JP2006328428A - Thermal stabilizer for halogen-including resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halogen-including resin composition wherein a zinc stabilizer having high safety is used instead of lead stabilizer to develop the same level of stability as that of the lead stabilizer. <P>SOLUTION: This thermal stabilizer includes dolomite compound and zinc salt of organic acid and the thermal stabilizer is mixed with halogen-including resin thereby to increase the thermal stability of the resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a heat-stabilized halogen-containing resin composition, and more specifically, a heat-stabilized halogen-containing resin composition comprising a halogen-containing resin and a zinc salt of a dolomite compound and an organic acid. About.

  Halogen-containing resins such as vinyl chloride resin are highly flame retardant and have excellent properties such as light resistance, recyclability, chemical resistance, building materials, piping, wire covering materials, various sheets, various films, containers, etc. Is widely used.

  The halogen-containing resin undergoes a degradation phenomenon such as thermal coloring of the resin and a decrease in physical properties such as strength due to thermal decomposition accompanied by dehydrohalogenation during the thermoforming process. In order to solve such problems, it is common to add a stabilizer for improving the thermal stability of the halogen-containing resin.

  As stabilizers for improving the thermal stability of halogen-containing resins (hereinafter referred to as “thermal stabilizers”), metal salts of organic acids such as fatty acids, aromatic carboxylic acids and amino acids have been conventionally used. Specifically, lead salts and cadmium salts have satisfactory functions as heat stabilizers, and lead stabilizers have been used in large quantities. However, their use is limited due to the great toxicity problem. As a heat stabilizer alternative to these, zinc salts of organic acids with high safety are attracting attention.

  However, compared to lead-based stabilizers, zinc-based heat stabilizers do not have the sufficient heat-stabilizing effect, and the combination of highly safe zinc-based stabilizers has the same level of heat-stabilizing effect as lead-based stabilizers. There is a need for a thermal stabilization system that can be applied to the containing resin.

  An object of the present invention is to provide a halogen-containing resin composition having high safety and excellent thermal stability.

  As a result of intensive studies to solve the above problems, the present inventors have made remarkable thermal stabilization with respect to halogen-containing resins when a dolomite compound is used in combination with a zinc salt stabilizer of an organic acid. It has been found that the effect is exhibited, and the present invention has been completed.

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

  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.

  The dolomite-based compound used in the present invention is not particularly limited, and dolomite (that is, dolomite) that is widely produced in nature and used in wall materials, refractories for iron making, and the like can be used. Further, dolomite has a chemical composition of calcium carbonate and magnesium carbonate double salt, and a calcium carbonate-magnesium carbonate double salt obtained by chemical synthesis, that is, synthetic dolomite can also be used. The composition of the synthetic dolomite used in the present invention may be a mixture of calcium and magnesium in a certain ratio, and the weight ratio in terms of CaO and MgO is preferably in the range of 5:95 to 95: 5. When synthetic dolomite outside this ratio range is used, the heat stabilization effect according to the present invention cannot be sufficiently obtained.

  In addition, it is possible to use derivatives obtained by modifying these natural and / or synthetic dolomite without largely changing the metal element composition, such as firing and calcination. Specifically, the dolomite is heated to 700 to 800 ° C. Dolomite cement that can be heated by heating, light-burned dolomite that can be heated at 900-1000 ° C., dead-burned dolomite hard-fired at a high temperature of 1600-1800 ° C., and bituminous slaked lime that has been digested by adding water to light-burning dolomite And synthetic magdro clinker. Furthermore, natural minerals and synthetic double salts in which the ratio of calcium to magnesium is in the same range as the above-mentioned synthetic dolomite, such as akermanite (Ca2MgSi2O7), diopside (CaMg (SiO3) 2) and various slags, were similarly modified. Derivatives can also be used. Needless to say, any mixture of these may be used.

  These dolomite and its derivatives are collectively referred to herein as dolomite compounds, but these dolomite compounds are produced in large quantities industrially in large quantities, such as steelmaking, pottery, building materials, agriculture, etc. Since it is used in a wide range of industries, it can be obtained easily and inexpensively with stable quality. Especially, when lightly burned dolomite is used, the thermal stability of the resulting halogen-containing resin composition becomes particularly good.

  Moreover, you may use together the surface treating agent currently used industrially in the range which does not inhibit the effect of this invention as needed. Specifically, coupling agents such as silane, aluminum and phosphoric acid, and cationic, anionic and nonionic surfactants such as atearic acid, zinc atearate and calcium atearic acid, and polymeric dispersants Etc. However, in order to sufficiently obtain the effect of improving the heat stability by the treatment agent of the present invention, these surface treatment agents are used in the present invention at most in the same amount or the same amount as the compound used for the surface treatment of the dolomite compound. It is preferable to stop below the amount.

  The amount of the dolomite compound used in the present invention is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more with respect to 100 parts by weight of the halogen-containing resin. If the amount is less than 0.01 parts by weight, the desired heat stabilizing effect is not sufficiently exhibited. On the other hand, when more than 30 parts by weight of the dolomite compound is used, the thermal stabilization effect may not be further improved. Moreover, although a dolomite type compound can be added to about 200 weight part, Preferably it is used at 150 weight part or less. When the amount is more than 200 parts by weight, the thermal stabilization effect of the present invention is not lowered, but the physical properties of the halogen-containing resin composition may be lowered in the same manner as a normal 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 is rough, which may cause deterioration in quality such as physical properties.

  In the heat stabilizer for halogen-containing resin of the present invention, an organic acid zinc salt used together with a dolomite compound 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, terephthalic acid , Trimellitic acid, glutamic acid, lysine, pyrrolidonecarboxylic acid, aspartic acid, glycine and the like.

  The amount of the organic acid zinc salt used is usually 0.01 to 20 parts by weight relative to 100 parts by weight of the halogen-containing resin when used as a heat stabilizer for halogen-containing resins.

  In the heat stabilizer for halogen-containing resin of the present invention, in addition to the dolomite compound (or the surface-treated dolomite compound) and the zinc salt of the organic acid, in order to further suppress the thermal coloring of the resin, You may mix | blend a polyhydric alcohol compound and / or (beta) -diketone compound.

  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 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.

  In particular, since a partially esterified product obtained by esterifying 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 has a high molecular weight, it is thermoformed. It is preferable because it has additional advantages such as no sublimation during processing, no mold contamination, improved processability of the resin, and improved dispersibility of powders (dolomite compounds, etc.) in the resin. .

  Examples of the higher fatty acid 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.

  Examples of the dibasic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and sebacic acid.

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

  The molecule can be arbitrarily designed and used in accordance with the function and blending system of the target halogen-containing resin composition. Such partially esterified products of pentaerythritol and / or dipentaerythritol and higher fatty acids having 10 to 22 carbon atoms and / or dibasic acids having 4 to 10 carbon atoms are disclosed in JP-A 53- 6350, JP-B-57-61289, JP-A-55-066939, etc. can be easily produced industrially, and although it is a part, it is commercially available. ing.

  The use amount of the polyhydric alcohol compound is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the halogen-containing resin. If it is less than 0.01 part by weight, the synergistic heat stabilization effect by the polyhydric alcohol compound may not be sufficiently exhibited. On the other hand, when it exceeds 10 parts by weight, the physical properties of the halogen-containing resin compound may be lowered. As the polyhydric alcohol compound used in the present invention, the above may be used alone, or two or more 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 arbitrarily used. Specifically, benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, benzoylacetylethylmethane, diacetylmethane, triacetylmethane, dibenzoylmethane, distearoylmethane, stearoylacetylmethane, lauroyl Acetylmethane, benzoylformylmethane, etc. are mentioned.

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

  The usage-amount of (beta) -diketone compound is 0.01-10 weight part normally with respect to 100 weight part of halogen containing resin, Preferably it is 0.05-5 weight part. If it is less than 0.01 part by weight, the synergistic heat stabilization effect by β-diketone may not be sufficiently exhibited. On the other hand, when it exceeds 10 parts by weight, the physical properties of the halogen-containing resin compound may be lowered. These β-diketone compounds may be used alone or in combination of two or more.

  Moreover, in the heat stabilizer or halogen-containing resin composition of this invention, you may mix | blend various additives in the range which does not inhibit the effect of this invention as needed. For example, plasticizers, fillers, antioxidants, ultraviolet absorbers, flame retardants, lubricants, pigments, antistatic agents, antifogging agents, etc. that are usually used in halogen-containing resin compositions can be blended. An organophosphorus compound, an epoxy compound, etc. can also be mix | 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 copolymer. Etc., and these alloys may be used. An alloy of these halogen-containing resins and non-halogen-containing resins such as polyethylene, polypropylene, polystyrene, polyphenylene ether, polyamide, and polycarbonate may also be used. The olefin resin produced using a Ziegler-type catalyst contains a halogen-containing catalyst residue. The olefin resin containing such a halogen-containing catalyst residue is also included in the halogen-containing resin referred to in the present invention.

  When kneading / molding / processing the heat-stabilized halogen-containing resin composition of the present invention, there are no particular limitations on the blending method, kneading method, order, molding method, and the like.

  Further, in order to clarify the characteristics of the present invention, examples will be described. However, the present invention is not limited to the examples.

[Production Example 1]
58.3 parts of magnesium hydroxide (parts are parts by weight; the same applies hereinafter) and 74.1 parts of calcium hydroxide are suspended and dissolved in 2000 parts of water, and carbon dioxide gas is blown in for 3 hours while stirring at 10 ° C. It is. The precipitate was filtered and dried under a carbon dioxide atmosphere at 50 ° C. or lower to obtain 152.3 parts of calcium carbonate-magnesium carbonate double salt (synthetic dolomite). The ratio of calcium and magnesium of 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 fired at 1000 ° C. for 1 hour to obtain a lightly burned synthetic dolomite.

[Production Example 3]
Diopside (CaMg (SiO 3) 2) was fired at 1000 ° C. for 1 hour to obtain a light burned diopside.

[Production Example 4]
Add 73 parts of adipic acid and 284.5 parts of stearic acid to 136 parts of pentaerythritol, stir at 230 ° C. for 2 hours to carry out an esterification reaction. 55%).

[Examples 3-5, 7-14, Reference Examples 1, 2, 6, Comparative Examples 1-5]
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 at 180 ° C. using a gear oven (static thermal stability test), a dynamic thermal stability test at 200 ° C. using a lab plast mill, and a Congo red test at 180 ° C. went. In the thermal coloring test, the time until the sheet browned or partially blackened, and in the dynamic thermal stability test, the time until the resin was decomposed and the kneading torque started to increase was measured. These test results are shown in Table 1. In addition, the symbol in a table | surface is the following transparency.
* 1: “1000Z” (degree of polymerization 1050) manufactured by Shin Daiichi Vinyl Co., Ltd. was used.
* 2: All used Tagen Lime Industry Co., Ltd.
* 3: “Planelizer ST-210” (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd., a compound mainly composed of adipic acid ester of dipentaerythritol, OH number 900)
* 4: “Planelizer ST-220” (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd., a compound mainly composed of an adipate ester derivative of pentataerythritol, OH number 900)

Claims (10)

A heat stabilizer for a halogen-containing resin, comprising a dolomite-based compound selected from either light-burned dolomite and bituminous slaked lime and a zinc salt of an organic acid. The heat stabilizer for halogen-containing resin according to claim 1, wherein the average particle size of the dolomite compound is 100 μm or less. The heat stabilizer for halogen-containing resins according to claim 1, further comprising a polyhydric alcohol compound and / or a β-diketone compound. 4. The heat stabilizer for halogen-containing resin according to claim 3, wherein the polyhydric alcohol compound is pentaerythritol, dipentaerythritol, or one obtained by esterifying them with a basic acid. The polyhydric alcohol compound is a partially esterified product obtained by esterifying 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. The heat stabilizer for halogen-containing resins according to any one of claims 3 to 4. A halogen-containing resin composition comprising the thermal stabilizer for a halogen-containing resin according to claim 1. 0.01 to 200 parts by weight of a dolomite-based compound selected from either light-burned dolomite or bituminous slaked lime with respect to 100 parts by weight of a halogen-containing resin, and 0.01 to 20 parts by weight of an organic acid zinc salt There is a halogen-containing resin composition. 0.01 to 200 parts by weight of a dolomite-based compound selected from either light-burned dolomite or bituminous slaked lime with respect to 100 parts by weight of a halogen-containing resin, 0.01 to 20 parts by weight of an organic acid zinc salt, A halogen-containing resin composition, wherein the polyhydric alcohol compound is 0.01 to 10 parts by weight. 0.01 to 200 parts by weight of a dolomite-based compound selected from either light-burned dolomite or bituminous slaked lime with respect to 100 parts by weight of a halogen-containing resin, 0.01 to 20 parts by weight of an organic acid zinc salt, A halogen-containing resin composition, wherein the β-diketone compound is 0.01 to 10 parts by weight. 0.01 to 200 parts by weight of a dolomite-based compound selected from either light-burned dolomite or bituminous slaked lime with respect to 100 parts by weight of a halogen-containing resin, 0.01 to 20 parts by weight of an organic acid zinc salt A halogen-containing resin composition comprising 0.01 to 10 parts by weight of a polyhydric alcohol compound and 0.01 to 10 parts by weight of a β-diketone compound.