JPS6181462A - Stabilizer for halogen-containing resin - Google Patents

Abstract

PURPOSE:To produce a halogen-containing resin composition having high discoloration resistance and improved long-term thermal stability, by substituting a part of a hydrotalcite compound having carbonate group with a dibasic acid, and adding a specific amount of the reaction product to a halogen-containing resin. CONSTITUTION:100pts. (wt.) of a halogen-containing resin (e.g. vinyl chloride- ethylene copolymer) is added with 0.01-10pts., preferably 0.1-10pts. of a reaction product obtained by reacting a hydrotalcite compuond of formula (0<x<=0.5; m<0) with a dibasic acid (e.g. oxalic acid, maleic acid, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel chlorogen-containing resin composition with excellent thermal stability. The present invention relates to a heat stabilizer for halogen-containing resins which is substituted with a dibasic acid or a mixture of a dibasic acid and a water-soluble-basic acid to form a t-reaction.

Conventional technology/~A-gen-containing resin, '# Polyvinyl chloride resin is inherently thermally unstable, and may cause damage within one molecular chain due to heating during dripping or surface temperature rise due to sunlight during use. A decomposition reaction due to dehalogenation occurs, resulting in 1 coloration 9
A decrease in mechanical strength is observed. Stabilizers are added to completely prevent such defects.

However, conventionally used stabilizers contain heavy metals such as cadmium and lead, and have the disadvantage of being toxic. In addition, as less toxic stabilizers, organic acid lead salts, organic acid alkaline earth metal salts, organic tin compounds, β-amic a
It has been used in combination with element-containing nonmetallic compounds such as tonic acid esters, polyols, etc. but.

These stabilizers have the disadvantage of causing coloration during molding, and there is a strong demand for improvement in long-term thermal stability.

In recent years, attempts have been proposed to improve the long-term thermal stability by adding a bitrotaphresite compound to a halogen-containing resin, as seen in Japanese Patent Publication No. 58-46146.

However, these compounds* have a greater ability to capture the /NO generated by decomposition than resins containing 10-gen as a stabilizing effect;
It has the disadvantage of promoting the formation of polyene and causing strong coloring due to its tendency to pull out rogens. There are many.

SUMMARY OF THE INVENTION The present inventor has solved the drawback that hydrotalcite compounds used in resins containing 7% oxygen generate strong coloring during molding processing despite maintaining excellent long-term thermal stability. As a result of intensive studies, we have developed a reaction product of a 7-hydrotalnite compound having a carbonate group and a dibasic acid or a mixed acid of a water-soluble basic acid and a dibasic γ acid to a resin containing /%O. The present invention has been completed by discovering that by adding these compounds, coloration can be significantly prevented and long-term thermal stability can also be maintained.

The hydrotalcite compound having a carbonate group used in the present invention is a hydrous double salt compound of magnesium and aluminum represented by the following general formula, and may be an extracted, natural product or a synthetic product.

Mf(1-X)AtX(OH), Co, 8 mH, 0O
(X≦15. Katsuta represents a positive number.

The dibasic acid used in the present invention is oxalic acid.

Maleic acid, fumaric acid, itaconic acid, malonic acid.

Succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid.

Examples include acids and acid anhydrides such as golic acid, tartaric acid, citric acid, and sulfuric acid. In addition, as water-soluble basic acids, acetic acid,
Pionic acid, butyric acid, benzoic acid.

Glycolic acid, lactic acid, salicylic acid, perchloric acid.

Examples include hydrochloric acid, nitric acid, acrylic acid, draw+7 benzoic acid, glycine, glycocholic acid, and glutamate/acid.

The reaction product of the idrotalnite compound used in the present invention is obtained by heating a mixed acid of the idrotalnite compound and a dihydrothalnite acid or a water-soluble -1-a base acid in water, for example. It can be obtained by partially replacing the carbonate groups of the talcide compound with acid, and drying this.

Since 1 mol of a hydrotalcite compound has 1 mol of carbonate group, the reaction amount of a dibasic acid or a mixed acid of a water-soluble basic acid and a dibasic acid is 1 mol to 1.0 mol of this carbonate group α0. is the quantity to be replaced.

What is the /%Oge/containing resin used in the present invention?

For example, homopolymers and copolymers obtained by polymerization of vinyl halides, vinylidene halogenides, etc., and copolymers with these copolymerizable compounds, such as vinyl chloride-ethylene copolymers.

JJKHResin obtained by rogenizing polyoffine resins such as polyethylene and polypropylene.

For example, chlorinated polyethylene V7. Chlorinated polypropy.

Examples include chlorinated polyolefin resins such as Ren. Furthermore, the present invention can also be used in polymer blends of halogen-containing resins and -.a-gen-free resins 1, such as Bd, MB, KVA, Petazier/resins, and the like.

The amount of the reaction (mixture) product of the present invention added to 100 parts by weight of these halogen-containing resins is (101 to 10 parts by weight, preferably 1 to 10 parts by weight cL).

Field of Application The combined use of the composition of the present invention with known substances commonly used as stabilizer components does not in any way reduce the effects of the present invention. These commonly used stabilizers are:
Metal organic acid salts.

Organic 7-osphite compounds, organic tin compounds, antioxidants, ultraviolet absorbers, metal oxides, metal hydroxides, polyols, nitrogen-containing nonmetallic compounds.

Examples include epoxy compounds. In addition, plasticizers, pigments, fillers 1 blowing agents, antistatic agents, antifogging agents,
Plate-out prevention agent 9 There is no problem in adding surface treatment agents, erasing agents, flame retardants, etc. to the formulation.

Next, an example of preparation of the reaction product in the present invention will be shown. D manufactured by Kyowa Chemical Industry Co., Ltd. as a hydrotalcite compound
F (using T-4A, q, DI (using T-4A, 7?
: If, in a chemical formula! i4?4.5A4(Of(),.

CO,・558. Expressed as O, 1 mole is 5 (17,4F).

On the other hand, a dibasic acid or a mixed acid of a dibasic acid and a water-soluble basic acid is added to the carbonate group contained in the hydrotalcite compound (1
Dissolve in water an amount to replace 1 mole to 1 mole of DF
(obtained by adding T-4A and thoroughly mixing while heating. Also, if necessary, a small amount of a surfactant may be used to improve the dispersion of Di(T-4A).

Next, the present invention will be explained using a practical example #1. However, the present invention is not limited to the following examples.

Reaction Example A) Water zoocctcx Water-rV Inoic acid 9.8 f f approx.
Heat and melt at ~80°C to obtain 5α7? of DHT-4A. and 1 cL of surfactant (Suba/20 Kao Soap n>) was added, heated and stirred for about 2 hours, then taken out, dried at 100°C, and crushed to obtain 54.8 f of a reaction product.

Reaction Example 71!1flJB) 70X perchloric acid aqueous solution 7.1 was dissolved in 150F, and DF (T-4Ai5 [17] was added thereto and heated and stirred at about 70°C. After about 50 minutes, 11ft of adipic acid
- After further heating and stirring for about 1 hour and 50 minutes, the mixture was taken out, dried at 100°C, and pulverized to obtain about 612 of the 9 reaction product.

In order to see the effect of the reaction products obtained by the methods according to Reaction Examples A and B, the samples were thoroughly mixed according to the following recipe, and 6x
A 12-inch test roll was rolled at 175°C for 4 minutes to form a sheet with a thickness of approximately 15%, and then rolled and kneaded at 7-
Cut out 2 cIIRX 23 test pieces from each sample, place them in a gear oven set at 180°C to 2°C, and take out each test piece at regular intervals and visually observe the degree of coloration.9.

Blend composition pvc Zeo/10jEiP 100 parts by weight Town plasticizer DOP 50 #Epoxidized soybean oil 11 Zinc stearate α5I Dipentaerythritol α21 Reaction product of this application 1t* rhyz reaction product A
DHT-4A 1 mol Adivic acid 1 mol 9
z Maleia anhydride #R1 mol CI
Malayan anhydride tank α5 mol 0' Oxalic acid 1 mol f5
z Tartaric acid 1 mol iF
z Malic acid 1 mol G l
Anhydrous Malay Diagram α 75 mole Perchloric acid α5 Molbi I Anhydrous Frey 4 Ryo α 5 mole Perchloric acid 1 mole I ′ Adipine' II C175
Molar perchlorine d 0.5 mol or 1 The numerical value of the degree of coloring is based on the following correspondence.

1 Colorless or slightly yellow 2 Pale yellow 3 Yellow 4 Yellowish brown 5 Reddish brown 6 Black Patent applicant 8 Production 7 Koo Organic Chemical Co., Ltd. Procedural Amendment 1982 L/Month 8th Director of the Patent Office Manabu Shiga Tonohi 1 , Indication of the case 1982 Patent Application No. 204564 Z Name of the invention Halogen-containing resin stabilizer Process Amendment person Relationship to the case Patent applicant +y-'yT Ukunihon Pasihon f, Tsu Address 103
1-2-2 Nihonbashi Honmachi, Chuo-ku, Tokyo Contact phone number: 05-245-0661 (Main) 4. Number of inventions increased by amendment: None 5. Subject of amendment: 4fiJ of the title of the invention in the application and the specifications Book [Issue 54]
11 Contents of Paper & Amendment (1) In the title of the invention column of the application, amend "Rogen-containing resin stabilizer" to "Rogen-containing resin composition."

(2) On page 1 of the specification, line 3, column 1, title of the invention, amend it to ``halogen-containing resin stabilizer'', ``trans-halogen-containing resin composition.''

(3) Amend the scope of claims on page 1 of the specification as a separate sheet.

Hand and arm correction hexagram (spontaneous) 2. Claims (1) A reaction product in which a part of the carbonate group of a hydrotalcite r-arsenite compound having a carbonate group in 100 parts by weight of a halogen-containing resin is replaced with a dibasic acid. A halogen-containing resin composition, characterized in that the thermal stability of the halogen-containing resin is improved by adding 10 parts by weight of α01 to 10 parts by weight.

(2) The acid that replaces a portion of the carbonate groups of the hydrotalcite f-hybrid compound having a carbonate group is characterized in that it is a mixed acid of a dibasic acid and a water-soluble-basic acid.

Paraboloid.

1. Indication of the incident: 1982 Patent Application No. 204564? , Name of the invention: 1. Name of the invention: 1. Name of the invention: 1. ll series Patent applicant address: 1-2-2 Nihon 4 Honmachi, Chuo-ku, Toboto! Contact phone number Q 5-245-06614, Number of inventions increased by amendment None 5, Patent of specification subject to amendment, N Ueda of scope of request, and detailed description of invention.

Contents of amendment (1) The claims of the specification are amended as shown in the attached sheet.

(2) Details! From page f1, line 20 to page 2, line 1, "or mixed acid of dibasic acid and water bath-basic acid"
Delete.

(3) From page 63, line 20 to page 4, line 1, [or water bathing - mixture of basic acid and dibasic acid]
Delete J.

(4) From page 4, line 16 of the specification to page 5, line 1, "Also, water bathable basic acids include Kuitan, Gropio/[-&, 83 revised, benzoic acid, glycol. Acid, lactate, narityl, peroxidase, hydrochloric acid, nitric acid, and doroacrylic acid, hydroxybenzoic acid, glycine, glycocholic acid,
Glutamic acid etc. are scattered. ” to be deleted.

(5) Clear 4FA #5, page 5, line 4, ``Or, water-soluble-basic acid mixture I!Ii!j'' should be deleted. Around 2nd year 1: Delete 1 extra part of the wage mixture (λ).

(7) Akira, old 47th page, from line 7 to line 8, the name that deletes "or 21 groups of me and the 1st life of bathing -] Mixture of 菟 group 1-λ".

(8) Light R; 18 pages 5 "From 1 to 10 lines [70) 1; +tA L12 g +R water bath 7.1
f water 1501vc gs DHT-4A
f 5 :l 7 f 1JT
The mixture was heated and stirred at 70°C. , 550
Shirutan, Ajibi 7#111'/JO and about 1 hour 5
0 Soup slowly stirring? After this, the mixture was taken out, dried and crushed at 100°C to obtain about 612 pieces of 9 reaction products. ” to be deleted.

(9) Specification, page 8, line 11, “Anti-Shi I Column A.

Correct BJ to "reaction charge A."

+1 (j Delete the three lines (), H, and I in the table on page 9 of the details and correct it as shown in the table below.

+Jη Specification d Page 10, lines 7 to 12 "G I Maleic anhydride 175 mole Persalt: R acid [15 mole [(1g Maleic anhydride [L5 mole Perchloric acid 1 mole I I Adipic acid α75 mole Delete.

L・1t[-2, Claims/% Cll-free resin having a carbon group in 100 parts by weight/・ido-talcite compound having a part of carbonate group replaced with a dibasic acid, reaction product 1 From t-α01 Direct Welfare Department []4i
6. Rogen-containing resin Bi
? Parabolic.

Claims (2)

[Claims] (1) Adding 0.01 to 10 parts by weight of a reaction product obtained by substituting a part of the carbonate group of a hydrotalcite compound with a dibasic acid to 100 parts by weight of the halogen-containing resin. A halogen-containing resin stabilizer characterized by improving the thermal stability of halogen resins. (2) A hydrotalcite compound having a carbonate group is characterized in that the acid that replaces a portion of the carbonate group is a mixed acid of a dibasic acid and a water-soluble-basic acid. A halogen-containing resin stabilizer according to claim 1.