JP3176751B2 - Stabilizer for chlorine-containing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer for a chlorine-containing polymer, and more particularly, to a stabilizer for a chlorine-containing polymer having little initial coloring and excellent heat stability.

[0002]

2. Description of the Related Art It has long been known that amino acids and functional derivatives thereof have a thermal stabilizing effect on chlorine-containing polymers such as vinyl chloride resins. For example, Tokiko Sho 52
Japanese Patent No. -30176 discloses that 0.01 to 5 parts by weight of an α-amino acid, α-amino acid functional derivative, polyamide or polypeptide polymer and 0.5 to 12 parts by weight of alkali are contained per 100 parts by weight of a chlorine-containing polymer. A stabilized chlorine-containing polymer composition comprising an earth metal-based inorganic stabilizer is described.

Japanese Patent Application Laid-Open No. 54-55047 discloses a heat-stable chlorinated composition comprising 0.1 to 10 parts by weight of a metal salt of an amino acid or a derivative thereof per 100 parts by weight of a vinyl chloride resin. A vinyl resin composition is described. Further, JP-A-63-301248 discloses that 0.1 to 10 parts by weight of zinc glycinate and / or zinc glutamate and 0.01 to 5.0 parts by weight of a basic organozinc compound are added to 100 parts by weight of a halogen-containing resin. A novel halogen-containing resin composition formulated by weight is described.

[0004]

Although amino acids and functional derivatives thereof have a thermostabilizing effect at high temperatures, their sustainability is still not sufficiently satisfactory. The problem is that the so-called blackening occurs within a relatively short time. Combining zinc amino acids with zinc higher fatty acids improves the persistence to some extent but is not yet fully satisfactory. Amino acids and their functional derivatives tend to color the vinyl chloride resin red, which is already observed in the early stages of compounding the resin.

Accordingly, an object of the present invention is to provide a stabilizer for a zinc-containing amino acid-based polymer having excellent thermal stability and durability. Another object of the present invention is to provide a stabilizer for a chlorine-containing polymer, which has an improved intended coloring tendency and has remarkably excellent thermal stability at high temperatures.

[0006]

According to the present invention, there is provided an amino acid zinc / higher fatty acid zinc homogeneous composition obtained by reacting a zinc excess amino acid zinc with a higher fatty acid or an ammonium salt thereof in an equivalent amount or more per excess zinc. A stabilizer for a chlorine-containing polymer is provided.

In the stabilizer for a chlorine-containing polymer according to the present invention, 0.5 to 30% by weight of the β-diketone or β-keto acid ester per homogeneous composition is used together with the zinc amino acid / higher fatty acid zinc composition. It is preferred to contain.

[0008]

According to the present invention, a zinc-excess amino acid zinc is produced, and the amino acid zinc is reacted with a higher fatty acid or an ammonium salt thereof in an amount equivalent to or more than the zinc content. As compared with the above composition, a uniform composition of zinc amino acid / higher fatty acid zinc having significantly improved thermal stability can be obtained. See Table 1 below. The mixture of zinc amino acid and zinc higher fatty acid shows a blackening time of 30 to 40 minutes when mixed with a vinyl chloride resin and subjected to a heat resistance test at 185 ° C., according to the mixing method. When the mixing method is adopted, the blackening time is extended to about 70 minutes, and the thermal stability from rank 2 to rank 4 is improved.

The improvement in thermal stability according to the present invention has been found as a phenomenon as a result of a number of experiments, and the reason is not clear. However, in the reaction-mixing method of the present invention, the amino acid zinc is contained in the product. It is recognized that the higher fatty acid zinc is mixed at the molecular level, and that the thermal stability is improved due to the close interaction between the two. Product of the invention (homogeneous composition)
Then, the amino acid zinc (A) and the higher fatty acid zinc (B) are present in a molar ratio of A: B = 1: 0.001 to 1: 0.2, particularly 1: 0.001 to 1: 0.1. When the amount of the higher fatty acid zinc (B) is less than the above range or more than the above range, the thermal stability tends to be lower than when the amount is within the above range.

[0010] The preferred heat stabilizer of the present invention is 0.5 to 30 parts by weight of the above-mentioned homogeneous composition of zinc amino acid and zinc higher fatty acid.
% By weight, in particular from 1.0 to 20% by weight of .beta.-diketone or .beta.-keto acid ester. By containing a β-diketone or β-keto acid ester, the zinc amino acid zinc coloring tendency is remarkably improved, and the thermal stability is also remarkably improved (see Table 2 described later). If the amount of the β-diketone or β-keto acid ester is lower than the above amount, the effect of preventing the initial coloring is insufficient, while if it is higher than the above range, the blackening is accelerated.

Further, the preferred heat stabilizer of the present invention is 2.9 to the above-mentioned homogeneous composition of zinc amino acid and zinc higher fatty acid.
From 80 to 80% by weight, especially from 30 to 70% by weight of polyhydric alcohol. Polyhydric alcohol chelate nucleophilically zinc chloride, which is generated from the chemical reaction between the zinc compound such as the product of the present invention and PVC and causes a sudden PVC deterioration phenomenon called burning due to its strong Lewis acidity. It can delay and significantly improve the thermal stability. If the amount of the polyhydric alcohol is less than the above blending amount, the burning retarding effect is low,
In some cases, processing troubles such as mold sticking of a molding machine may be induced.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

<Production method> As the amino acid in the present invention, any amino acid having an amino group and a carboxyl group bonded to the same carbon atom, for example, a compound of the formula

RCH (NH ₂ ) COOH wherein R is an amino acid residue. Suitable examples are glycine, alanine,
Leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, pyroglutamic acid, lysine, algin, phenylalanine, tyrosine, histidine, tryptophan,
Pronin, oxypronin and the like.

Among these, glycine is preferred. Zinc-rich amino acid zinc, the basic amino acid zinc, is most advantageously obtained by reacting an amino acid solution with zinc white. In general, it is preferable to gradually add zinc white to the amino acid solution and carry out the reaction with stirring. The reaction temperature is not particularly limited, but is suitably in the range of 30 to 90 ° C. Zinc white is 0.005 to 0.2 per mole of zinc amino acid.
It is preferred to add 5 mol, especially 0.01 to 0.1 mol excess.

The reaction between the zinc-excess amino acid zinc and the higher fatty acid can be carried out in various manners. Advantageously, the suspension of the zinc-rich amino acid zinc formed by the above reaction is added to the higher fatty acid. Is added in the form of an emulsion of a partial ammonium soap to cause a reaction. As a result, a uniform composition of zinc amino acid and zinc higher fatty acid is produced. This synthesis method is extremely advantageous because the two-stage reaction is continuously performed in a single system. After the reaction, the product liquid is evaporated to dryness,
Furthermore, it is dried at a temperature of about 110 ° C. and pulverized to obtain a product.

Alternatively, a complex can be obtained by recovering zinc-excess amino acid zinc in the form of a powder and reacting the powder with a higher fatty acid in a solid phase. Solid-phase reactions include ball mills, jet mills, atomizers,
This can be advantageously performed by using a crusher such as a thunder crusher. As the higher fatty acid, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, such as stearic acid, palmitic acid, lauric acid, and ricinoleic acid, alone or as a mixture is used.

<Stabilizer> In the present invention, the above zinc amino acid / higher fatty acid zinc homogeneous composition is used as a stabilizer in the form of a composition with a β-diketone compound. As β-diketone or β-keto acid ester, those conventionally known for this use, for example, 1,3-cyclohexadione, methylenebis-1,3-cyclohexadione, 2-
Benzyl-1,3-cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexanedione, benzoyl-P −
Chlorobenzoylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, bis (4-chlorobenzoyl) methane, bis (methylene-3,4-dioxybenzoyl) methane, butanoylacetone, distearoylmethane, acetylacetone, stearoylacetone, bis (cyclohexanoyl) -methane and dipivaloylmethane, Methyl acetoacetate, ethyl acetoacetate, acetoacetate such as propyl acetoacetate, methyl propionyl acetate, propionyl acetate such as ethyl propionyl acetate, benzoate Le methyl acetate, benzoyl acetate such as benzoyl butyl acetate can be used.

The heat stabilizer of the present invention is desirably used in combination with a heat stabilizing aid. Such heat stabilizing aids include pentaerythritol, dipentaerythritol,
Polyhydric alcohols such as mannitol, sorbitol, glycerin, polysaccharides and derivatives thereof, tert-butylphenol, nonylphenol, dinonylphenol
, Cyclohexylphenol, phenylphenol,
Octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol
, Ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, t
ert-nonylphenol, decylphenol, ter
Examples include phenols such as t-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, and methyl-tert-octylphenol.

These stabilizers are used in an amount of 2.9 to 80% by weight, especially 3% by weight, based on the zinc amino acid / higher fatty acid zinc complex.
It is preferably used in an amount of 0 to 70% by weight. In addition, the stabilizer includes a compounding agent known per se, for example, an organic chelating agent, a plate-out inhibitor, a release agent, an antistatic agent, an antifogging agent, an ultraviolet absorber, an antioxidant, an insect repellent, an insect repellent. ,
Organic components such as antibacterial agents, fragrances, and coloring agents can be used together. Furthermore, this compounding agent contains various metal soaps, waxes, resins, surfactants, including the aforementioned main components,
Surface treatment can also be performed in advance with various coupling agents.

The organic components used for loading and surface treatment include:
The content is preferably in the range of 0.5 to 10% by weight, particularly 2 to 8% by weight for each compounding agent. Other stabilizers that synergistically contribute to the stabilization of the stabilizer of the present invention and the chlorine-containing polymer include those described below.

1. Zeolite-based stabilizer: zeolite A,
Synthetic zeolites such as zeolite X and zeolite Y, partially or completely neutralized products thereof, or aluminosilicates of their metal ions (eg, calcium, magnesium, zinc ions) converted products.

2. Hydroxides, basic salts and silicates of alkaline earth metals and zinc: hydroxides such as calcium hydroxide, magnesium hydroxide, zinc hydroxide and strontium hydroxide. Formula (oxide standard)

Embedded image in MO · qMX ₂ / m formula, M is an alkaline earth metal or zinc, X is an acidic oxide anion or an organic anion of an inorganic, m is the valence of the anion X, q is 0. A basic salt having a composition of 1 to 10, especially 0.5 to 5. In particular, basic calcium carbonate, basic magnesium carbonate, basic zinc carbonate, basic calcium stearate, basic zinc stearate, basic magnesium palmitate and the like.

Formula (based on oxide)

Embedded image MO · kSiO ₂ formula, M represents an alkali earth metal or zinc, k is 0.
A silicate having a composition of 1 to 10, especially 0.5 to 5.

Examples of the chlorine-containing polymer include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and 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-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorine Propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, Examples thereof include vinyl chloride-acrylonitrile copolymer and internally plasticized polyvinyl chloride.

The heat stabilizer of the present invention is preferably used in an amount of 0.1 to 10 parts by weight, particularly 0.3 to 7 parts by weight, per 100 parts by weight of these chlorine-containing polymers. Further, when the stabilizer of the present invention is used as a chlorine-containing resin composition in the form of a mixture with a chlorine-containing resin, as described later in Example 2, the effects of the present invention can be sufficiently exerted even by ordinary light mixing. Spar mixer, Henschel mixer, thunder crusher, ball mill, jet mill, etc., the invention stabilizer and the chlorine-containing resin, when passing through a mixing step capable of achieving intimate mixing of both under high-speed shearing, more of the stabilizer of the invention The function and effect can be improved.

[0025]

The present invention is further described in the following examples. However, the invention is not limited to these cases.

Embodiment 1 FIG. A stabilizer comprising a uniform composition of zinc amino acid / higher fatty acid zinc according to the present invention was prepared by a wet method described below. Put 500 ml of water in a reaction vessel
Warm up. Under stirring, 2 mol of the amino acids from Table 1 are added. When the amino acids are dissolved, the zinc oxide powder is gradually added in a predetermined amount shown in Table 1 so as to be in excess of zinc, and held for about 1 hour. Put 300 ml of water in another container and raise the temperature to 70 ° C.
A predetermined amount of the higher fatty acid shown in Table 1 and ammonium hydroxide (1/5 mole of the higher fatty acid) are added to prepare a partial emulsion.
This emulsion is added to the zinc-rich amino acid zinc solution, and
Let stir for 0 minutes. Thereafter, drying was carried out at 110 ° C. to remove water, and thus stabilizers of Sample Nos. 1 to 6 comprising crystals of the homogeneous composition of zinc amino acid / higher fatty acid zinc were obtained. After that, it was pulverized with a ball mill for 4 hours before use.

Embodiment 2 FIG. A stabilizer comprising a homogeneous composition of zinc glycine / zinc stearate according to the present invention was prepared by the following dry method. A zinc-excess glycine zinc solution was prepared at a ratio of 150 g (2 mol) of glycine and 84.6 g (1.04 mol) of zinc oxide in the same manner as in Example 1, and thereafter, 11 g
After drying at 0 ° C. to remove water, a crystal powder was obtained. The total amount of the crystal powder and 22.7 g (0.08 mol) of stearic acid powder were put into a ball mill, and pulverized and mixed for 4 hours to obtain a sample No. 7 comprising a uniform composition of zinc glycine / zinc stearate.
Was obtained.

Comparative Example 1 500 ml of water is put in a reaction vessel, heated to 70 ° C., and 150 g (2 mol) of glycine is added under stirring. When glycine is dissolved, zinc oxide 81.
4 g (1 mol) is gradually added and maintained for about 1 hour. Since then 1
After drying at 10 ° C. to remove water, crystals of neutral salt of glycine zinc were obtained, which was designated as Sample No. 8. Then, it was pulverized with a ball mill for 4 hours before use.

Comparative Example 2 The total amount of neutral glycine zinc crystal powder obtained in the same manner as in Comparative Example 1 and 25.3 g (0.04 mol) of zinc stearate powder were placed in a ball mill, pulverized and mixed for 4 hours, and mixed with zinc glycine / zinc stearate. The mixture was obtained and designated as Sample No. 9. The stabilizers obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were combined with the following ingredients as common ingredients by "ordinary light mixing" and subjected to a sheet test. PVC (Zeon 103EP) 100 parts by weight Zinc stearate 1.5 parts by weight Dipentaerythritol 0.2 parts by weight Stearoyl benzoylmethane 0.05 parts by weight Sample Nos. 1 to 9 1.3 parts by weight

This composition was kneaded with a roll heated to 160 ° C. for 6 minutes to prepare a sheet having a thickness of 0.5 mm. This was put into a gear oven at 185 ° C., taken out every 10 minutes, and the hue of the sheet was observed. However, the relationship between the sheet hue and the degree of discoloration was visually determined according to the following criteria.

Table 1 Sample Nos. 1 to 7 are stabilizers comprising a uniform composition of zinc amino acid / higher fatty acid zinc obtained by the production method of the present invention, and Sample Nos. 8 and 9 are comparative examples.
It can be seen that the homogeneous amino acid / higher fatty acid zinc composition obtained in the present invention has better heat stability than the comparative example, and the time to blackening of the sheet is longer by 20 to 40 minutes.

Embodiment 3 FIG. The sheet test was performed in the same manner as in Examples 1 and 2, except that the mixing conditions of the resin compounding agent were changed using the stabilizers of the present invention of Sample Nos. 1 to 7. Examples of intimate mixing using a high-speed rotary mixer are shown in A,
Table 2 shows a comparison between the two, with B being a light normal mixing example. As is evident from Table 2, the stabilizer according to the present invention has a higher thermal stability as it is more intimately mixed with the resin.

Embodiment 4 FIG. And Comparative Example Using a stabilizer consisting of Sample No. 2 according to the present invention, in combination with β-diketone and polyhydric alcohol in the following formulation,
The formulations of Sample Nos. 11-17 are tested for these effects. 100 parts by weight of PVC (Zeon 103EP) 1.5 parts by weight of zinc stearate 1.3 parts by weight of glycine zinc of sample No. 2 β-diketone Table 3 Polyhydric alcohol Table 3

These compounds were thoroughly mixed by a high-speed mixer. This composition was kneaded with a roll heated to 160 ° C. for 6 minutes to prepare a sheet having a thickness of 0.5 mm. This was put into a gear oven at 185 ° C., taken out every 10 minutes, and the hue of the sheet was observed. The evaluation is the same as in Example 1. It is clear from the results in Table 3 that the uniform composition of zinc amino acid / higher fatty acid zinc obtained in the present invention has improved initial coloring and improved heat stability sustainability by combining β-diketone and polyhydric alcohol. I understand.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

According to the present invention, the use of the stabilizer of the present invention does not require special mixing conditions, especially when compounding a resin, is excellent in handleability during resin processing, has little initial coloring, and is particularly stable at high temperatures at high temperatures. Thus, it is possible to obtain a chlorine-containing resin molded article having excellent properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 27/06 C08K 5/07-5/098 C08K 5/16-5/357 C09K 15/20-15 / twenty four

Claims (4)

(57) [Claims] 1. A chlorine-containing polymer stabilizer comprising a zinc amino acid / higher fatty acid zinc homogeneous composition obtained by reacting a zinc-excess amino acid zinc with a higher fatty acid or an ammonium salt thereof in an equivalent amount or more per excess zinc. 2. The stabilizer for chlorine-containing polymers according to claim 1, wherein the zinc-excess zinc amino acid contains 0.001 to 0.2 mol of excess zinc per mol of zinc amino acid. 3. The composition according to claim 1, wherein the composition comprises the amino acid zinc / higher fatty acid zinc homogeneous composition and 0.5 to 30% by weight of the homogeneous composition of β-diketone or β-keto acid ester. 4. The stabilizer for a chlorine-containing polymer according to item 1. 4. The chlorine according to claim 1, wherein the homogeneous composition contains zinc amino acid and zinc higher fatty acid in a molar ratio of 1: 0.001 to 1: 0.2. Polymer containing stabilizer.