JPH11335502A - Thermal stabilizer and thermally stabilized resin composition containing halogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain high safety and excellent thermal stability by combining a dolomitic compound and a zinc salt of an organic acid. SOLUTION: Dolomitic compounds are not particularly limited and there can be employed natural dolomites and synthetic dolomites comprising a double salt of calcium carbonate and magnesium carbonate. Preferably dolomitic compounds have a calcium/magnesium wt. ratio, in terms of CaO and MgO, of 5:95 to 95:5. As the dolomitic compound is preferably used a light-burned dolomite obtained by light burning of a double salt compound having the aforementioned calcium/magnesium wt. ratio to bring about particularly excellent thermal stability of a halogen-containing resin composition. With 100 pts.wt. of the halogen-containing resin are admixed about 0.01-150 pts.wt. of the dolomitic compound and about 0.01-20 pts.wt. of a zinc salt of an organic acid. As a thermal stabilizer there can be further compounded a polyhydric alcohol and/or a β-diketone compound.

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 heat-stabilized halogen-containing resin containing a dolomite compound and a zinc salt of an organic acid. And a halogen-containing resin composition.

[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 sheets, It is widely used as various films and containers.

[0003] During the thermoforming, the halogen-containing resin undergoes thermal decomposition accompanied by dehydrohalogenation, which 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.

[0004] stabilizers to improve thermal stability of the halogen-containing resin (hereinafter referred to as "thermal stabilizer") as the sub <br/> years, fatty acids, aromatic carboxylic acids, organic acids such as amino acids Metal salts are used. Specifically, lead salts and cadmium salts have satisfactory functions as heat stabilizers, and in particular, lead-based stabilizers have been used in large quantities. However, their use is limited due to their significant toxicity problems. As a heat stabilizer instead of these, zinc salts of organic acids having high safety are attracting attention.

However, the heat stability effect of the zinc-based heat stabilizer is not sufficient as compared with the lead-based stabilizer, and the same level of heat stabilization as that of the lead-based stabilizer is achieved by blending a highly safe zinc-based stabilizer. There is a need for a thermal stabilization system that can impart effects to halogen-containing resins.

[0006]

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

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when a dolomite compound is used in combination with a zinc salt stabilizer of an organic acid, a halogen is produced. The inventors have found that a remarkable thermal stabilizing effect is exhibited for the contained resin, and have completed the present invention.

That is, the present invention provides a heat stabilizer for a halogen-containing resin comprising a dolomite compound and a zinc salt of an organic acid, and a heat-stabilized halogen-containing resin containing the heat stabilizer. A molded product obtained by molding the composition and the halogen-containing resin composition.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The dolomite compounds used in the present invention are not particularly limited, and are dolomite (ie, dolomite) which is widely used naturally and is used for wall materials, refractories for steelmaking, and the like. Can be used. Further, dolomite has a chemical composition of a double salt of calcium carbonate and magnesium carbonate, and a double salt of calcium carbonate and magnesium carbonate obtained by chemical synthesis, that is, a synthetic dolomite can also be used. The composition of the synthetic dolomite used in the present invention,
It is sufficient that calcium and magnesium are mixed in a certain ratio, and the weight ratio of CaO and MgO is 5:95.
A range of ~ 95: 5 is preferred. When a synthetic dolomite outside this ratio range is used, the heat stabilizing effect according to the present invention cannot be sufficiently obtained.

[0010] Derivatives obtained by modifying these natural and / or synthetic dolomite without greatly changing the metal element composition such as calcination and slaking can be used. Dolomite cement obtained by heating at 800 ° C, lightly-burned dolomite obtained by heating at 900 to 1000 ° C, dead-burned dolomite hard-burned at a high temperature of 1600 to 1800 ° C, and water were added to lightly-burned dolomite for digestion. For example, there are slaked lime, synthetic mud clinker and the like. Further, akermanite (Ca ₂ MgSi ₂ O ₇ )
It is also possible to use natural minerals having a calcium / magnesium ratio in the same range as the above-mentioned synthetic dolomite, and derivatives obtained by modifying synthetic double salts in the same manner, such as diopside (CaMg (SiO ₃ ) ₂ ) and various slags. it can. Furthermore, it goes without saying that any mixture of these may be used.

These dolomite and its derivatives are collectively referred to herein as dolomite-based compounds. These dolomite compounds are industrially produced in large quantities, and include steelmaking, ceramics, building materials, Since it is used in an extremely wide range of industries such as agriculture, it is of stable quality and can be obtained easily and at low cost. Above all, when lightly fired dolomite is used, the heat stability of the obtained halogen-containing resin composition becomes particularly good.

[0012] If necessary, an industrially used surface treating agent may be arbitrarily used insofar as the effects of the present invention are not impaired. Specifically, silane-based, aluminum-based,
Examples of the coupling agent include phosphoric acid-based coupling agents, cationic, anionic, nonionic surfactants such as atearic acid, zinc atearate, and calcium atearate, and polymer-based dispersants. However, in order to sufficiently obtain the effect of improving the thermal stability of the treatment agent of the present invention, these surface treatment agents are at most the same amount or the same amount as the compound used for the surface treatment of the dolomite compound in the present invention. It is preferred to keep it below the amount.

The amount of the dolomite compound used in the present invention is usually 0.1 to 100 parts by weight of the halogen-containing resin.
It is at least 01 parts by weight, preferably at least 0.05 parts by weight. If the amount is less than 0.01 part by weight, the intended heat stabilizing effect cannot be sufficiently exhibited. On the other hand, when more than 30 parts by weight of the dolomite compound is used, the heat stabilizing effect may not be further improved. The dolomite-based compound can be added up to about 200 parts by weight, preferably 150 parts by weight.
Used in parts by weight or less. If more than 200 parts by weight,
Although the thermal stabilizing effect of the present invention is not reduced, there is a possibility that the physical properties of the halogen-containing resin composition may be reduced as in the case of the usual filler.

The average particle size of the dolomite compound used in the present invention is preferably 100 microns or less, more preferably 10 microns or less. If it is larger than 100 microns, the surface of the resin composition after molding may be rough, resulting in a decrease in quality such as a decrease in physical properties.

The zinc salt of an organic acid used together with the dolomite compound in the heat stabilizer for a halogen-containing resin of the present invention will be described. Examples of organic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, stearic acid, behenic acid, benzoic acid, salicylic acid, oleic acid, malic acid, succinic acid, adipic acid,
Examples include terephthalic acid, trimellitic acid, glutamic acid, lysine, pyrrolidonecarboxylic acid, aspartic acid, glycine and the like.

The amount of the zinc salt of an organic acid is usually 0.01 to 2 parts per 100 parts by weight of the halogen-containing resin when used as a heat stabilizer for the halogen-containing resin.
It may be 0 parts by weight.

In the heat stabilizer for a halogen-containing resin of the present invention, in addition to a dolomite compound (or a surface-treated dolomite compound) and a zinc salt of an organic acid, the thermal coloring of the resin is further suppressed. Polyhydric alcohol compounds and / or
Alternatively, a β-diketone compound may be blended.

Examples of the polyhydric alcohol compound that can be used in the present invention include pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, sorbitol, glycerin, polyglycerin and the like. Further, those obtained by chemically modifying a part of the hydroxyl groups of these polyhydric alcohols by esterification, etherification, or the like can be used.

Among the polyhydric alcohol compounds, pentaerythritol, dipentaerythritol, or those obtained by esterifying them with a basic acid are particularly preferable.

Particularly, a partially esterified product of pentaerythritol and / or dipentaerythritol esterified with a higher fatty acid having 10 to 22 carbon atoms and / or a dibasic acid having 4 to 10 carbon atoms has a high molecular weight. Additional advantages such as no sublimation during heat molding and no mold contamination, improved processability of the resin, and improved dispersibility of powder (dolomite compounds, etc.) in the resin. Is preferred.

Examples of the higher fatty acids include capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 1,2-hydroxystearic acid, oleic acid,
Linoleic acid and the like.

The dibasic acids include, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid and the like.

A dibasic acid having 4 to 10 carbon atoms contributes to a low sublimation effect and a heat stabilizing effect, and a higher fatty acid having 10 to 22 carbon atoms contributes to a processability improving effect and a good dispersibility effect of the treated powder. I do.

The molecule can be arbitrarily designed and used according to the function and the blending system of the target 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 6350
JP, JP-B-57-61289, JP-A-55-61289
Can be easily manufactured industrially by a known method described in, for example, US Pat.
It is commercially available.

The amount of the polyhydric alcohol compound to be used is generally 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. 0.01
If the amount is less than parts by weight, the synergistic heat stabilizing effect of the polyhydric alcohol compound may not 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, the above-mentioned compounds may be used alone, or two or more kinds may be used in combination.

As the β-diketone compound that can be used in the present invention, for example, those disclosed in Japanese Patent Publication No. 52-47949 and manufactured industrially can be used arbitrarily. Specifically, benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, benzoylacetylethylmethane,
Examples include diacetylmethane, triacetylmethane, dibenzoylmethane, distearoylmethane, stearoylacetylmethane, lauroylacetylmethane, benzoylformylmethane and the like.

Further, metal salts of these β-diketones, for example, salts of lithium, sodium, magnesium, aluminum, potassium, calcium, zinc and the like may be used.

The amount of the β-diketone compound to be used is generally 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the halogen-containing resin. If the amount is less than 0.01 parts by weight, the synergistic thermal stabilization effect of β-diketone may not 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. These β-diketone compounds may be used alone or in combination of two or more.

Further, in the heat stabilizer or the halogen-containing resin composition of the present invention, various additives may be blended, if necessary, as long as the effects of the present invention are not impaired. For example, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a flame retardant, a lubricant, a pigment, an antistatic agent, an antifogging agent, and the like which are usually used in a halogen-containing resin composition can be blended. An organic phosphorus compound, an epoxy compound and the like can also be blended.

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

[0032]

EXAMPLES In order to further clarify the features of the present invention,
Although the present invention will be described by way of an example, the present invention is not limited to this example.

[Production Example 1] Magnesium hydroxide 58.3
Parts (parts are parts by weight; the same applies hereinafter) and 74.1 parts of calcium hydroxide were suspended and dissolved in 2,000 parts of water, and carbon dioxide gas was blown thereinto for 3 hours while stirring at 10 ° C. The precipitate is filtered and dried under a carbon dioxide atmosphere at 50 ° C. or less, and calcium carbonate-magnesium carbonate double salt (synthetic dolomite) 1
52.3 parts were obtained. The ratio of calcium and magnesium in the obtained double salt was 54:46 in terms of CaO and MgO.

[Production Example 2] The calcium carbonate-magnesium carbonate double salt (synthetic dolomite) obtained in Production Example 1 was calcined at 1000 ° C for 1 hour to obtain lightly fired synthetic dolomite.

[Production Example 3] Diopside (CaMg (Si
O ₃ ) ₂ ) was fired at 1000 ° C. for 1 hour to obtain a lightly burnt diopside.

[Production Example 4] 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.

Examples 1-1 to 14 and Comparative Examples 1-1 to
5] The halogen-containing resin composition having 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, a dynamic thermal stability test at 200 ° C. using a Labo Plastomill, and a Congo Red test at 180 ° C. went. 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. The symbols in the table are as follows. * 1: “1000Z” manufactured by Shin-Daiichi PVC Co., Ltd. (degree of polymerization: 10
50) was used. * 2: All used Tagen Lime Industry Co., Ltd. * 3: “Prene Riser ST-210” (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd., a compound mainly composed of adipic acid ester of dipentaerythritol, OH value: 90)
0) * 4: "Prene Riser ST-220" (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd., a compound mainly composed of an adipate ester derivative of pentataerythritol, OH value 900)

[0038]

[Table 1]

[0039]

As described above, according to the present invention, the heat stability of a halogen-containing resin such as a vinyl chloride resin can be remarkably improved by using a highly safe heat stabilizer.

Claims (8)

[Claims] 1. A heat stabilizer for a halogen-containing resin, comprising a dolomite compound and a zinc salt of an organic acid. 2. The heat stabilizer for a halogen-containing resin according to claim 1, further comprising a polyhydric alcohol compound and / or a β-diketone compound. 3. The heat stabilizer for a halogen-containing resin according to claim 1, wherein the dolomite-based compound is a natural dolomite and / or a synthetic dolomite comprising a double salt of calcium carbonate and magnesium carbonate. 4. The dolomite compound whose calcium and magnesium weight ratio is 5: 9 in terms of CaO and MgO.
The heat stabilizer for a halogen-containing resin according to any one of claims 1 to 3, wherein the ratio is from 5 to 95: 5. 5. A dolomite compound whose calcium and magnesium weight ratio is 5: 9 in terms of CaO and MgO.
4. The heat stabilizer for halogen-containing resins according to claim 1, comprising lightly fired dolomite obtained by lightly firing a 5-95: 5 double salt compound. 6. A halogen-containing resin composition comprising the heat stabilizer for a halogen-containing resin according to claim 1. 7. A halogen-containing resin composition comprising 0.01 to 150 parts by weight of the heat stabilizer for a halogen-containing resin according to claim 1 to 100 parts by weight of the halogen-containing resin. . 8. A halogen-containing resin molded article obtained by molding the halogen-containing resin composition according to claim 6 or 7.