JPH0565379A - Stabilizer composition for chlorinated resin - Google Patents

Abstract

PURPOSE:To provide the subject composition which can improve the heat resistance and colorability and also has a remarkable effect of improving the transparency. CONSTITUTION:The objective composition is obtained by uniformly dispersing 100 pts.wt. hydrotalcite compound in 10-1000 pts.wt. organic phosphorous acid ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-containing resin stabilizer composition, and more particularly to a chlorine-containing resin stabilizer composition in which a hydrotalcite compound is uniformly dispersed in an organic phosphite ester. Is.

[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.

Conventionally, for this purpose, various metal salts of organic or inorganic acids, organotin compounds, etc. have been used in combination.

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 properties such as colorability and heat resistance are not sufficient, and various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds for the purpose of improving colorability, The use of an organic sulfur compound, a phenol compound, a β-diketone compound, etc. has been proposed, but it cannot be said to be sufficient yet, and further improvement was required.

In addition to the above-mentioned organic stabilizing aids,
Inorganic stabilizing aids have also been utilized. Among them, hydrotalcite significantly improves heat resistance. However, hydrotalcite deteriorates the coloring property, and since it is an inorganic compound, it cannot be said that it has good compatibility with a resin and its transparency is poor.
Therefore, depending on the purpose, it is difficult to add a large amount, and the stabilizing effect is still insufficient.

[0007]

Means for Solving the Problems The present inventors have made various studies in view of the above situation, and as a result, 100 parts by weight of the hydrotalcite compound is added to 10 to 10 organic phosphites.
Stabilizer composition obtained by uniformly dispersing in 100 parts by weight,
As a stabilizer for chlorine-containing resins, they have found that, in addition to improving their heat resistance and colorability, they also have a remarkable effect on their transparency, and completed the present invention.

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

The hydrotalcite compound used in the stabilizer composition of the present invention is a magnesium and aluminum represented by the following general formula (I) or a double salt compound consisting of zinc, magnesium and aluminum, and has a crystal structure. It may be dehydrated water.

Mg _y1 Zn _y2 Al _x · (OH) ₂ · (CO ₃ ) _{x / 2} · mH ₂ O (I) (In the general formula (I), x, y ₁ and y ₂ are respectively represented by the following formulas. It represents a number that satisfies the condition represented, and m represents 0 or an arbitrary integer: 0 <x ≦ 0.5, y ₁ + y ₂ = 1−x, 0.1 ≦
y ₁ <1, 0 ≦ y ₂ <0.8)

The hydrotalcite compound may be a natural product or a synthetic product. As a synthesis method, Japanese Patent Publication No. 46-2280 and Japanese Patent Publication No. 50-3
Known methods described in, for example, Japanese Patent Publication No. 0039 and Japanese Patent Publication No. 51-29129 can be exemplified. Further, the hydrotalcite compound in the present invention can be used without being limited by its crystal structure, crystal particle size and the like.

As the hydrotalcite compound used in the stabilizer composition of the present invention, the surface of the hydrotalcite compound is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate salt, Those coated with an organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt, a higher fatty acid amide, a higher fatty acid ester or a wax can also be used.

Examples of the organic phosphite used in the stabilizer composition of the present invention include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite and tris (nonylphenyl) phosphite. Fight, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,4
6-di-tert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (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 penta diphosphite, phenyl-4,4'-isopropylidenediphenol-pentaerythritol diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,
4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4
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 above-mentioned organic phosphite ester is in a liquid state, and particularly has a refractive index of 1.45 to 1.60, preferably 1.5.
If the one in the range of 0 to 1.55 is used, a stabilizer composition having high transparency can be obtained. In addition, the refractive index can be adjusted to a desired one by using the other solvent in combination.

In the stabilizer composition of the present invention, 100 parts by weight of the hydrotalcite compound is added to 10 to 1000 parts by weight of the organic phosphite, preferably 50 to 500 parts by weight.
It is evenly dispersed in parts by weight. That is, it is usually obtained by adding the above hydrotalcite compound into the above organic phosphite, stirring the mixture at room temperature to 200 ° C. for 2 hours to 10 hours, and completely dispersing it uniformly. At this time, it is considered that the hydrotalcite compound and the organic phosphite ester are interacting with each other.

The stabilizer composition of the present invention may contain another solvent in order to improve the dispersibility of the hydrotalcite compound. When the powdered organic phosphite ester is used, the hydrotalcite compound can be dispersed using another solvent.

The stabilizer composition of the present invention can be added alone to the chlorine-containing resin, or can be mixed with another stabilizer composition and added to the chlorine-containing resin.

The amount of the stabilizer composition of the present invention added to the chlorine-containing resin is 100 parts by weight of the chlorine-containing resin.
It is preferably 0.1 to 10 parts by weight, preferably 0.05 to 5 parts by weight as the hydrotalcite compound and 0.01 to 5 parts by weight as the organic phosphite.

The chlorine-containing resin to which the stabilizer composition of the present invention is stabilized includes 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 terpolymer , Vinyl chloride-acrylic acid ester Coal, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-chlorine-containing resin such as vinyl chloride-urethane copolymer and the chlorine-containing resin 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. ..

The stabilizer composition of the present invention comprises Li, K, Na, Mg,
The combined use of an organic acid salt of a metal such as Sr, Ca, Ba, Zn, Cd, Sn, Pb significantly improves the stabilizing effect.

As the organic acid residue constituting the above-mentioned metal organic acid salt, carboxylic acid, phenols, acid phosphates, acid phosphites and the like are useful.

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 tri- or tetravalent carboxylic acid di- or triester compounds.

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

Examples of the acid phosphate include:
Examples thereof include mono / distearyl acid phosphate, mono / diphenyl acid phosphate, and mono / dinonyl phenyl acid phosphate.

Further, examples of the acid phosphite include phenyl acid phosphite, nonyl phenyl acid phosphite, octyl acid phosphite,
Stearyl acid phosphite and the like can be mentioned.

The amount of the organic acid salt of the 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.

In order to obtain a non-toxic or low-toxic chlorine-containing resin composition, among the commonly used organic acid salts of the above-mentioned metals,
If a non-toxic or low-toxic one is selected and used, a chlorine-containing resin composition that is non-toxic or low-toxic and has good thermal stability can be obtained.

The stabilizer composition of the present invention may contain an alkyltin stabilizer.

Examples of the above-mentioned alkyl tin stabilizers include mono / dimethyl tin, mono / dibutyl tin, mono / dioctyl tin alone and as a mixture, mercaptide, malate and laurate.

The amount of the above-mentioned alkyl tin stabilizer 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.

The stabilizer composition of the present invention exhibits an excellent synergistic effect when used in combination with a non-metal stabilizing aid.

Examples of the non-metal stabilizing aid include, for example,
Β-diketone compounds such as dehydroacetic acid, dibenzoylmethane, stearoylbenzoylmethane, ester-containing β-diketone compounds, pentaerythritol, dipentaerythritol, sorbitol, mannitol, pentaerythritol or stearic acid half ester of dipentaerythritol, bis (dipentaethane) Polyhydric alcohol compounds such as thritol) adipate, glycerin, tris (2-hydroxyethyl) isocyanurate, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil,
Epoxidized tall oil fatty acid ester, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) ) Isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-
An epoxy compound such as epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate may be mentioned.

The stabilizer composition of the present invention comprises ester-based plasticizers such as phthalate ester-based plasticizers and adipate-based plasticizers, polyester-based plasticizers, phosphate ester-based plasticizers, chlorine-based plasticizers, and other plasticizers. A plasticizer or the like can be appropriately used in combination depending on the application.

The stabilizer composition of the present invention can be improved in light stability if it is used in combination with a light stabilizer, and therefore it is possible to appropriately select and use them in combination depending on the purpose of use.
These light stabilizers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based,
Hindered amine type, various metal salts or metal chelates,
In particular, nickel or chromium salts or chelates are included.

In addition, if necessary, the stabilizer composition of the present invention contains, for example, a cross-linking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an antiplateout agent, a surface treatment agent, a lubricant, and a hardener. A flame retardant, a fluorescent agent, a fungicide, a bactericide, a photodegradation agent, a non-metal stabilizer, a processing aid, a release agent and the like can be used in combination.

The chlorine-containing resin composition to which the stabilizer composition of the present invention is added can be used for all processing methods and applications.

As this processing method, calendar processing,
Extrusion processing, injection processing, blow processing, powder slash processing, paste processing, casting processing,
Other processing methods can be mentioned.

The chlorine-containing resin composition to which the stabilizer composition of the present invention has been added may be used as automobile interior / exterior materials, steel plate building materials, marking films, hard sheets, plates, pipes, profile extrusion products, wrap films, agricultural products. Film, flooring,
Mention may be made of leather, wallpaper, tarpaulins and all other chlorine-containing resin products.

[0039]

EXAMPLES Next, the stabilizing effect of the stabilizer composition of the present invention will be specifically shown by Examples. However, the invention is not limited to the examples given below.

Example 1 Hadlotalcite and organic phosphite were placed in a flask and stirred at a predetermined temperature for a predetermined time to obtain a liquid stabilizer composition.

The obtained stabilizer composition (No. 1 to No. 15)
Is shown in Table 1.

[0042]

[Table 1]

Example 2 The following composition was roll-kneaded and then pressed to form a sheet having a thickness of 1 mm. About this sheet
The thermal stability at 0 ° C was measured. Similarly, a 3 mm sheet was prepared and the initial colorability and transparency were evaluated.

The initial coloring property was evaluated on a scale of 10, with 1 indicating no discoloration and 10 indicating extremely remarkable coloring.

The results are shown in Table 2.

<Blending> Polyvinyl chloride resin 100 parts by weight Di (C _9-11 ) alkyl phthalate 50 Epoxidized soybean oil 3 Ba-stearate 0.8 Zn-stearate 0.4 Dibenzoylmethane 0.05 Stabilizer Composition (Table 2) 0.5

[0047]

Example 3 The following mixture was roll-kneaded and then pressed to form a sheet having a thickness of 1 mm. About this sheet
The thermal stability at 0 ° C was measured.

Further, this sheet is set in a mold, and the polyol for urethane foam and polyisocyanate are stirred and quickly poured into the mold to form a urethane foam layer, and a urethane backing sheet (urethane foam layer 10 m
m) was created.

Using this urethane backing sheet, 110
Coloring (heat aging) after heat aging at 400 ° C for 400 hours and 60 in a fade meter with a plaque panel temperature of 83 ° C.
The coloring (light resistance) after 0 hour light irradiation was observed. Coloring in both heat aging test and weather resistance test is 1 (no coloration) to 1
It was displayed in 10 stages of 0 (remarkably colored).

The results are shown in Table 3 below.

<Compounding> Polyvinyl chloride resin 100 parts by weight Di (C _8-12 alkyl) phthalate 70 Epoxidized soybean oil 3.0 Calcium carbonate 20 Titanium oxide 10 Zinc octylate 0.5 Barium stearate 1.0 Perchlorine Barium acid 0.1 Stabilizer composition (Table 3) 0.6

[0053]

Example 4 The following formulation was tested by the method of Example 2 for thermal stability, initial colorability and transparency. A film having a thickness of 0.1 mm was prepared with a kneading roll, and the film was used for a weather resistance test by outdoor exposure. The weather resistance test observes the surface condition of the film after 10 months and 20 months of outdoor exposure, and the evaluation criteria are 10 steps.
1 indicates almost no discoloration, and 10 indicates a blackish brown state.

The results are shown in Table 4.

<Compounding> Vinyl chloride resin (degree of polymerization: 1300) 100 parts by weight di-2-ethylhexyl phthalate 50 tricresyl phosphate 5 epoxidized linseed oil fatty acid octyl 2 Zn stearate 0.5 Ca stearate 0.8 dibenzoyl Methane 0.1 Sorbitan monopalmitate 1.5 Methylenebisstearic acid amide 0.5 Octadecyl-3- (3 ′, 5′-di-t-butyl-0.1 4′-hydroxyphenyl) propionate Ca ditetradecyl Phosphite 0.9 Sodium perchlorate 0.2 Stabilizer composition (Table 4) 1.0

[0057]

From the results of the respective examples, when the hydrotalcite and the organic phosphite are separately added to the chlorine-containing resin, the transparency and the colorability are poor. Compared to that,
It is clear that when a dispersion of hydrotalcite in an organic phosphate ester is added to a chlorine-containing resin in advance, not only the transparency and the colorability are significantly improved but also the weather resistance is significantly improved. Is.

[0059]

INDUSTRIAL APPLICABILITY The stabilizer composition of the present invention is used as a stabilizer for a chlorine-containing resin in addition to improving its heat resistance and colorability.
The transparency also has a remarkable effect.

Claims (1)

[Claims] 1. A stabilizer composition for a chlorine-containing resin, comprising 100 parts by weight of a hydrotalcite compound uniformly dispersed in 10 to 1000 parts by weight of an organic phosphite.