JP2581699B2 - Novel halogen-containing resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel halogen-containing resin composition having excellent heat stability. More specifically, in producing neutral or basic zinc glycine by reacting glycine with zinc oxide or zinc hydroxide in the presence of water, the water present in the reaction system is mixed with zinc oxide or zinc hydroxide. It has been found that there is a remarkable correlation between the amount and the thermal stability after blending, whereby a composition having an unprecedented thermal stability can be obtained. The present invention relates to a halogen-containing resin composition using the zinc glycine.

2. Description of the Related Art In general, a halogen-containing resin, particularly a vinyl chloride resin, is liable to be deteriorated by the action of heat and light, resulting in discoloration, decomposition, a decrease in mechanical strength, a change or a decrease in appearance, and the like. Has a problem that the commercial value of the product is lowered and the product cannot be used for a long time.

However, JP-A-54-55047 discloses that a metal salt of an amino acid or a derivative thereof is blended with a vinyl chloride resin to obtain a composition having excellent heat stability. It has become clear that amino acid metal salts or derivatives thereof are considerably superior in terms of thermal stability, transparency, processability, and the like. As the amino acid metal salt, calcium salt, zinc salt and the like are used, the stabilization time is extremely long,
In addition, it has the advantages that the rate of dehydrochlorination is extremely low or that the physiological toxicity is relatively low.

However, those skilled in the art have demanded that the technical content disclosed herein be further improved, and in developing a halogen-containing resin composition containing zinc glycine, zinc glutamate, or a basic organic zinc compound. What has been reached is that of Nissan Fuero Organic Chemical Co., Ltd.
This is as specified in Japanese Patent Publication No. 1248.

That is, a halogen-containing resin composition obtained by mixing 0.1 to 10 parts by weight of zinc glycine and / or zinc glutamate and 0.01 to 0.5 part by weight of a basic organic zinc compound with respect to 100 parts by weight of a halogen-containing resin is obtained at a predetermined temperature. A thermal stability test shows that the degree of coloration and blackening time have been significantly improved.

Problems to be Solved by the Present Invention While studying the preparation conditions of zinc glycine, the present inventors have keenly noticed that the thermal stability of the resin composition has a considerably strong correlation with the preparation conditions of the zinc glycine. As a result of research, the present invention has been completed.

Originally, zinc glycine was prepared using zinc oxide, glycine,
It was performed in an aqueous system and had little technical interest due to the low preparation effort. Since the produced glycine zinc has a relatively simple composition, it has been considered that there is no difference in the properties of the product regardless of the preparation.

For example, BWLow, FLHirshfeld, FMRichards, etc.
As shown in m. Chem. Soc. 81, 4412 (1959), as a method for producing zinc glycine, 1 mol of glycine and 0.5 mol of zinc oxide are dissolved in a large amount of water while boiling and then recrystallized. Or a method specified in the above-mentioned Japanese Patent Application No. 62-138022, that is, a predetermined amount of water and glycine are added to a reaction vessel,
Zinc oxide was added with stirring, heated to 70 ° C., heated for about 1 hour, dried at 110 ° C., and water was removed to obtain crystals. In particular, it was recognized that the amount of water in this reaction was convenient for the operation, but was not a factor controlling the reaction products.

In other words, when the amount of glycine is 1 mol and the amount of zinc oxide is 0.5 mol, regulation of the amount of water is hardly considered. However, the present inventors have found that, when the thermal stability of the resin compositions containing zinc glycine as a product is compared with each other, the stability differs depending on the amount of water present in the reaction system.

In addition, it was discovered that the basicity of the formed glycine zinc had a considerable effect on the thermal stability. This means that the ratio of glycine to zinc compound is an important factor during preparation. That is, the zinc glycine of the present invention is defined as 0.5 mol of zinc oxide or zinc hydroxide per 1 mol of glycine.
The term "molarly charged to give neutral zinc glycine" and the term "0.5 mole or more to be used as basic zinc glycine" are collectively referred to.

The input amount of zinc oxide or zinc hydroxide can be arbitrarily selected, but a preferable range is 0.5 mol or more and 3 mol or less. Addition of 3 mol or more is not preferable from the viewpoint of thermal stability because the basicity is too high. In that case, there is a method of appropriately neutralizing with another organic acid.

In the case of zinc oxide, the amount of water added during the preparation of the zinc glycine of the present invention is preferably 2 mol or less per 1 mol of glycine. However, the reaction does not proceed in an anhydrous state as viewed from the course of the reaction.

In addition, in the case of zinc hydroxide, the amount of water added to 1 mol of glycine may be 1 mol or less.

A predetermined amount of glycine and zinc oxide or zinc hydroxide are mixed and stirred, then a predetermined amount of water is added, and mixing is continued.
The reaction is usually completed within 30 minutes after the addition of water, but may take longer depending on the stirring conditions and basicity.
Alternatively, glycine and water may be mixed in advance to make glycine wet, and then zinc oxide or zinc hydroxide may be added and stirred.

After completion of the reaction, dry and pulverize at around 110 ° C and mix. In this case, as a pulverizing means, an impact pulverizer, a vibration ball mill, a jet pulverizer, a tower pulverizer, a colloid mill, a wet pulverizer, and other commercially available high-performance pulverizers can be used.

Even if iminodiacetic acid, nitrilotriacetic acid or the like is mixed in glycine used in the present invention, it does not impair the effect as a stabilizer at all.

The halogen-containing resin applied to the present invention is polyvinylidene chloride, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene,
Polyvinyl halides such as chlorinated polypropylene and brominated polyethylene, or resins obtained by halogenating polyolefins, vinyl chloride-glutane copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-styrene copolymer Copolymers, copolymers of halogen-containing resins such as vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, and ABS, MBS, EVA, butadiene, urethane ,
Halogen-containing resins in polymer blends with vinyl acetate and the like.

In applying the present invention, the blending ratio of the halogen-containing resin and the zinc glycine is usually in a preferable range of 0.1 to 10 parts by weight based on 100 parts by weight of the halogen-containing resin. This ratio is determined by two aspects: thermal stability and economy.

In applying the present invention, various stabilizers may be used in combination with the halogen-containing resin. For example, metal soaps, epoxy compounds, organic phosphites, antioxidants, ultraviolet absorbers, hydrotalcite compounds, surfactants, polyol compounds and their esters, diketone compounds, organic Use of phosphates, metal oxides and hydroxides, basic inorganic acid salts, perchlorates, plasticizers, pigments, blowing agents, flame retardants, etc. in combination with the expected thermal stability of glycine zinc It does not impede the effect of any.

Further, a basic organic zinc compound disclosed in JP-A-63-301248 can also be added. In this case, the thermal stability appears with a synergistic effect.

Any method of adding the stabilizer to the halogen-containing resin may be used as long as the function is not impaired. The stabilizer may be mixed simultaneously with the preparation of zinc glycine, or may be added individually.

Examples Next, examples will be described to explain the present invention.

(1) Zinc glycine Zinc glycine oxide or zinc hydroxide is charged in a predetermined amount into a desktop universal mixer (manufactured by Shinagawa Seisakusho), and mixing is continued for about 5 minutes. Next, a predetermined amount of water is added with mixing to produce zinc glycine. About 30 minutes after the introduction of water, the whole system becomes whiter than the initial stage of mixing, and the stirring is stopped at that time. The product is dried at 110.degree. C., then pulverized and incorporated into the halogen-containing resin.

In preparing the zinc glycine of the present invention, the ratios of the predetermined amounts of glycine, zinc oxide or zinc hydroxide, and water to be added to the reaction system were set as shown in Table 1 below. Group A, Group B, C
The group is a case where the added water ratio is small, and is an example according to the preparation method claimed in the present application.

On the other hand, groups A ', B' and C 'have a large added water ratio and are different from the preparation method claimed in the present application.

The numerical values in Table 1 are addition ratios (molar ratios) based on 1 mol of glycine.

(2) Halogen-containing resin composition The basic compounding ratio used in the examples is as follows.

(A) Example of general formulation (hard) Vinyl chloride resin (Zeon 103 EP) 100 parts by weight Zinc stearate 1.5 Calcium stearate 0.5 BHT 0.1 DPDP 0.5 Zinc glycine Raise the temperature. This was kneaded with a 6-inch roll at 190 ° C. for 4 minutes to form a sheet having a thickness of about 0.7 mm. Approximately 2 cm square test pieces were punched out from this, heated in a gear aging tester set at 185 ° C., and the time required until blackening was measured. Table 2 shows the results.

(B) General formulation example (soft) Vinyl chloride resin (Zeon 103 EP) 100 parts by weight DOP 40 Zinc stearate 0.5 Calcium stearate 0.3 BHT 0.1 DPDP 0.3 Zinc glycine Table-3 The mixture was kneaded for 3 minutes and processed into a test sheet having a thickness of about 0.7 mm. Then, a 2 cm square test piece was cut out from each sheet, heated in a gear aging tester set at 185 ° C., taken out one by one at predetermined time intervals, and the degree of coloring was visually determined. The results are shown in Table-3.

As can be seen from the results, in each of the examples in which a small amount of water was used during the production of zinc glycine, the coloring was reduced and the blackening time was increased.

(C) Example of combined use with basic organic zinc compound Vinyl chloride resin (Zeon 103 E-8P) 100 parts by weight Basic zinc acetate (Note) 0.3 BHT 0.1 Dehydroacetic acid 0.05 Zinc stearate 0.5 Calcium stearate 0.3 DPOP 0.1 Zinc glycine Table -4 (Note) Preparation of basic zinc acetate To 81.4 g (1 mol) of zinc oxide, add 150 ml (8.3 mol) of water, and with stirring, 67 g of a 90% aqueous acetic acid solution (1 g of acetic acid).
Mol) was added slowly. After the addition is completed, continue stirring for 30 minutes. Thereafter, drying and pulverization are performed.

(3) Formulation and thermal stability test Mixing at 80 ° C with a high-speed rotating mixer at a natural temperature and kneading at 190 ° C for 4 minutes with a 6-inch roll.
The sheet was processed into a sheet of 0.6 to 0.7 m / m. Each sheet was heated to 180 ° C. in a gear aging tester, and the time required for blackening was observed. The results are shown in Table-4.

Effect of the Invention Regarding the effect of zinc glycine, group A → group A ', group B →
A clear difference can be seen by comparing the B ′ group, the C group → the C ′ group.

That is, regardless of neutrality or basicity, the amount of water to be added at the time of preparing zinc glycine is limited to 2 moles as claimed in the present application, with respect to 1 mole of glycine. If it is longer than this, the blackening time is adversely affected, and a favorable result is not obtained.

Claims (1)

(57) [Claims] 1. A neutral or basic zinc glycine formed from 1 mol of glycine, 0.5 mol or more and 3 mol or less of zinc oxide or zinc hydroxide and 2 mol or less of water, based on 100 parts by weight of a halogen-containing resin. A novel halogen-containing resin composition containing 0.1 to 10 parts by weight.