JPH0570647A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having remarkably improved plate- out tendency in processing and giving a molded article having improved colora bility and weather resistance by adding a specific aluminum salt of an organic phosphorous acid ester to a chlorine-containing resin. CONSTITUTION:The objective composition is produced by incorporating (A) a chlorine-containing resin with (B) an organic phosphorous acid ester aluminum salt of formula I [R<1> and R<2> are 1-30C alkyl, aryl, etc.; X is OH or group of formula II (c) is 1 or 2; (d) is 0 or 1; (c+d) is 1 or 2); (a) is 1 or 2; (b) is 0 or 1; (a+b) is 1 or 2]. The amount of the component B is preferably 0.1-3 pts.wt. based on 100 pts.wt. of the component A. The component B is produced e.g. by reacting an aluminum alkoxide such as aluminum isopropoxide with an organic phosphite such as tetradecyl phosphite and hydrolyzing the reaction product.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a stabilized chlorine-containing resin composition, more specifically, a stabilized chlorine-containing resin obtained by adding an organic phosphite salt of aluminum to a chlorine-containing resin. It relates to a composition.

[0002]

2. Description of the Related Art Chlorine-containing resins are prone to thermal decomposition mainly due to dehydrochlorination during heat molding processing, resulting in deterioration of mechanical properties and deterioration of color tone. , Causes 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, several kinds of metal salts of various organic acids or inorganic acids, organotin compounds and the like have been conventionally combined and added to a chlorine-containing resin.

However, combinations of these various metal salts such as Cd / Ba, Ba / Zn, Ca / Zn, Ba /
When a Ca / Zn system or the like is used, the performance such as colorability and weather resistance is insufficient, so various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus for the purpose of improving colorability are used. The use of compounds, organic sulfur compounds, phenol compounds, β-diketone compounds, etc., and various UV absorbers, hindered amine stabilizers, etc. for the purpose of improving weather resistance has been proposed, but it cannot be said to be sufficient yet, and further improvements will be made. There was a need. In addition, in recent years, in order to increase the speed of the processing machine, it is required to increase the processing temperature, and at the same time, the plate-out property is required to be more excellent.

Under these circumstances, it has been proposed to use a reaction product of a carboxylic acid metal salt and an organic triphosphite in order to improve thermal stability (Japanese Patent Publication No. 51-8980, Japanese Patent Laid-Open No. 4980/980).
No. 8-29834), it has been proposed to add a metal alkyl phosphite salt to improve photodegradation (Japanese Patent Publication No. 40-940), and a specific substitution for improving weather resistance and plate-out. It has been proposed to add a phosphite salt having a group (Japanese Patent Publication No. 15822/1989).
In addition to suppressing deterioration due to heat and light, an organic phosphite salt of a metal having a hindered structure has been proposed in order to improve plate-out properties (Japanese Patent Publication No. 64-11064). However, the effect was still insufficient and was not satisfactory in practice.

[0007]

Means for Solving the Problems The present inventors have made various studies in view of the above-mentioned circumstances, and as a result, as a result, chlorine-containing resins have been found to have aluminum organic compounds represented by the general formula (I) represented by the following chemical formula 1. The present invention has been completed by finding that the addition of at least one kind of phosphite ester has a remarkable effect on the plate-out property during processing, in addition to the improvement of the coloring property and the weather resistance of the product.

[0008]

[Chemical 2] (In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group having 1 to 30 carbon atoms, a is 1 or 2, b is 0 or 1, a
+ B is 1 or 2, c is 1 or 2, d is 0 or 1,
c + d represents 1 or 2. )

The chlorine-containing resin composition of the present invention will be described in detail below.

In the above general formula (I), the alkyl groups represented by R ₁ and R ₂ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
Examples include tert-butyl, amyl, tert-amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl. Examples of the arylalkyl group represented by R ₁ and R ₂ include benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like. Examples of the aryl group represented by R ₁ and R ₂ include phenyl, naphthyl, biphenyl and the like. Examples of the alkylaryl group represented by R ₁ and R ₂ include tolyl, xylyl, ethylphenyl, butylphenyl, tert-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl, decylphenyl, dodecylphenyl and the like. ..

Therefore, examples of the organic phosphite salt of aluminum used in the present invention include the compounds (No. 1 to No. 13) of the following chemical formulas 3 to 15:

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical formula 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

The amount of the organic phosphite ester salt of aluminum added is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 100 parts by weight of the chlorine-containing resin.
~ 3 parts by weight.

The aluminum organic phosphite salt used in the present invention is, for example, hydrolyzed after reacting aluminum alkoxide and organic phosphite, or after reacting aluminum alkoxide and carboxylic acid. It can be easily produced by hydrolyzing with and reacting it with an organic phosphite.

According to such a synthetic method, a compound of the formula (I) wherein a + b = 3 may be simultaneously obtained together with the compound of the general formula (I). However, even such a mixture can be used in the present invention. Can be used.

Next, two specific synthesis examples of the organic phosphite ester salt of aluminum used in the present invention will be shown, but the present invention is not limited thereto.

[Synthesis Example 1] 1 (a =
Synthesis of the compound of 2, b = 0) 20.43 g of aluminum isopropoxide was dispersed in 40 ml of butyl diglycol, 55.6 g of tetradecyl phosphite was added with stirring, and the mixture was heated. Thirteen
The temperature was raised to 0 ° C., the reaction was carried out while dealcoholing, and after about 80% of the theoretical amount of isopropanol (12.1 g) flowed out, the alcohol was completely dealcoholized under reduced pressure.

Then, at 90 ° C., 1.8 g of water was added, and 10
It was hydrolyzed at 0 ° C. for 1 hour. The temperature was again raised to 130 ° C. and the alcohol was completely removed under reduced pressure. After cooling to room temperature, 200 ml of acetone was added to obtain 52.3 g of a white solid. As a result of liquid chromatography measurement performed on the obtained white solid, only one absorption was observed, and as a result of IR measurement, it was 2430 cm ^-1 (P-H).
Since absorption is observed at 80 cm ^-1 (O-H), the compound of No. It was confirmed that 1 (a = 2, b = 0) compound was produced.

[Synthesis Example 2] 2 (a =
Synthesis of the compound of b = 1) 20.43 g of aluminum isopropoxide was dispersed in 50 ml of toluene, and octylic acid was 28.8 while stirring.
4 g was added and heated. The temperature is raised to 130 ° C., and the reaction is carried out while dealcoholation, and the theoretical amount of isopropanol (1
After about 80% of 2.1 g) was flowed out, the alcohol was completely removed under reduced pressure.

Then, at 90 ° C., 1.8 g of water was added, and 10
It was hydrolyzed at 0 ° C. for 1 hour. The temperature was again raised to 130 ° C. and the alcohol was completely removed under reduced pressure. After cooling to room temperature, 200 ml of acetone was added to obtain 52.3 g of a white solid. As a result of liquid chromatography measurement performed on the obtained white solid, only one absorption was observed, and as a result of IR measurement, it was 1590 cm ⁻¹ (C = 0).
Since absorption was observed at 90 cm ^-1 (O-H), formation of hydroxyaluminum dioctoate was confirmed.

11.01 g of the hydroxyaluminum dioctoate synthesized above was dispersed in 30 ml of butyl diglycol and tetradecyl phosphite 1 was added with stirring.
5.8g was added. The temperature was raised to 130 ° C. and the reaction was performed for 2 hours. After cooling to room temperature, 200 ml of acetone was added to obtain 11.6 g of a white solid. As a result of liquid chromatography measurement performed on the obtained white solid, only one absorption was observed, and as a result of IR measurement, 1600 cm
^-1 (C = O), 2430cm ^-1 (PH), 3690cm
^Since absorption is observed in ^-1 (O-H),
o. It was confirmed that the compound 2 (a = b = 1) was produced.

The chlorine-containing resin used in the present invention is as follows. 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 Coalesce, 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 Polymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-urethane copolymers and other chlorine-containing resins and the chlorine-containing resins and polyethylene,
Α-Olefin polymers such as polypropylene, polybutene, poly-3-methylbutene or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrenes, acrylic resins, styrenes and other homopolymers. Examples thereof include copolymers with monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, methacrylic acid ester-butadiene-styrene copolymers, blended products with polyurethane, etc. ..

In addition, the composition of the present invention may contain Li, K, Na and M.
The combined use of an organic acid salt of a metal such as g, Sr, Ca, Ba, Zn, Cd, Sn, or Pb significantly improves the stabilizing effect.

Carboxylic acid, phenols, etc. are useful as the organic acid residue constituting the organic acid residue of the metal.

Examples of the carboxylic acid 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 Acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid,
Mercaptopropionic acid, octyl mercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid , Ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid and other monocarboxylic acids, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid,
Divalent carboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanoic acid, pyromellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids.

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

Further, in order to obtain a non-toxic or low-toxic chlorine-containing resin composition, a non-toxic or low-toxic one of the above-mentioned commonly used organic acid metal salts can be selected and used to obtain a non-toxic or low-toxicity and heat resistance. A chlorine-containing resin composition having good stability can be obtained.

The amount of the organic acid salt of the above metal added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

Further, the composition of the present invention can be prepared by adding Li, K, Na,
By using a metal such as Mg, Sr, Ca, Ba, Zn, Cd, Sn, or Pb, or a halogen oxyacid salt of ammonia, an organic amine compound or an organic quaternary ammonium compound, the stabilizing effect is remarkably improved.

As the halogen oxyacid salt, perchlorate,
Examples thereof include periodate, perbromate, chlorate, bromate, iodate, chlorite, hypochlorite, and bromate. It may be salt,
Further, it may be dissolved in a solvent such as alcohol, or may be dissolved in alcohol and then dehydrated.

Further, these halogen oxyacid salts are described in, for example, JP-A-59-140261 and JP-A-59-7.
It may be obtained by treating hydrotalcites or silicate minerals with perchloric acid or the like as described in JP-A-8874 and JP-A-59-113636.

The amount of the halogen oxygen salt or perchloric acid-treated product added is 0.00 based on 100 parts by weight of the chlorine-containing resin.
01 to 1 part by weight is preferable, and 0.01 to 1 part by weight is particularly preferable.

By using an organic phosphite compound and / or an epoxy compound in combination with the composition of the present invention, an excellent synergistic effect is exhibited.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono, di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, diphenyl decyl 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-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4′-isopropylidene diphenol pentaerythritol diphosphite, tetra (C _12-15
Mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol 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 and the like.

The amount of the organic phosphite compound added is
It 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.

The above-mentioned epoxy compound which can be used in the composition of the present invention includes epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized beef tallow oil, epoxidized castor oil and epoxy. Safflower oil, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, 2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,
Examples thereof include 2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate.

The amount of the epoxy compound added is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The composition of the present invention includes ester-based plasticizers such as phthalic acid ester-based plasticizers and adipic acid ester-based plasticizers, polyester-based plasticizers, phosphate ester-based plasticizers,
Chlorine-based plasticizers and other plasticizers can be appropriately used depending on the application.

In addition to the composition of the present invention, pentaerythritol, dipentaerythritol, sorbitol, mannitol, pentaerythritol or a stearic acid half ester of dipentaerythritol, bis (dipentaetasthritol) adipate, glycerin, tris (2).
-Hydroxyethyl) isocyanurate and other polyhydric alcohol compounds, as well as stabilizing aids such as β-diketone compounds such as dehydroacetic acid, dibenzoylmethane, stearoylbenzoylmethane, and carboxymethylbenzoylmethane to improve its stability. It can be further improved.

The composition of the present invention comprises synthetic hydrotalcites, zinc-modified hydrotalcites obtained by substituting a part of magnesium with zinc, or those except for crystal water thereof, various zeolites, calcium phosphate, Inorganic compounds such as calcium oxide, magnesium silicate, magnesium phosphate, magnesium oxide, and magnesium hydroxide can also be used appropriately according to the application.

If a photostabilizer is added to the composition of the present invention, the photostability can be improved. Therefore, these can be appropriately selected and used according to the purpose of use. These light stabilizers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, hindered amine-based, various metal salts or metal chelates, particularly nickel or chromium salts or chelates.

In addition, 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 antiplateout agent, a surface treatment agent, a lubricant, a flame retardant, A fluorescent agent, an antifungal agent, a bactericidal agent, a photodegradation agent, a non-metal stabilizer, a processing aid, a release agent and the like can be included.

[0055]

EXAMPLES 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 given below.

Example 1 A sheet having a thickness of 1 mm was prepared with a kneading roll using the following composition, and a thermal stability test at 190 ° C. and initial colorability, transparency and plate-out property tests were conducted. I did. At the same time, a weather resistance test was performed with a weatherometer. Both initial colorability and transparency were evaluated on a scale of 10, with 1 being the best and the higher the value being, the worse. Plate-out value is the ppm of plate-out dye measured by the Watching Red method. The weather resistance test measured the time for the sheet to turn black.

The results are shown in Table 1.

[Composition] Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 Di-2-ethylhexyl phthalate 50 Epoxidized soybean oil 2 Monooctyl diphenyl phosphite 0.5 Zn stearate 0.5 Ba stearate 0.8 DHT-4A ^{* 1} 0.05 Test compound (Table 1) 0.5 * 1 Hydrotalcite manufactured by Kyowa Chemical Co., Ltd.

[0059]

Example 2 A test was conducted in the same manner as in [Example 1] using the following formulation.

The results are shown in Table 2.

[Compound] parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 di-2-ethylhexyl phthalate 50 epoxidized soybean oil 2 tetra (C _12-15 mixed alkyl) bisphenol A diphosphite 0.5 Zn stearate 3 Ca stearate 0.3 Alkamizer 4 ^{* 2} 0.2 Sodium perchlorate 0.05 Test compound (Table-2) 0.5 * 2 Zinc-modified hydrotalcite manufactured by Kyowa Chemical Co., Ltd.

[0063]

[Example 3] Using the following composition, the mixture was kneaded by a roll and then pressed to form a sheet having a thickness of 1 mm, and this sheet was subjected to a thermal stability test in an oven at 190 ° C. It was Further, the thickness of the kneading roll was 0.
A 1 mm film was prepared and subjected to a weather resistance test and an elongation residual ratio test by outdoor exposure.

The weather resistance test was carried out by observing the surface condition of the film after 1 year and 2 years of outdoor exposure, and the evaluation standard was 10%.
Expressed in stages. 1 indicates a state with almost no discoloration, 1
0 indicates a blackish brown state. 1 (colorless) ← ──────── →→ (black-brown) 10 The residual elongation rate is indicated by the residual rate (%) in comparison with the elongation before exposure of the film after 1 year of outdoor exposure.

The results are shown in Table 3.

[Composition] Parts by Weight Vinyl Chloride Resin (Polymerization Degree 1300) 100 Di-2-ethylhexyl phthalate 50 Tricresyl Phosphate 5 Epoxidized Flaxseed Oil Fatty Acid Octyl 2 Zn Stearate 0.8 Ba Stearate 0.5 Di Benzoylmethane 0.1 Sorbitan monopalmitate 1.5 Methylenebisstearic acid amide 0.5 Octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate 0.1 Sample compound table Three

[0068]

The effect of adding an organic phosphite such as barium, calcium, magnesium or zinc to the chlorine-containing resin is small, and especially when considering other properties such as transparency, colorability and plate-out property. , Its effect is insufficient. However, as in the present invention, by adding a basic organic phosphite, it is clear that the weather resistance is improved, and particularly, the transparency, the coloring property, and the plate-out property are significantly improved. is there.

[0070]

EFFECTS OF THE INVENTION The chlorine-containing resin composition of the present invention has markedly improved plate-out property during processing, in addition to colorability and weather resistance.

Claims (1)

[Claims] 1. A stabilized chlorine-containing resin composition obtained by adding at least one kind of an organic phosphite salt of aluminum represented by the general formula (I) of the following chemical formula 1 to a chlorine-containing resin. [Chemical 1] (In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group having 1 to 30 carbon atoms, a is 1 or 2, b is 0 or 1, a
+ B is 1 or 2, c is 1 or 2, d is 0 or 1,
c + d represents 1 or 2. )