JPH0236143B2 - SHINKIGANHAROGENJUSHISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized halogen-containing resin composition. Specifically, the present invention relates to a new stabilized halogen-containing resin composition obtained by adding a mixed product of a hydrotalcite compound with perchloric acid to a halogen-containing resin. Conventional halogen-containing resins, such as vinyl chloride resins,
Chlorinated polyethylene resin etc. are mixed with plasticizers, stabilizers, colorants, fillers, lubricants, etc. as appropriate.
As a halogen-containing resin composition, it is widely used in various molded products. Halogen-containing resins are also EVA,
Polymer blends with MBS, ABS, acrylic resin, etc. are also being made. This blend product is also called a halogen-containing resin in a broad sense. However, halogen-containing resin compositions, such as vinyl chloride resin compositions, tend to undergo thermal decomposition reactions due to dehydrochlorination reactions within molecular chains at a processing temperature of around 175°C during molding, and conventional halogen-containing resin compositions Stabilization efforts have focused on suppressing this decomposition reaction, but this has not always been satisfactory. Furthermore, molded products often undergo thermal deterioration during use; for example, in the summer, the surface temperature of molded products used outdoors can rise to over 80°C due to the energy of sunlight. . In addition, wire coating materials are continuously exposed to a high temperature atmosphere during use, so according to JIS C3005, deterioration tests have been attempted at temperatures between 90℃ and 120℃.
Halogen-containing resin compositions that can meet these requirements have not always been satisfactory. Improving the durability of polymeric materials whose main raw material is petroleum is an important issue from the viewpoints of resource saving, energy saving, and ensuring safety. The inventors
In order to improve the durability of molded products, deterioration at around 70°C to 140°C (this is called low-temperature aging, hereinafter the same) and deterioration at around 175°C to 200°C during processing (this is called heat aging). (hereinafter the same)), developed a new halogen-containing resin composition, and completed the present invention. That is, the present invention comprises (A) 100 parts by weight of a halogen-containing resin and (B) a mixture of 0.001 to 2 moles of perchloric acid per mole of hydrotalcite compound.
This is a stabilized halogen-containing resin composition characterized in that it consists of parts by weight. Mixtures used in the invention
(B) is characterized by improving heat aging during processing of a halogen-containing resin composition and at the same time obtaining a molded product with excellent low-temperature aging prevention. When preparing the mixture (B) used in the present invention, if the molar ratio of perchloric acid to 1 mol of the hydrotalcite compound is 2 or more, the effect will be rather reduced. Further, at a value of 0.001 or less, no mixing effect is observed. If the amount of the mixed product (B) added is 0.001 parts by weight or less based on 100 parts by weight of the halogen-containing resin in the halogen-containing resin composition, no blending improvement effect is observed. In addition, if it exceeds 100 parts by weight, an improvement effect can be seen, but it is no longer relevant from an economic standpoint. The present invention includes adding the above-mentioned mixed product (B),
A halogen-containing resin composition is obtained, and examples of the halogen-containing resin include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, Brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, 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- Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer , vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and the like. Furthermore, the use of the above-mentioned mixed product (B) of the hydrotalcite compound of the present invention and perchloric acid in combination with a known substance that is normally used as a stabilizer component does not reduce the effects of the present invention in any way. . These commonly used stabilizers include metal organic acid salts, organic phosphite compounds, antioxidants,
Examples include ultraviolet absorbers, metal oxides, polyols, and nitrogen-containing nonmetallic compounds. Among these combined stabilizers, the combination of polyols and nitrogen-containing nonmetallic compounds with the above mixed product (B) of the present invention has a particularly great synergistic effect in preventing discoloration during heat aging and low temperature aging. The present inventors have discovered that. Examples of the polyols mentioned here include bentaerythritol, diventaerythritol, mannitol, sorbitol, glycerin, polysaccharides, and derivatives thereof. Further, as the nitrogen-containing nonmetallic compound, urea, melamine, α-phenylindole, diphenylthiourea, tris(2-hydroxyethyl)isocyanurate, etc. are used. The hydrotalcite compound used in the present invention is a salt of Mg and Al, and has the chemical formula MgxAl ₂
(OH) _y Represented by CO ₃ · zH ₂ O, x; 4 to 6, y;
12-16, z; 3-5, which may be a synthetic product or a natural product. Furthermore, baked products such as these may also be used. An example of a compound of hydrotalcite compounds is DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd. (hereinafter referred to as
It is written as DHT-4A. ) or Kyoward 1100 (hereinafter referred to as Kyoward 1100), the chemical formula can be expressed as Mg4.5Al ₂ (OH) ₁₃ CO ₃・3.5H ₂ O, 1
The mole is 507.4g. The perchloric acid used in the present invention may be a commonly available commercial product or may be used after diluting it with water. In this case, 1 mole of perchloric acid is converted to 100%,
1 mole is 100.5g. Next, the above-mentioned mixed product (B) according to the present invention is prepared, for example, by the following three methods. A Hydrotalcite compound is placed in a mixing tank equipped with a stirrer, and while stirring, a predetermined amount of perchloric acid aqueous solution is gradually added dropwise, and the mixture is mixed until a uniform state is obtained. B Prepared by method A above and further dried at 100°C or higher. C. Dilute a predetermined amount of perchloric acid in a mixing tank equipped with a stirrer filled with water in advance, and add a predetermined amount of hydrotalcite compound while stirring. After thorough stirring, take out and filter or dry if necessary. When the prepared product obtained by the above method is blended into a halogen-containing resin composition, the weight part of the above mixed product (B) is calculated in terms of solid content excluding free water from the preparation. Next, the effects of the halogen-containing resin composition according to the present invention will be shown by examples. The degree of coloring in Examples was expressed using the following numerical values. 10 Colorless 9-8 Pale yellow 7-6 Yellow 5-4 Yellow-brown 3-2 Reddish-brown 1 Black In addition, the mixture (B) used in the examples contains perchloric acid per mole of hydrotalcite compound. Samples for evaluation were prepared according to one of the preparation methods A, B, and C described in the main text of the specification at the molar ratio shown in Table 1 below.

[Table] Example 1 In order to examine the effects of the halogen-containing resin composition according to the present invention, the following formulation was mixed using a kneading roll.
The mixture was kneaded at a roll temperature of 180° C. for 5 minutes to prepare a test sheet with a thickness of 0.5 mm. Heat aging at 180°C and low temperature aging at 120°C were measured using a gear aging tester. Initial coloration was also investigated at the same time. The results are shown in Table 2. The evaluation of heat aging was expressed by the time taken for blackening. Initial coloration and low-temperature aging were expressed as numerical values of coloration degree. For comparison, similar tests were conducted with DHT-4A as the sample, with perchloric acid alone, with DHT-4A and perchloric acid added at the same time when blending without mixing them in advance, and with no sample. The results are also shown in Table 2. Compounded polyvinyl chloride 100 parts by weight DOP 50 〃 Barium stearate 0.5 〃 Zinc stearate 0.2 〃 Sample mixture (B) Table 2 shows the amounts added

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[Table] Example 2 When polyols and nitrogen-containing nonmetallic compounds were used in combination with the composition of the present invention, further improvement effects were obtained. Example 1 using the formulation shown below
The effect was investigated using the same method. The results are shown in Table 3. Compounded polyvinyl chloride 100 parts by weight ABS 20 〃 DOP 30 〃 Barium nonyl phenate 0.5 〃 Zinc octoate 0.2 〃 Sample (mixture (B)) 0.5 〃 Polyols or nitrogen-containing nonmetallic compounds (tertiary
(see table) 0.5 〃

[Table] Example 3 To examine the effect of using chlorinated polyethylene as the halogen-containing resin, a test was conducted in the same manner as in Example 1 using the formulation shown below. The results are shown in Table 4. Compound chlorinated polyethylene elasthrene 303B ^*3
100 Parts by weight Dibutyltin malate 2.0 〃 Dibutyltin laurate 1.0 〃 Rikemar S-200 ^*4 1.0 〃 Sample (Mixture (B)) 0.5 〃 *3 Elasthren 303B manufactured by Showa Denko Corporation Chlorinated polyethylene *4 Rikemar S-200 manufactured by Riken Vitamin Lubricant

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Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of halogen-containing resin and (B) a mixture of 0.001 to 2 moles of perchloric acid per mole of hydrotalcite compound 0.001 to 100
A stabilized halogen-containing resin composition comprising parts by weight.