JPH11279355A - Thermally stabilized halogen-containing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having improved safety and heat resistance by mixing a halogen-containing resin with a natural proteinaceous filler and/or a synthetic polyamino acid powder, a polyhydric alcohol and/or esterified product obtained by eterifying a part of hydroxy group of the polyhydric alcohol, and a zinc salt of an organic acid. SOLUTION: It is desirable that the natural proteinaceous filler used is a keratin protein powder or a collagen protein powder. The synthetic polyamino acid powder used is a homopolymer of a single amino acid or a derivative thereof or a copolymer of a plurality of amino acids and/or of derivatives thereof. The amount of the natural proteinaceous filler or the synthetic polyamine acid powder is 0.01-20 pts.wt. per 100 pts.wt. halogen-containing resin. The polyhydric alcohol used is desirably pentaerythritol or dipentaerythritol and is used is an amount of 0.001-10 pts.wt. per 100 pts.wt. resin. The zinc salt of the organic acid, for example, zinc acetate is used in an amount of 0.01-20 pts.wt. per 100 pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-stabilized halogen-containing resin composition, and more particularly to a halogen-containing resin containing natural protein filler and / or synthetic polyamino acid powder, polyhydric alcohol and / or polyhydric alcohol. The present invention relates to a heat-stabilized halogen-containing resin composition comprising a partially esterified hydroxyl group and an organic acid salt of zinc.

[0002]

2. Description of the Related Art Halogen-containing resins such as vinyl chloride resins have high flame retardancy and have excellent properties such as light resistance, recyclability, chemical resistance, etc., and are used for building materials, piping, electric wire covering materials, various films, Very widely used as containers and the like. The halogen-containing resin undergoes thermal decomposition during demolding by thermal decomposition accompanied by dehydrohalogenation, and causes a quality deterioration phenomenon such as thermal coloring of the resin and a decrease in physical properties such as strength. In order to solve such problems, it is common to add a stabilizer for improving the thermal stability of the halogen-containing resin.

[0003] As a stabilizer for improving the thermal stability of a halogen-containing resin (hereinafter referred to as "thermal stabilizer"), metal salts of organic acids such as fatty acids, aromatic carboxylic acids and amino acids have hitherto been used. I have. Specifically, lead salts and cadmium salts have satisfactory functions as heat stabilizers, but their use is limited because of their serious toxicity problems. As an alternative to these heat stabilizers, zinc organic acid salts have attracted attention. Although a zinc-based heat stabilizer is often used in combination with a calcium salt or a barium salt, it may cause a so-called “zinc burn” coloring problem.

[0004] In order to solve the problem of "zinc burn" caused by a zinc-based heat stabilizer, various stabilizing aids such as organic phosphorus compounds, epoxy compounds, organic sulfur compounds, polyhydric alcohol compounds, β-diketones are generally used. Combinations of compounds and the like have been proposed and put to practical use. In particular, polyhydric alcohols such as pentaerythritol and dipentaerythritol and esterified products of some of the hydroxyl groups thereof have a remarkable effect of preventing "zinc burn" from JP-B-51-0210.
No. 8, JP-A-54-108845, JP-B-5-108845
Nos. 7-61289 and JP-B-57-18546. However, there is a need for a heat stabilization system capable of imparting a higher level of heat stabilization effect to a halogen-containing resin than the heat stabilization effect of such a zinc-based heat stabilizer and stabilization aid. It is desired to be achieved by blending a highly safe zinc-based stabilizer.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a halogen-containing resin composition having high safety and excellent heat resistance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and have found that a natural protein-based filler and / or a synthetic polyamino acid powder can be mixed with an organic acid salt-based stabilizer of zinc and a polyvalent compound. It has been found that when used in combination with an alcohol-based stabilizing aid, a remarkable heat stabilizing effect is exerted on a halogen-containing resin, and the present invention has been completed.

That is, the present invention comprises a halogen-containing resin blended with a natural protein-based filler and / or a synthetic polyamino acid powder, a polyhydric alcohol and / or an esterified product of a partial hydroxyl group thereof, and an organic acid salt of zinc. It is a heat-stabilized halogen-containing resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a natural protein filler used in the present invention, a powder obtained from a protein which is widely present in nature and which is widely used industrially as a filler for synthetic leather or the like is used. And keratin protein powder, collagen protein powder, soy protein powder, fibroin protein powder and the like. Two or more natural protein-based fillers can be arbitrarily mixed and used. Among them, when keratin protein powder and collagen protein powder are used, the effect of the present invention, that is, the heat stabilizing effect is particularly excellent, and it is possible to supply a resin composition having more excellent heat stability.

Keratin protein powders include animal hair, hair,
Those obtained by finely pulverizing feathers, claws, corners and the like can be mentioned. Its production method is described in JP-A-57-163392,
No. 2416, for example. Examples of animal hair referred to here include animal hair obtained from animals such as sheep, goats, camels, and alpacas. Examples of the feathers mentioned here include feathers obtained from poultry such as chickens, ducks and geese, water birds such as duck, and birds such as pigeons and ostriches.

[0010] As the collagen protein powder, those obtained by pulverizing natural leather such as cow skin, pig skin, goat skin and sheep skin can be used arbitrarily. A method for producing a collagen protein-based powder is described in JP-A-52-156901 and JP-A-62-77327.
JP, JP-A-2-83044, JP-A-2-96
No. 600, etc., which are industrially manufactured and used can be arbitrarily used.

The synthetic polyamino acid powder used in the present invention includes synthetically produced amino acids and / or amino acids used in fillers such as synthetic leather, cosmetics and various medical materials.
Alternatively, it is a polymer containing an amino acid derivative as a constituent component, and its synthesis method may be chemical synthesis or fermentative synthesis. Chemical synthesis methods include an acid chloride method, a heat solid phase polymerization method, an active ester method, an azide method, and the like.
74)) and the like, and among them, a polymerization method using an amino acid N-carboxylic anhydride (NCA) as a raw material is capable of adjusting the molecular weight, and is actually industrialized.

The synthetic polyamino acid powder used in the present invention comprises:
It may be a homopolymer of a single amino acid or an amino acid derivative, or a copolymer of a plurality of amino acids and / or amino acid derivatives.
A copolymer with another polymer such as an epoxy resin may be used, and these two or more polymers may be arbitrarily mixed and used. Examples of the types of amino acids constituting the synthetic polyamino acids used in the present invention include glycine, alanine, valine, norvaline, isoleucine, phenylalanine, tyrosine, threonine, methionine,
Monoaminomonocarboxylic acids such as serine, cysteine, cystine, thyroxine, asparagine and glutamine; monoaminodicarboxylic acids such as aspartic acid and glutamic acid; lysine, ornithine, α, γ-diaminobutyric acid, hydroxylysine, arginine and histidine (Hereinafter, referred to as "polyaminomonocarboxylic acid"). Among them, a synthetic polyamino acid powder containing an amino acid having a structure of polyaminomonocarboxylic acid, which has an amino group on a polymer side chain, is preferable in view of the heat stabilizing effect. The types of amino acid derivatives constituting the synthetic polyamino acid used in the present invention include glutamic acid-γ-methyl ester, glutamic acid-γ-benzyl ester, aspartic acid-β-methyl ester, (N-carbobenzoxy)-
Examples include lysine, esters of ethylene glycol and aspartic acid, and among others, synthetic polyamino acid powder containing an amino acid derivative having the structure of polyaminomonocarboxylic acid, which has an amino group on its polymer side chain. Those are desirable in terms of the heat stabilizing effect. Specific examples of the amino acid derivative having a polyaminomonocarboxylic acid structure include a monoamide compound of aspartic acid and ethylenediamine, a monoamide compound of glutamic acid and hexamethylenediamine, and a monoamide compound of glutamic acid and N, N-dimethyl-1,3-diaminopropane. Monoamide compound, N
-Methyllysine and the like. Methods for producing these synthetic polyamino acid powders are described in JP-A-1-127039, JP-A-4-153221, and JP-A-5-93.
No. 305 has been proposed, and those manufactured industrially can be used arbitrarily. Powder production methods include emulsion polymerization during polymerization and precipitation of powder polymer, method of adding a poor solvent to a solution of synthetic polyamino acid to precipitate powder polymer, and molding of synthetic polyamino acid into a film or fibrous form. There is a method of cutting and pulverizing the cut material, but the difference in the method does not affect the effect of the present invention.

The average particle size of the natural protein filler and / or the synthetic polyamino acid powder used in the present invention is desirably 100 microns or less, and more desirably 10 microns or less. If it is larger than 100 microns, the surface of the resin composition after the molding becomes rough, and the quality such as the physical properties deteriorates, which is undesirable.

The amount of the natural protein-based filler and / or synthetic polyamino acid powder used in the present invention is 0.01 to 20 parts by weight, preferably 0.05 to 20 parts by weight, per 100 parts by weight of the halogen-containing resin. 10 parts by weight. 0.01
If the amount is less than 10 parts by weight, the intended heat stabilizing effect is not sufficiently exerted. On the other hand, if the amount is more than 20 parts by weight, the physical properties of the halogen-containing resin compound may be reduced. In the present invention, the natural protein-based filler and the synthetic polyamino acid powder may be used alone or in any combination.

The polyhydric alcohol compound used in the present invention includes pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, sorbitol, glycerin, polyglycerin and the like. Further, those compounds in which some of the hydroxyl groups of these compounds are chemically modified by esterification, etherification, or the like can be used.

Of the polyhydric alcohols, particularly, pentaerythritol and dipentaerythritol have a high heat stabilizing effect, and their use is desirable. Further, those obtained by esterifying pentaerythritol or dipentaerythritol with a basic acid have a high heat stabilizing effect, and are therefore desirable.
Particularly, pentaerythritol and / or dipentaerythritol and a higher fatty acid having 10 to 22 carbon atoms (for example, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 1,2 -Hydroxystearic acid,
Oleic acid, linoleic acid, etc.) and / or 4 to 4 carbon atoms
Since the esterified product of a partial hydroxyl group with 10 dibasic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, etc.) has a high molecular weight, there is no sublimation during heat processing. It is desirable because it has additional advantages such as not causing mold contamination, improving workability, and being excellent in dispersibility in resin. The use of a dibasic acid has a low sublimation effect, the dibasic acid having 4 to 10 carbon atoms has a thermal stabilizing effect, the presence of a higher fatty acid and the carbon atoms having 10 to 22 carbon atoms.
Contributes to the processability improving effect and the good dispersibility effect. The molecule can be arbitrarily designed and used in accordance with the intended function and blending system of the halogen-containing resin composition. An esterified product of a partial hydroxyl group of such pentaerythritol and / or dipentaerythritol with a higher fatty acid having 10 to 22 carbon atoms and / or a dibasic acid having 4 to 10 carbon atoms is disclosed in No. 6350, Japanese Patent Publication No. 57-61
No. 289, JP-A-55-069693 and the like, it can be industrially easily produced by a known method, and it is commercially available, though partially.

The amount of the polyhydric alcohol compound used is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the halogen-containing resin. If the amount is less than 0.01 part by weight, the intended heat stabilizing effect cannot be sufficiently exhibited. On the other hand, if it exceeds 10 parts by weight, the physical properties of the halogen-containing resin composition may be reduced. As the polyhydric alcohol compound used in the present invention, those exemplified above may be used alone, or a plurality of types of compounds may be used in combination.

Examples of the organic acid in the organic acid salt of zinc used in the present invention include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, stearic acid, behenic acid, benzoic acid, salicylic acid and oleic acid. Examples include acid, malic acid, succinic acid, adipic acid, terephthalic acid, trimellitic acid, glutamic acid, lysine, pyrrolidone carboxylic acid, aspartic acid, glycine and the like. The amount of the organic acid salt of zinc to be used may be 0.01 to 20 parts by weight based on 100 parts by weight of the halogen-containing resin, that is, the amount used usually as a heat stabilizer.

In the present invention, if necessary, an organic phosphorus compound, an epoxy compound, a β-diketone compound or the like can be further used in combination. There is no particular limitation on the use of plasticizers and fillers usually used in halogen-containing resin compositions. Further, if necessary, other additives such as an antioxidant, an ultraviolet absorber, a flame retardant, a lubricant, a pigment, an antistatic agent, an antifogging agent, etc. may be used at all.

Examples of the halogen-containing resin used in the present invention include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-butadiene. Copolymers and the like, and these alloys may be used. Also, alloys of these halogen-containing resins and non-halogen-containing resins such as polyethylene, polypropylene, polystyrene, polyphenylene ether, polyamide, and polycarbonate may be used. The olefin resin produced using a Ziegler-type catalyst contains a halogen-containing catalyst residue, and the olefin resin containing such a halogen-containing catalyst residue is also included in the halogen-containing resin according to the present invention.

When the heat-stabilized halogen-containing resin composition of the present invention is kneaded, molded, and processed, there is no particular limitation on the compounding method, kneading method, order, molding method and the like.

[0022]

EXAMPLES In order to further clarify the features of the present invention, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[Production Example 1] Pentaerythritol 136
73 parts of adipic acid and 284.5 parts of stearic acid were added to the mixture, and the mixture was stirred at 230 ° C. for 2 hours to perform an esterification reaction.
An adipic / stearic acid mixed partial ester of pentaerythritol (esterification ratio: 45 to 55%) was obtained.

[Production Example 2] Production method of wool powder 1 kg of defatted chips obtained by defatting wool that had been sufficiently defatted with 1,1,1-trichloroethane into chips having a length of several millimeters with a cutter was mixed with 5 liters of a 0.1N sodium hydroxide aqueous solution. In addition, the mixture was partially hydrolyzed at 80 ° C. for 30 minutes while stirring at normal pressure. This was filtered, redispersed in water, neutralized with a hydrochloric acid solution, washed, and then subjected to a ceramic ball mill for 2 hours.
Fine particles were formed by a wet method for 4 hours. After centrifuging this,
Dried, 900 g wool powder with an average particle size of 5-10 microns
I got

[Production Example 3] Method for producing feather powder 1 kg of a feather chip of a waterfowl (goose) treated in the same manner as in Production Example 2 was dispersed in 5 liters of a 0.1N aqueous sodium hydroxide solution, and a 10-liter pressurized container was prepared. At 12
The mixture was partially hydrolyzed with stirring at 0 ° C. for 30 minutes. Less than,
The same treatment as in Production Example 2 was repeated to obtain an average particle size of 5-1.
920 g of 0-micron feather fine powder was obtained.

[Production Example 4] Production method of aminated methyl polyglutamate N-carboxy-γ-methyl-L-glutamic anhydride (1000 g) was suspended in ethyl acetate (6 L), diethanolamine (1 g) was added, and the mixture was stirred at room temperature for 8 hours. . 5 L of methanol was added to the obtained ethyl acetate solution of poly-γ-methyl-L-glutamate, and the mixture was stirred. The precipitated poly-γ-methyl-L-glutamate was filtered, washed with methanol, dried, and pulverized with a feather mill. A 10-20 micron poly-γ-methyl-L-glutamate powder was obtained. 50 g of this poly-γ-methyl-L-glutamate powder was suspended in a mixed solution of 500 mL of methanol and 500 mL of ethylenediamine, followed by gentle stirring at 65 ° C. for 8 hours. After filtration, the resultant was washed with water and methanol to obtain an aminated polymethyl glutamate. This aminated polymethyl glutamate is 65% of the carboxyl group of the polymer side chain.
Was confirmed to be amidated with ethylenediamine by elemental analysis and 1H-NMR.

Examples 1-1 to 13 and Comparative Examples 1-1 to
9] The composition shown in Table 1 was kneaded at 155 ° C for 5 minutes using a hot roll, and then pressed at 155 ° C for 5 minutes using a hot press to prepare a sheet having a thickness of 3 mm. Using the obtained sheet, a thermal coloring test (static thermal stability test) at 180 ° C. using a gear oven and a dynamic thermal stability test at 200 ° C. using a Labo Plastomill were performed. The thermal coloring test measured the time until the sheet turned brown or partially blackened, and the dynamic thermal stability test measured the time during which the resin was decomposed and the kneading torque started to increase. Table 1 shows the test results.

[0028]

[Table 1]

Examples 2-1 to 10 and Comparative Examples 2-1 to 2-1
6] The composition shown in Table 2 was 3 mm thick in the same manner as in Example 1.
Created a sheet. Using the obtained sheet, a thermal coloring test (static thermal stability test) at 180 ° C. using a gear oven was performed. Table 2 shows the test results.

[0030]

[Table 2]

[0031]

As described above, according to the present invention, a highly safe zinc-based stabilizer is used in combination with a polyhydric alcohol-based stabilizer and a natural protein-based filler and / or a synthetic polyamino acid powder. By doing so, the heat-resistant durability of a halogen-containing resin such as a vinyl chloride resin can be remarkably improved, and application to building materials, electric wire covering materials, various films, and the like is expected.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 89:00)

Claims (6)

[Claims] 1. A halogen-containing resin obtained by blending a halogen-containing resin with a natural protein filler and / or a synthetic polyamino acid powder, a polyhydric alcohol and / or an esterified product of a partial hydroxyl group thereof, and an organic acid salt of zinc. Composition. 2. 0.01 to 20 parts by weight of a natural protein-based filler and / or synthetic polyamino acid powder, 100 to 100 parts by weight of a halogen-containing resin, and 0.01 to 10 parts of a polyhydric alcohol or a partially hydroxylated ester thereof. 2 parts by weight, 0.01 to 20 parts by weight of an organic acid salt of zinc.
The halogen-containing resin composition according to the above. 3. The heat-stabilized halogen-containing resin composition according to claim 1, wherein the natural protein-based filler is a keratin protein powder and / or a collagen protein powder. 4. The synthetic polyamino acid powder comprises an amino acid having a polyaminomonocarboxylic acid structure and / or an amino acid derivative as a polymer component.
Or the heat-stabilized halogen-containing resin composition according to 2 above. 5. The halogen-containing resin composition according to claim 1, wherein the polyhydric alcohol is pentaerythritol and / or dipentaerythritol. 6. An esterified product of a partial hydroxyl group of a polyhydric alcohol, comprising at least one of pentaerythritol and dipentaerythritol, a higher fatty acid having 10 to 22 carbon atoms and a dibasic acid having 4 to 10 carbon atoms. 3. The halogen-containing resin composition according to claim 1, which is an esterified product of a partial hydroxyl group with at least one of the above.