JP3534918B2 - Stabilized chlorine-containing resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a stabilized chlorine-containing resin composition, more specifically, a stabilized chlorine-containing resin obtained by adding a phosphorus-containing metal salt and a lithium-modified hydrotalcite compound. The present invention relates to a chlorine-containing resin composition.

[0002]

2. Description of the Related Art Chlorine-containing resins are prone to thermal decomposition mainly due to dehydrochlorination during heat molding, resulting in deterioration of mechanical properties and deterioration of color tone. , Causing a significant disadvantage.

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

For this purpose, various metal stabilizers such as metal salts of various organic acids or inorganic acids and organotin compounds have been used in combination for the above purpose, and almost satisfactory in terms of thermal stability. The results have been obtained.

However, when these various metal-based stabilizers are used, the performances such as colorability and weather resistance are not sufficient, and various stabilizing aids such as epoxy compounds and polyvalent compounds are used for the purpose of improving colorability. It has been proposed to use alcohols, organic phosphorus compounds, organic sulfur compounds, phenol compounds, β-diketone compounds, etc., and various ultraviolet absorbers, hindered amine light stabilizers, etc. for the purpose of improving weather resistance, but they are not sufficient. I couldn't say that I needed to improve.

Particularly in recent years, in consideration of adverse effects on the environment or the human body, use of cadmium-barium, lead or organotin stabilizers has been shunned, and barium-zinc stabilizers, calcium-zinc stabilizers, etc. Although it is required to shift to stabilizers having low toxicity, various performances of these are not sufficient as compared with the former.

[0007] Hydrotalcite compounds have an excellent effect of improving heat resistance, and in many cases, they are used in combination in order to make up for the insufficient heat resistance of the above-mentioned low-toxicity stabilizers. Among the organic acid metal salts, phosphorus-containing metal salts are also included. Since it has an excellent effect of improving weather resistance, it is also used in weather resistance applications such as agricultural materials.

Various methods have been proposed for adding the above-mentioned hydrotalcite compound and phosphorus-containing metal salt to a chlorine-containing resin in combination. For example, JP-A-60-219246 discloses a halogen-containing resin containing perchloric acid. It has been proposed to use ionic hydrotalcites in combination with an organic phosphate metal salt. JP-A 1-256553 discloses a hydrotalcite compound, a higher alcohol phosphoric acid ester metal salt, and a vinyl chloride resin. A fog-proof agricultural coating material obtained by adding a fluorine-containing compound together has been proposed, and in JP-A-4-236253, vinyl chloride resin is added.
Agricultural films comprising trixylyl phosphate, organophosphate metal salt, magnesium hydroxide and hydrotalcite in combination have been proposed, but the hydrotalcites described in these and the organophosphate metal salt in combination are used. In such a case, no particularly satisfactory weather resistance improving effect was obtained.

Further, JP-A-5-179052 and JP-A-6-248109 propose that an alkaline metal-aluminum complex similar to hydrotalcite is used as a stabilizer for resins such as chlorine-containing resins. However,
Even if these are added to the chlorine-containing resin together with the phosphorus-containing metal salt, a sufficient effect of improving weather resistance cannot be obtained.

Therefore, an object of the present invention is to provide a chlorine-containing resin composition which is excellent in heat stability and colorability and is also excellent in weather resistance.

[0011]

Means for Solving the Problems As a result of various studies, the present inventors have found that a chlorine-containing resin contains at least one specific phosphorus-containing metal salt and at least one specific lithium-modified hydrotalcite compound. It was found that the chlorine-containing resin composition obtained by adding the above can achieve the above object.

The present invention has been made on the basis of the above findings, and a chlorine-containing resin is represented by the following general formulas (I) and (II) represented by the following [Chemical formula 3] (the same as the above [Chemical formula 1]). At least one selected from the group consisting of phosphorus-containing metal salts, and (b) a general formula of the following [Chemical formula 4] (the same as the above-mentioned [Chemical formula 2])
The present invention provides a stabilized chlorine-containing resin composition obtained by adding at least one lithium-modified hydrotalcite compound represented by (III).

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The stabilized chlorine-containing resin composition of the present invention will be described in detail below.

In the phosphorus-containing metal salt represented by the above general formulas (I) and (II) used in the chlorine-containing resin composition of the present invention, the alkyl group represented by R ₁ and R ₃ in the formula is , For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl. , Hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl, etc., and the arylalkyl group includes, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, etc., and the aryl group Examples include phenyl, naphthyl, biphenyl and the like, The Rukiruariru group, for example, tolyl, xylyl, ethylphenyl, butylphenyl, t-butylphenyl, octylphenyl,
Nonylphenyl, dinonylphenyl, decylphenyl,
Examples include dodecylphenyl and the like.

Therefore, examples of the phosphorus-containing metal salt include compounds No. 1 to No. 16 of the following [Chemical formula 5] to [Chemical formula 20].

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

[0033]

[Chemical 20]

In the above compounds No. 1 to No. 16, in the formula,
M represents an alkaline earth metal atom, a zinc atom or an aluminum atom, a represents 0 when M represents an alkaline earth metal atom or a zinc atom, and 1 represents M when M represents an aluminum atom. Examples of the alkaline earth metal atom include calcium and barium.

The amount of the phosphorus-containing metal salt added is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin. Here, if the addition amount is less than 0.005 parts by weight, the effect is insufficient, and if the addition amount is more than 5 parts by weight, the effect is not improved, and the workability is deteriorated and plate out occurs. There is a fear that will occur.

The lithium-modified hydrotalcite compound represented by the above general formula (III) used in the present invention is synthesized by a known method for producing hydrotalcites, and X is 0.5 to 4.5, preferably Is 1.0 to 3.0, Y is 0.1 to 3.0, preferably 0.2 to 2.0, Z is 1.0 to 8.0, and preferably 2.0 to 6. .0,
n represents the number of crystal waters of 0 to 30.

The above lithium-modified hydrotalcite compound
As the object, for example, Li_1.8Mg_0.6Al _Four(OH)₁₃CO₃・ 3.6H
₂O, Li₂Mg₁Al_Four(OH)₁₄CO₃・ 4H₂O, Li_1.6Mg_1.2Al_Four(OH)₁₄C
O₃, Li _2.4Mg_0.3Al_Four(OH)₁₃CO₃・ 4.6H₂O, Li_3.2Mg_2.4Al
₂(OH)₁₂CO₃・ 3.3H₂O, Li_2.4Mg_0.8Al₆(OH)₂₀CO₃・ 5.2H₂O
Etc. Alternatively, a commercially available product may be used,
Examples of commercially available products include “LMA” [Fuji Chemical Co., Ltd.
Manufactured] and the like.

On the surface of the lithium-modified hydrotalcite compound, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzene sulfonate, higher grade Those coated with a fatty acid amide, a higher fatty acid ester or wax can also be used.

The amount of the lithium-modified hydrotalcite compound added is preferably 0.01 to 5 parts by weight, more preferably 0.05, based on 100 parts by weight of the chlorine-containing resin.
~ 3 parts by weight. If the addition amount is less than 0.01 parts by weight, the stabilizing effect is insufficient, and if it exceeds 5 parts by weight, the original physical properties of the resin may be impaired.

In the present invention, both the phosphorus-containing metal salt and the lithium-modified hydrotalcite compound are used as stabilizers. The phosphorus-containing metal salt and the lithium-modified hydrotalcite compound can be separately blended in the chlorine-containing resin, or they can be mixed and used, and in this case, if necessary. It can also be used as a so-called complex stabilizer containing other stabilizer components.

Examples of the chlorine-containing resin used in the present invention include 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, 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 terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer,
Chlorine-containing resin such as vinyl chloride-urethane copolymer and the above-mentioned chlorine-containing resin and α-olefin polymer such as polyethylene, polypropylene, polybutene, poly-3-methylbutene or ethylene-vinyl acetate copolymer, ethylene-propylene copolymer Polyolefins such as coalesces and copolymers thereof, polystyrene, acrylic resins, copolymers of styrene with other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, methacryl Examples thereof include acid ester-butadiene-styrene copolymer and blended products with polyurethane.

The chlorine-containing resin composition of the present invention also comprises
Plasticizers, other stabilizers and other additives which are usually used in chlorine-containing resin compositions can also be used in combination.

As the above-mentioned plasticizer, any plasticizer usually used in chlorine-containing resins can be optionally used. Examples of the plasticizer include triphenyl phosphate,
Phosphate plasticizer systems such as tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethylphosphate, tributylphosphate, trioctylphosphate, tri (butoxyethyl) phosphate octyldiphenylphosphate; dibutylphthalate, butylhexylphthalate, A phthalate plasticizer such as diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; dioctyl adipate, diisononyl adipate,
Adipate plasticizers such as diisodecyl adipate and di (butyldiglycol) adipate; as polyhydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butane Dibasic acids such as diol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and 12-hydroxystearic acid, caprolactone, etc. may be used. If necessary, a monohydric alcohol or monocarboxylic acid is used as a stopper. Other plasticizers; tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers Examples thereof include plasticizers and biphenyltetracarboxylic acid plasticizers.

When the chlorine-containing resin composition of the present invention is used for an agricultural film or sheet, it is preferable to use a phosphate type plasticizer and an ester type plasticizer in combination among the above plasticizers. In that case, it is preferable to use 1 to 100 parts by weight of the ester plasticizer with respect to 1 part by weight of the phosphate plasticizer.

Other stabilizers usable in the present invention include:
Metal salts of organic carboxylic acids and phenols, hydrotalcite compounds, epoxy compounds, organic phosphite compounds, pure organic stabilizing aids, metal salts of perchloric acid, perchloric acid treated hydrotalcite or perchloric acid treated Other perchlorates such as silicates and various light stabilizers can be mentioned.

The metal constituting the above-mentioned metal salt of organic carboxylic acid and phenol is lithium, potassium,
Examples thereof include sodium, calcium, barium, magnesium, strontium, zinc, tin, cesium, aluminum and organic tin.

Examples of the organic carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,
Enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid,
Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid,
Monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cuminic acid, n-propylbenzoic acid Acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, elaidic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octylmercapto Monovalent carboxylic acids such as propionic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, Divalent carboxylic acids such as fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid or their monoesters or monoamide compounds; butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids such as melophanoic acid and pyromellitic acid.

Examples of the above-mentioned phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol. , Isooctylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyl tertiary-octylphenol, etc. To be

The above-mentioned metal salts of organic carboxylic acids and phenols are acid salts, neutral salts, basic salts or overbased complexes obtained by neutralizing part or all of the bases of basic salts with carbonic acid. May be.

The addition amount of the organic carboxylic acid and the metal salt of phenols is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin. is there. When both are used in combination, the addition amount of each may be the same or different.

Examples of the hydrotalcite compound include magnesium and aluminum represented by the general formula (IV) of the following [Chemical Formula 21], or a hydrous double salt compound consisting of zinc, magnesium and aluminum. Further, it may be a compound in which a part of the magnesium component is replaced with zinc.

[0052]

[Chemical 21]

The hydrotalcite compound may be a natural product or a synthetic product. As a method for synthesizing the synthetic product, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, and Japanese Patent Publication No. 51-29129.
The publicly known methods described in JP-A No. 61-174270 and JP-A No. 61-174270 can be exemplified. In addition, in the present invention, the hydrotalcite compound can be used without being limited by the crystal structure, the crystal particle size and the like.

On the surface of the hydrotalcite compound, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzene sulfonate, higher fatty acid amide Those coated with higher fatty acid ester or wax can also be used.

The amount of the above-mentioned hydrotalcite compound added is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

Examples of the epoxy compound include bisphenol type and novolac type epoxy resins, alicyclic epoxy compounds such as vinylcyclohexene diepoxy, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, Epoxidized beef tallow oil, epoxidized safflower oil, epoxidized methyl stearate, -butyl, 2-ethylhexyl, -stearyl ester,
Examples thereof include epoxidized polybutadiene, epoxidized tall oil fatty acid ester, and epoxidized linseed oil fatty acid ester.

The amount of the epoxy compound added is preferably 0.01 to 20 relative to 100 parts by weight of the chlorine-containing resin.
Parts by weight, more preferably 0.05 to 10 parts by weight.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,
4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenylacid phosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, 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 (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,2
4,6-Tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-
4,4'-isopropylidenediphenol-pentaerythritol diphosphite, tetra (C ₁₂ ~ ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated 4,4'-isopropylidenediphenol Polyphosphite, bis (octylphenyl)
Bis [4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, tetratridecyl-4,4'-butylidene bis (2-tert-butyl-) 5-methylphenol) diphosphite, hexa (tridecyl) -1,1,
3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, 9,10-
Examples thereof include dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol · 2,4,6-tri-tert-butylphenol monophosphite.

The amount of the organic phosphite compound added is
It is preferably 0.0 with respect to 100 parts by weight of the chlorine-containing resin.
It is 1 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.

Further, as the pure organic stabilizing aid,
Phenols such as bisphenol A; polyhydric alcohols such as pentaerythritol, dipentaerythritol, dipentaerythritol adipate, mannitol, sorbitol and ester compounds or partial ester compounds thereof; dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, Β-diketone compounds such as dehydroacetic acid and metal salts thereof;
2,6-dimethyl-1,4-dihydropyridine-3,5
Examples include organic nitrogen-containing compounds such as dicarboxylic acid didodecyl ester, 2-phenylindole and melamine.

The amount of the pure organic stabilizing aid added is preferably 0.001 with respect to 100 parts by weight of the chlorine-containing resin.
To 5 parts by weight, and more preferably 0.005 to 3 parts by weight.

Examples of the metal component constituting the metal salt of perchloric acid include lithium, sodium, potassium, strontium, barium, zinc, cadmium, lead and aluminum. These metal salts of perchloric acid are exemplified. May be an anhydride or a hydrous salt, or may be one dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate, or its dehydrated product.

Further, the perchloric acid-treated hydrotalcite is a perchloric acid-modified product in which a part or all of carbonic acid of the hydrotalcite compound represented by the above formula (IV) is replaced with perchloric acid.

The above-mentioned perchloric acid-treated hydrotalcite is
The surface is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an oleic acid alkali metal salt, an organic sulfonic acid metal salt such as a dodecylbenzenesulfonic acid alkali metal salt, a higher fatty acid amide, a higher fatty acid ester or wax. Things can also be used.

As the perchloric acid-treated silicate,
Silicate metal salts such as calcium silicate, magnesium silicate, barium silicate, and zinc silicate, and various siliceous clay minerals or processed products thereof, such as kaolin, bentonite, mica powder, talc, diatomaceous earth, acid clay, activated clay and zeolite Alternatively, a synthetic silicate treated with an aqueous solution of perchloric acid can be used. Among these perchloric acid-treated silicates, calcium silicate, magnesium silicate, barium silicate, kaolin, bentonite, talc, acid clay, activated clay and A treated product of zeolite is preferable.

The above-mentioned perchloric acid-treated hydrotalcite or the above-mentioned perchloric acid-treated silicate can be obtained by, for example, adding hydrotalcite or silicate to a dilute aqueous solution of perchloric acid and stirring, and then filtering if necessary. It can be easily produced by dehydration or drying. in this case,
The molar ratio of hydrotalcite or silicate to perchloric acid can be set arbitrarily, but in general, 1 mol of hydrotalcite or silicate gives 0.1 mol of perchloric acid.
It is preferable to use it in a ratio such that it is 1 to 2 mol.

The addition amount of the metal salt of perchloric acid, hydrotalcite treated with perchloric acid or silicate treated with perchloric acid is
It is preferably 0.001 to 10 parts by weight, and more preferably 0.005 to 100 parts by weight of the chlorine-containing resin.
5 parts by weight. When these are used in combination, the addition amount may be the same or different.

As the light stabilizer, benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted acrylonitrile compounds, various metal salts or metal chelates, particularly nickel or chromium salts or chelates, hindered amines. Examples include compounds.

Further, in order to make the chlorine-containing resin composition of the present invention a non-toxic or low-toxic composition, a non-toxic or low-toxic one is selected from the above-mentioned commonly used organic acid metal salts. For example, a chlorine-containing resin composition that is non-toxic or low-toxic and has good thermal stability can be obtained.

In addition, if necessary, the chlorine-containing resin composition of the present invention includes, for example, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, a plate-out prevention agent, a surface treatment agent, Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, photodegradants, non-metal stabilizers, processing aids, release agents and the like can be included.

The chlorine-containing resin composition of the present invention may be processed by various methods such as calender molding, extrusion molding, injection molding, press molding, blow molding, paste molding and powder molding. Method is used.

Since the chlorine-containing resin composition of the present invention has excellent weather resistance, it can be suitably used for agricultural materials such as agricultural films and sheets which require particularly high weather resistance. it can.

[0073]

EXAMPLES Next, the chlorine-containing resin composition of the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

[Example 1] Using the following formulation, kneading with a roll to prepare a 0.5 mm sheet, the thermal stability was evaluated by measuring the blackening time in an oven at 190 ° C, and then the From roll-up sheet, 180 ℃, 20 minutes, 10
Pressing was performed under the condition of 0 kg / cm ² to prepare a sheet having a thickness of 1 mm, and the coloring property was visually evaluated. Also,
A film having a thickness of 0.1 mm was prepared with a kneading roll, and a weather resistance test of the film by outdoor exposure was performed. In the weather resistance test, the surface condition of the film was observed after 10 months and 20 months of outdoor exposure.

The evaluation standard of the coloring test is expressed in 10 steps,
1 indicates that it is almost colorless, yellowing increases as the value increases, and 10 indicates that it is almost brown. In addition, the evaluation criteria for the weather resistance test are also expressed in 10 levels, as in the color test.
1 shows almost no discoloration, 5 or more shows a browning part, and 10 shows that the whole is black brown. 1 (colorless) ← ──────── →→ (black brown) 10

The results are shown in [Table 1] below.

[0077] [Distribution] Weight part Vinyl chloride resin (polymerization degree 1300) 100 Di-2-ethylhexyl phthalate 45 Tricresyl phosphate 5 Epoxidized linseed oil fatty acid octyl 2 Zinc stearate 0.5 Dibenzoylmethane 0.1 Sorbitan monopalmitate 1.5 Methylenebisstearic acid amide 0.5 Octadecyl-3- (3 ', 5'-tert-butyl-4'-0.1 Hydroxyphenyl) propionate 3,9-bis [1,1-dimethyl-2- {tris (1,2,2 0.1 , 6,6-Pentamethyl-4-piperidyloxycarbonylo Xy) butylcarbonyloxy} ethyl] -2,4,8,10 -Tetraoxaspiro [5.5] undecane No4 Ba salt (M = Ba, a = 0 in the compound of the above [Chemical formula 8]) 0.5 Hydrotalcite compound (see [Table 1] below) 0.5

[0078]

[Table 1]

In addition, * 1 to * 8 in the above [Table 1] represent the following (hereinafter the same). * 1: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O * 2: Li _1.8 Mg _0.6 Al ₄ (OH) ₁₃ CO ₃ · 3.6H ₂ O * 3: Li ₂ Mg ₁ Al ₄ (OH) ₁₄ CO ₃・ 4H ₂ O * 4: Li _1.6 Mg _1.2 Al ₄ (OH) ₁₄ CO ₃ * 5: Li _2.4 Mg _0.3 Al ₄ (OH) ₁₃ CO ₃・ 4.6H ₂ O * 6: Li _3.2 Mg _2.4 Al ₂ (OH) ₁₂ CO ₃ · 3.3H ₂ O * 7: Li _2.4 Mg _0.8 Al ₆ (OH) ₂₀ CO ₃ · 5.2H ₂ O * 8: Basic lithium magnesium aluminum carbonate (manufactured by Fuji Chemical Co., Ltd.) (Li content = 2.6% by weight, Li: Mg:
Al (molar ratio) = 9: 3: 20)

Example 2 Except that the following formulation was used:
The test was conducted in the same manner as in Example 1. The results are shown in [Table 2] below.

[0081] [Distribution] Weight part Vinyl chloride resin (polymerization degree 1300) 100 Di-2-ethylhexyl phthalate 50 Tricresyl phosphate 5 Epoxidized linseed oil fatty acid octyl 2 Zinc stearate 0.5 Dibenzoylmethane 0.1 Sorbitan monopalmitate 1.5 Methylenebisstearic acid amide 0.5 Octadecyl-3- (3 ', 5'-tert-butyl-4'-0.1 Hydroxyphenyl) propionate Tetra (2,2,6,6-tetramethyl-4-piperidyl) 0.05 Butane tetracarboxylate LT-2 0.1 Sample compound [Table 2]

[0082]

[Table 2]

Incidentally, Nos. 2, 4, 6, 8, 13 in the above [Table 2]
Are the compounds exemplified as the phosphorus-containing metal salt.

From the results of the above [Table 1] and [Table 2], the following is clear. The weather resistance of the chlorine-containing resin is a compound selected from the group consisting of the phosphorus-containing metal salts represented by the general formulas (I) and (II) or the lithium-modified hydrotalcite represented by the general formula (III). When the compound is used alone (Comparative Examples 1-1,1-5,2-2), the effect is small, and when the phosphorus-containing metal salt and the lithium-unmodified hydrotalcite compound are used in combination. (Comparative Example 1-
4,2-4), the combined effect is not remarkable.

On the other hand, when both the phosphorus-containing metal salt and the lithium-modified hydrotalcite compound are contained (Examples 1-1 to 1-7, 2-1 to 2-9), each is used alone. It shows a great effect that cannot be predicted from the case of addition.

[0086]

EFFECTS OF THE INVENTION The chlorine-containing resin composition of the present invention is excellent in thermal stability and colorability, and is also excellent in weather resistance. Further, the chlorine-containing resin composition of the present invention is particularly suitable for applications such as agricultural films used under severe conditions.

Continuation of the front page (56) Reference JP-A-4-359945 (JP, A) JP-A-4-261452 (JP, A) JP-A-7-118473 (JP, A) JP-A-8-311284 (JP , A) Special table 10-508281 (JP, A) Special table 10-504050 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 27/04-27/08

Claims (2)

(57) [Claims] 1. A chlorine-containing resin, and (b) at least one selected from the group consisting of phosphorus-containing metal salts represented by the following general formulas (I) and (II), and (b) A stabilized chlorine-containing resin composition obtained by adding at least one lithium-modified hydrotalcite compound represented by the following general formula (III). [Chemical 1] [Chemical 2] 2. The stabilized chlorine-containing resin composition according to claim 1, which is used as an agricultural material.