JPS63301248A - New halogenated resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition of good heat stability, comprising a halogenated resin, a zinc glycinate and/or zinc glutamate and a basic organozinc compound. CONSTITUTION:ZnO is added to an aqueous solution of glycine and/or glutamic acid, and the mixture is kept at 70-80 deg.C for several hr and dried at about 110 deg.C to obtain zinc glycinate and/or zinc glutamate (B). A reaction product obtained by mixing an aqueous solution of a carboxylic acid (e.g., acetic acid) with an aqueous dispersion of ZnO is dried by heating, and the dried product is ground to obtain a basic organozinc compound (C). 100pts.wt. halogenated resin (A) (e.g., PVC) is mixed with 0.1-10pts.wt. component B and 0.1-5.0pts.wt. component C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel halogen-containing resin composition with excellent thermal stability. More specifically, the present invention relates to a novel halogen-containing resin composition with good thermal stability, in which glycine or a zinc salt of glutamic acid and a basic organic zinc compound of monocarboxylic acid or dicarboxylic acid are blended into a halogen-containing resin.

・In general, halogen-containing resins, especially vinyl chloride resins, are susceptible to deterioration due to the effects of heat and light, resulting in discoloration, decomposition, reduction in mechanical strength, and changes/deterioration in appearance. This causes problems such as lowering the commercial value of the molded product and making it unsustainable for long-term use.

Against this background, various stabilizers have been developed to stabilize halogen-containing resins. Well-known stabilizers include, for example, cadmium-barium-based, lead-based, calcium-zinc-based, barium-zinc-based compounds, or organotin-based compounds.

In addition, as stabilizers against light, benzotriazole type,
There are benzophenones, hindered amines, etc.

However, these stabilizers are not always satisfactory due to problems such as being very expensive, toxicity, performance as a stabilizer, and environmental pollution.

However, JP-A-54-55047 discloses blending an amino acid metal salt or a derivative thereof with a vinyl chloride resin to obtain a composition with excellent thermal stability.

It has become clear that amino acid metal salts or their derivatives are considerably superior in terms of thermal stability, transparency, processability, and the like. Calcium salts, lead salts, zinc salts, and the like are used as the amino acid metal salts, and they have advantages such as extremely long stabilization times, extremely low dehydrochlorination rates, and relatively low physiological toxicity.

In addition, the amino acids include monoaminomonocarboxylic acid,
Monoaminodicarboxylic acids and the like are used. Further, as a substituent for the amino acid, an alkyl group or an alkoxy group having at most 10 carbon atoms is preferred. These amino acids can be used alone or in combination of two or more.

The amount of the amino acid metal salt or its derivative added is preferably 1 to 8 parts by weight per 100 parts by weight of the vinyl chloride resin.

Although the above-mentioned JP-A-54-55047 has better performance as a stabilizer than the conventional metal salts of the same type, the stabilization time is longer, and the search for a stabilizer effective in preventing the decomposition of the resin. is strongly desired by those skilled in the art.

The inventor of the present application further pursued the effects of the zinc salt disclosed in JP-A-54-55047, discovered new characteristics of the amino acid zinc salt, and completed the present invention. That is, it has become clear that the thermal stabilization of halogen-containing resins is dramatically improved by using a basic organic zinc compound in combination, rather than using a certain type of amino acid zinc salt alone as a stabilizer.

The present invention further develops the characteristics of zinc-based compounds and newly discovers a composition containing a stabilizer made of a combination of two types of zinc-based compounds.

1 Riza! Bean The present invention is a composition in which a halogen-containing resin is blended with an amino acid zinc salt and a basic organic zinc compound in a fixed ratio.

The amino acid zinc salt applied to the present invention is prepared by the following method.

(1) Metathesis method Amino acids are dispersed and dissolved in a predetermined amount of water. In that state, add a concentrated aqueous solution of caustic soda to the amino acid dispersion and
Make a sodium amino acid aqueous solution by heating to ~60℃,
An aqueous solution of zinc sulfate is gradually added dropwise into the solution while stirring to promote double decomposition and produce zinc amino acid salts. Thereafter, ethanol was added to crystallize Glauber's salt, and the mixture was filtered and separated. The filtrate, which was as free from Glauber's salt as possible, was collected and allowed to stand for 20 hours to precipitate crystals of amino acid zinc salt. Thereafter, the crystals were dried at 110° C. for more than ten hours to completely remove moisture, and the desired amino acid zinc salt was obtained.

The amount ratio of amino acid and caustic soda in the powder method is equimolar,
The quantitative ratio of amino acid sodium salt to zinc sulfate is determined from a metathesis reaction using zinc as a divalent ion.

The concentration of the aqueous solution of caustic soda and the concentration of zinc sulfate in an aqueous solution may be determined in consideration of the convenience of handling the substance in solution, and therefore there are no strict regulations.

The amount of ethanol added to crystallize Glauber's salt is also determined based on operational convenience.

(2) Direct method Add zinc oxide while stirring the amino acid aqueous solution,
After holding at 0-80°C for several hours, it is dried at 110″C to obtain the desired amino acid zinc salt.

The final method is the so-called direct method.

The ratio of amino acids to zinc oxide is determined by the basicity of the amino acids and the ionic value of zinc. The concentration of the amino acid aqueous solution is determined by convenience of operation, and there are no particularly strict regulations.

As mentioned above, the amino acid zinc salt applied to the present invention can be prepared by double decomposition method,
Either direct method may be used for the preparation, and no results have been obtained that are particularly distinguishable between the two in terms of their effects as additives.

Amino acids applicable to the present invention are monoaminocarboxylic acids,
Examples include monoamino dicarboxylic acid and diamino monocarboxylic acid. However, from a comprehensive viewpoint, glycine and glutamic acid are preferable from the viewpoint of their effectiveness as stabilizers.

The basic organic zinc compound applied to the present invention is obtained by reacting carboxylic acid with zinc oxide. It can be obtained by adding zinc oxide in excess of the amount ratio required for neutralization of carboxylic acid and zinc oxide during the reaction.

To prepare a basic organic zinc compound, both a carboxylic acid or an aqueous solution of a carboxylic acid and an aqueous dispersion of zinc oxide are prepared separately, and then the two are gradually mixed with stirring. If necessary, the mixture may be heated during stirring or may be stirred at room temperature. During several tens of minutes of stirring, a reaction product is obtained, which is then heated and dried, and the final solid obtained is pulverized as finely as possible.

In this adjustment, the ratio of carboxylic acid to zinc oxide must be strictly controlled depending on the basicity of the product. However, the concentration of the aqueous solution of carboxylic acid, the amount of dispersion of zinc oxide in water, etc. can be selected according to the convenience of operation (no special regulations are necessary).

Carboxylic acids applicable to the present invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, trimethylacetic acid, hexanoic acid,
Octanoic acid, decanoic acid, lauric acid, tridecanoic acid, 2
-Ethylhexoic acid, nonanoic acid, benzoic acid, butylbenzoic acid, toluic acid, cinnamic acid, aminobenzoic acid, phenylacetic acid, hydroxybenzoic acid, acrylic acid, crotonic acid, acetoacetic acid, glycolic acid, lactic acid, hydroacrylic acid , monocarboxylic acids having 18 carbon atoms or less, such as propiolic acid, methacrylic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linuric acid, tall oil fatty acid, persatic acid, thioglycolic acid, and mercaptopropionic acid, oxalic acid, These include dicarboxylic acids or acid anhydrides such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, azelaic acid, levulinic acid, phthalic acid, fumaric acid, malic acid, iminodiacetic acid, and tartaric acid.

As the carboxylic acid applied to the present invention, each of the above-mentioned substances can be used alone, but in addition, several types of substances may be used in combination. That is, as a starting material for the basic organozinc compound, the carboxylic acid that reacts with zinc oxide may be a single component or a composite component. Further, in the case of a composite carboxylic acid, the ratio between the two is determined by taking into account the total basicity of each component and the amount of zinc oxide.

There are two possible effects of amino acid zinc salts and basic organic zinc compounds applied in the present invention on halogen-containing resins.

Amino acid zinc salts are sometimes incorporated alone into halogen-containing resins to function as heat stabilizers. On the other hand, basic organozinc compounds are used and blended with amino acid zinc salts, and have the effect of promoting the function of amino acid zinc salts (encouraging function) and the effect of substituting for the functions of amino acid zinc salts (alternative function).

The halogen-containing resin to which the present invention is applied is polyvinylidene chloride, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, etc. or resins obtained by halogenating polyolefins, vinyl chloride-geltan copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-styrene copolymer, vinyl chloride-ethylene copolymer, vinyl chloride- Copolymers of halogenated resins such as propylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate copolymers, as well as ABSSMBS and EVA.

These include halogen-containing resins in polymer blends with butadiene, urethane, vinyl acetate, etc.

In applying the present invention, the blending ratio of the halogen-containing resin, the amino acid zinc salt, and the basic organic zinc compound is usually 0.1 to 10 parts by weight of the amino acid zinc salt, and 0.1 to 10 parts by weight of the amino acid zinc salt to 100 parts by weight of the halogen-containing resin. The organic zinc compound is 0.01
The preferred range is 5.0 parts by weight. This ratio is determined from two aspects: thermal stability and economic efficiency.

Amino acid zinc salts interact, and it is possible to use different amino acid zinc salts in combination.

In that case, the above 0.1 to 10% as the total amino acid zinc salt
Parts by weight ranges are preferred. Furthermore, basic organozinc compounds have both a supporting function and a substituting function for amino acid zinc salts. Therefore, in actual use, the blending amount can be increased or decreased within these ranges based on the balance between the two.

When applying the present invention, various stabilizers may be used in combination with the halogen-containing resin. For example, metal soaps, epoxy compounds, organic phosphite esters, antioxidants, ultraviolet absorbers, hydrotalcite compounds, surfactants, polyol compounds and their esters, diketone compounds, organic Phosphorus MJlt, metal oxides and hydroxides, bases.

The combined use of inorganic acid salts, plasticizers, pigments, blowing agents, flame retardants, etc. does not in any way inhibit the thermal stability effects expected from zinc amino acids and basic organic zinc compounds.

Also, JP-A-59-140261, JP-A-61-81
A synergistic effect of excellent stability can be obtained by using a mixed product of perchloric acid or an acid-treated product with the hydrotalcite compounds disclosed in JP-A-61-83245.

acupuncture inflammation EXAMPLES In order to demonstrate the effects of the present invention, examples will be given and explained.

However, the examples do not limit the scope of the present invention.

Prior to blending the additives, the adjustment of each additive will be described.

(1) Zinc glycine (amino acid zinc salt by direct method) 300 mj of water in the reaction vessel! , glycine 75g (1 mol)
40.7 g (0.5 mol) of zinc oxide was added with stirring, and the temperature was raised to 70°C and held for about 1 hour.

Thereafter, it was dried at 110°C to remove moisture and obtain crystals. Finely powder and mix into halogen-containing resin.

(2) Zinc glutamate (amino acid zinc salt by direct method) In a reaction vessel, add 300 mjL of water and 147 g of glutamic acid (1
, 0 mol) and while stirring, add 81.4 g of zinc oxide (
1 mol) and adjusted according to the above zinc glycinate. Thereafter, it is dried at 110°C, pulverized, and blended into a halogen-containing resin.

(3) Preparation of basic organic zinc compound 1501111 water was added to 81.4 g (1 mol) of zinc oxide, and while stirring, 67 g (1 mol as acetic acid) of a 90% acetic acid aqueous solution was gradually added. After adding the entire amount, continue stirring for another 30 minutes. After that, it is dried and crushed.

Note that when acetic acid was used as the carboxylic acid as described above, the reaction with zinc oxide was carried out at room temperature; however, when a higher carboxylic acid was used, heating was carried out as appropriate.

The basicity of the product was controlled by the molar ratio of zinc oxide and carboxylic acid.The molar ratio of both was set for each compound as shown in the table below.

A 1 mol Acetic acid 1.0 mol8 1
Benzoic acid 1. O E 1 Acetic acid 1.0 Lauric acid 0.
2H11,0 Adipine 0.3' (4) Degree of discoloration As a measure of thermal stability, a test piece was placed in an open gear at a predetermined temperature, and the degree of discoloration after a predetermined period of time was visually determined according to the following criteria.

Degree of discoloration Color tone 1 White color 2　　　　　Pale yellow 3 Yellow 4 Light brown 5 Brown 6 Quite dark brown 7 Black Example 1 The following composition was selected as a common formulation.

PVC (Zeon 103EP) 100 parts by weight DOP
40 Zinc stearate 0.2 Calcium stearate 0.1 Bisphenol A 0.1 Others (1)
Various basic organozinc compounds synthesized with zinc glutamate (3) synthesized with zinc glycine (2) (referred to as basic zinc in the table) These compounds were mixed in a high-speed rotating mixer and heated at 170°C.
The mixture was kneaded for 4 minutes using heated rolls to form a sheet with a thickness of 0.5 m/m. This was placed in a gear oven at 180'C, and after a predetermined period of time, it was taken out and the thermal change was observed.
(Left below) Example 2 The following composition was selected as a common formulation.

PVC (Theo 7103EP-8) 100 f
E amount Phloem Zinc stearate 0.5 Calcium stearate 0.2 Dehydroacetic acid
0.05B I T
0.1 Zinc glutamate synthesized with zinc glycine (2) synthesized in (1) (basic zinc is indicated in the table) These formulations were mixed in a high-speed rotating mixer and heated at 180°C.
The mixture was kneaded for 4 minutes using rolls heated to 100 mL to form a sheet with a thickness of 0.5 m/m. This was placed in a gear oven at 180°C and taken out after a predetermined period of time, and thermal changes were observed. (Hereinafter, blank spaces) In Example 1 of Hikari J Shishiku, the effect of the present invention is clear if Test Test 1 is used as a control.

A comparison of NtlLl and Nα2-6 shows the effect of adding a basic organozinc compound to 1.5 parts by weight of zinc glycinate. In this case, the composition of the basic organozinc compound has little difference in effect.

There is clearly a facilitative function.

Comparing Nα1 and Nα7 to 10, it is clear that even if the amount of amino acid zinc salt added is reduced, the stabilizing effect is obvious if the basic organic zinc compound is in a complementary amount.

In this case, basic organozinc compounds serve an alternative function.

It can be seen that a complementary relationship holds true even when the types of amino acid zinc salts are different for Inhibitors 11 and 12.

Regarding Example 2, it can be considered that the above results apply as is if 13 is used as a control.

Comparison of NCL13 and 14-17 shows the promoting effect of the basic organozinc compound. Further, NfllB-19 means the establishment of a complementary relationship between amino acid zinc salts.

Thus, from the examples, satisfactory effects as a novel halogen-containing resin composition with good thermal stability were demonstrated.

Patent Applicant: Nissan Ferro Organic Chemical Co., Ltd. Procedural Amendment June 1988 - 2, Name of the Invention: Novel Halogen-Containing Resin Composition 3, Person Making the Amendment Relationship in the Case Patent Applicant Address: Nihonbashi, Chuo-ku, Tokyo Honmachi 1-10-5 5. Number of inventions increased by amendment None 6. Scope of claims of the specification to be amended 1. Detailed description of the invention 7. Contents of the amendment (1) Scope of claims Correct as shown in the attached sheet.

(2) "Zinc glycinate" in lines 12 to I3 on page 12 of the specification is corrected to "zinc glycine."

(3) "Zinc glycinate" in lines 4 and 5 on page 19 of the specification is corrected to "zinc glycine."

Attachment 2, Claims For 100 parts by weight of the halogen-containing resin, 0.0% of the 91 countersunk stirrup and/or 0.000 g of the a combination lock is added. A novel halogen-containing resin composition containing 1 to 10 parts by weight and 0.01 to 5.0 parts by weight of a basic organic zinc compound.

Claims (1)

[Claims] A novel halogen-containing resin composition comprising 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 organic zinc compound to 100 parts by weight of the halogen-containing resin. thing.