alkyl) -4.4" - Isopropylidene diphenyl diphosphite, hydrogenated-4,4'isopropylidene diphenol polyphosphite, bis(octylphenyl).bisC4,4'n-butylidene bis(
2-tert-butyl-5-methylphenol)] ・1.6
-Hexanediol diphosphite, tetratridecylbutylidene bis(2-tert-butyl 5-butylphenol) diphosphite, hexa(tridecyl) 1. ,
1. 3-1 Lis(2-methyl-5-butyl-4-
Examples include hydroxyphenyl)butane-1-liphosphite.

The amount of these organic phosphites 1 to 1 to 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 chloride-containing resin.

The epoxy compounds that can be used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil,
Epoxidized 1-l oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, 1-Lis(epoxypropyl) isocyanurate, 3-(2-xenoxy)-1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene dieboxide, dicyclopentadiene dieboxide , 34-epoxycyclohexyl 6-methylepoxycyclohexanecarboxylate, and the like.

The amount of these epoxy compounds added is preferably 0.01 to 20 parts by weight, particularly 0.5 to 10 parts by weight, per 100 parts by weight of the chlorine-containing phase fat.

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.

If a light stabilizer is added to the m-paraboloid of the present invention, the light stability can be improved, so it is possible to appropriately select and use these depending on the purpose of use.

These light stabilizers include hensifenones, hensitriazoles, salicylates, substituted acrylonitriles, hindered acrylonitriles, various metal salts or metal chelates, especially nickel or chromium salts or chelates, and the like.

If necessary, the composition of the present invention may include, for example, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an antiplate-out agent, a surface treatment agent, a lubricant, a flame retardant, a fluorescent agent, etc. ,
Antifungal agents, fungicides, photodegradants, nonmetallic stabilizers, processing aids,
A mold release agent and the like can be included.

[Example] Next, the stabilizing effect of the composition of the present invention will be specifically illustrated by Examples. However, the invention is not limited to the following examples.

Example 1 The following formulation was roll-kneaded and then pressed to produce a sheet with a thickness of 1 + nm. Regarding this sheet, the colorability after heat aging at 120°C for 3 days and the coloring property after heat aging at 190°C
Thermal stability was measured at

The results are shown in Table 3.

<Composition> Weight parts Polyvinyl chloride resin 100 di(C9-51) alkyl tucrate 50 Epoxidized soybean oil
3Ba-Olate
0.8Zn--Metatoluate
0.4 tetra(C,□-15 alkyl)・0.
4 bisphenol A diphosphite dibenzoylmethane barium perchlorate sample compound (Table 1) 0゜0゜5 0゜Table The colorability after heat aging is evaluated on a scale of 10, and 1 means no discoloration. 10 indicates that the coloring is extremely significant.

Example 2 The following composition was roll-kneaded and then pressed to produce a sheet with a thickness of 1 m+n. The thermal stability of this sheet at 190°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-backed sheet 1- (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.
It was displayed on a scale of 10 to 0 (severely colored).

The results are shown in Table 2 below.

<Composition> polyvinyl chloride resin Di (Ce-+z dearle) Epoxidized soybean oil calcium carbonate titanium oxide zinc octylate, Weight part 00 Phthalate 70 3.0 0 0 0.5 5 barium stearate Antimony pentoxide (Sb20.) Perchlorate (Table 2) No. table Comparative example 2 In 4, instead of antimony pentoxide = Antimony # was used.

In Example 2-7, DHT-4A (synthetic hydrotalcite manufactured by Kyowa Chemical) was used.

Example 3 A thickness of 1 m was prepared as in Example 1 using the following formulation:
A sheet of M was prepared, and the thermal stability of this sheet at 120°C and 190°C was measured.

The results are shown in Table 3.

Blend> Part by weight Polyvinyl chloride resin 50ABS resin
5ONBR10 Epoxidized soybean oil 10 Barium stearate Zinc laurate Barium perchlorate Sample compounds (Table 3) 0.8 0.4 0.1 1, 0 Table 3 Example 4 The following formulation was uniformly dispersed. The paste sol obtained by
Apply Q to a thickness of 5 mm on a stainless steel plate and hold at 200°.
C. for 5 minutes. The obtained sheet was placed in a mold, and the urethane foam polyol and polyisocyanate were stirred and quickly poured into the mold to form a urethane foam layer having a thickness of 10 mm, 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 4.

<Formulation> Parts by weight Calcium carbonate Epoxidized linseed oil Phenyl ditridecyl phosphite Barium octylate Tert-butyl benzoate Zinc antimony pentoxide Perchlorate metal salt (Table 4) 0 Table Comparative Example 4 In 4, Antimony trioxide was used instead of antimony pentoxide.

Example 5 The following formulations were mixed in a shell mixer to create a powder compound. This powder compound was made into a thickness of 3 mm and gelled for 4 minutes in car ozone at 230° C. to prepare a sheet with a thickness of 8 mm. This sheet was tested for thermal stability, heat aging resistance, and light resistance in the same manner as in Example 2.

The results are shown in Table 5.

Compounding> Part by weight Polyvinyl chloride resin 90 Polyvinyl chloride resin for Pace F- 10 Tri (C,, alkyl)
trimellitate 70 epoxidized soybean oil
5 Titanium dioxide 10
Zinc octylate 0.8 Barium stearate 1. 〇Antimony pentoxide 2. 0 Perchlorate (Table 5) 1.0 Table 5 Comparative Example 5 In 4, antimony dioxide was used instead of antimony pentoxide.

3 The following can be seen from the above embodiments.

When only antimony pentoxide is added, the effect of improving thermal stability at high temperatures is small, and the effect of improving thermal stability (thermal aging resistance) and light resistance at relatively low temperatures is hardly observed. In addition, when only metal perchlorate is added, although the effect of improving thermal stability (heat aging resistance) and light resistance at relatively low temperatures is observed to some extent, it is still insufficient, and The effect of improving stability is only small.

In addition, in the case of antimony dioxide, almost no improvement effect on thermal stability (heat aging resistance) and light resistance is observed even when used alone or in combination with metal perchlorate.

In contrast, the thermal stability at high temperatures of the composition of the present invention using both antimony pentoxide and metal perchlorate,
Thermal stability (heat aging resistance) and light resistance at relatively low temperatures are significantly better than expected from the results when these are added alone, and the effects of the present invention are extremely specific. Point 4 is clear.

(Effects of the Invention) The chlorine-containing resin composition of the present invention has extremely excellent thermal stability, heat aging resistance, and light resistance.

Claims (1)

[Claims] A stabilized chlorine-containing resin composition obtained by adding at least one of (a) antimony pentoxide and (b) a metal salt of perchloric acid to a chlorine-containing resin.