JPH0662825B2 - New halogen-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a stabilized halogen-containing resin composition.

More particularly, it relates to a stabilized novel halogen-containing resin composition obtained by adding a mixed product of a zinc-containing hydrotalcite-like compound with perchloric acid to a halogen-containing resin.

(B) Problems to be Solved by the Prior Art and Invention Generally, halogen-containing resins such as vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, and chlorinated polyethylene are resins that are heated by heating during molding. Remarkably colored or decomposed.

Stabilizers are added to prevent such drawbacks.

However, the stabilizers that have been conventionally used include heavy metals such as cadmium and lead, and have a drawback that they are toxic.

Further, a combination of a low-toxic stabilizer such as a zinc compound of organic acid, an alkaline earth metal salt of organic acid, an organic tin compound, a nitrogen-containing compound such as β-aminocrotonic acid ester and a polyol compound is also used.

However, the use of stabilizers having low toxicity causes coloration of the resin due to heating during molding and is inferior in thermal stability for a long period of time, so that improvement thereof has been strongly demanded.

In recent years, there has been proposed an attempt to improve long-term thermal stability by adding a hydrotalcite compound to a halogen-containing resin as seen in JP-B-58-46146. The compound has a large scavenging ability as a stabilizing effect on the halogen generated by the decomposition of the halogen-containing resin, but on the other hand, it tends to positively extract the halogen from the resin, thereby promoting the formation of polyene, It had the drawback of promoting strong coloring.

(C) Means for Solving the Problems The present inventors intend to eliminate the drawbacks when using a hydrotalcite compound having an excellent halogen-capturing ability as a stabilizer for a halogen-containing resin as described above. As a result of repeated studies, by blending a mixed product of a hydrotalcite-like compound containing zinc with perchloric acid in a halogen-containing resin, the coloration-preventing property is remarkably improved and the long-term thermal stability is also improved. The present invention has been completed and the present invention has been completed.

Thus, according to the present invention, Zn is 0.09-0.25 and Zn /
A mixed product obtained by mixing perchloric acid at a molar ratio of 1.50 to 0.30 mol with respect to 1 mol of a hydrotalcite-like compound containing a ratio of Mg is characterized by being added to a halogen-containing resin. Provided is a stabilized halogen-containing resin composition.

Generally, a hydrotalcite compound is a hydrous double salt compound of magnesium and aluminum represented by the following general formula (I), and includes natural products and synthetic products.

_{Mg 1 - xAlx (OH) 2} Ax / 2 · mH 2 O ... (I) where Shikichu 0 <x ≦ 0.5, A represents a CO ₃ or SO _4, m denotes a positive number.

In the above general formula, if multiplied by 8 each coefficient by substituting this into equation (I) For x = 0.25, the _{Mg 6 Al 2 (OH) 1} 6 · CO 3 · 8mH 2 O ... (II).

Further, the if Likewise 6.5 multiplied by the case of _{x = 0.308 Mg 4.5 Al 2 (} OH) 1 3 · CO 3 · 6.5mH 2 O ... (III).

The hydrotalcite-like compound containing zinc used in the present invention means Mg of the hydrotalcite-like compound.
Are those obtained by replacing a part of the Zn, for example, in the formula _{(II), Mg 5 Zn · Al 2 (} OH) 1 6 · CO 3 · 8mH 2 O In formula (III) Mg _3.5 Zn · Al ₂ (OH ) _{1 3} · CO ₃ · 6.5mH ₂ O.

Further, the ratio of Mg and Zn changes the molar ratio of the raw materials charged during the synthesis of the compound, and is disclosed in Patent Publication No. 47-32198.
It can be arbitrarily adjusted according to the method described in Japanese Patent Publication No. 48-29477.

In order to obtain a mixed product of the above-mentioned hydrotalcite-like compound containing zinc used in the present invention and perchloric acid, perchloric acid is added to 1 mol of the hydrotalcite-like compound containing zinc. It can be adjusted by a method of contacting and mixing in the range of 1.50 to 0.30 mol.

When the molar ratio of perchloric acid is greater than 1.50, the mixing uniformity of the hydrotalcite-like compound and perchloric acid is insufficient.

Further, when the amount is 0.30 mol or less, no compounding effect is observed.

The halogen-containing resin referred to in the present invention is, for example, a homo- or copolymer obtained by polymerization of vinyl halide, vinylidene halide, etc. and a copolymer with these copolymerizable compounds, for example, vinyl chloride-ethylene copolymer. Coalescing, etc.
Further, a resin obtained by halogenating a polyolefin resin such as polyethylene or polypropylene, for example, a chlorinated polyolefin resin such as chlorinated polyethylene or chlorinated polypropylene can be used. Further, the present invention can be applied to a polymer blend of a halogen-containing resin and a halogen-free resin, such as ABS, MBS, EVA, and butadiene resin.

The blended amount of the mixed product of the present invention with respect to the halogen-containing resin is 0.001 to 100 parts by weight, preferably 0.01 to 5.0 parts by weight, based on 100 parts by weight of the resin.

If the addition amount of the mixed product is 0.001 part by weight or less with respect to the halogen-containing resin, the compounding improving effect is not seen. Further, when the amount is 100 parts by weight or more, the improvement effect is observed, but the validity is lost from the economical point of view.

In addition, of the hydrotalcite-like compounds containing zinc
The ratio of Zn to Mg is 0.09 to 0.25 in terms of Zn / Mg.

(D) Scope of application of the invention In carrying out the present invention, the composition of the present invention can be obtained by adding one or more conventional additives to the resin together with the addition of the mixed product of the present invention. An excellent synergistic effect can be obtained in the meantime.

Examples of such additives include metal salts of organic acids, metal oxides, hydroxides, basic inorganic acid salts, hydrotalcite-like compounds, organic phosphite compounds, organic phosphoric acid metal salts, polyols, Examples thereof include nitrogen-containing non-metal compounds, antioxidants, light stabilizers, β-diketone compounds, epoxy compounds, and organic tin compounds.

The above-mentioned conventional additives are exemplified below by type.

Examples of the metal salt of an organic acid include Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cd, and Pb as examples of the metal serving as the metal component of the organic acid.

As the organic acid residue, there are the following carboxylic acid or phenol residues. Examples of carboxylic acids are acetic acid, propionic acid, caprylic acid, 2-ethylhexoic acid, lauric acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropion. acid,
Lauryl mercaptopropionic acid, benzoic acid, paratertiarybutylbenzoic acid, dimethylbenzoic acid, aminobenzoic acid, salicylic acid, aminoacetic acid, glutamic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, maleic acid, thiodipropionic acid, etc. Can be given.

Examples of phenols include phenol, nonylphenol, tertiary-butylphenol, octylphenol, isoamylphenol, cresol, xylenol and the like.

Examples of metal oxides include MgO, CaO, BaO and Al ₂ O ₃ .

As the hydroxide, Mg (OH) ₂ , Ca (OH) ₂ , Ba (O
H) ₂ , Al (OH) _{3 and the} like.

Examples of basic inorganic acid salts include MgO · Mg ₃ (PO ₄ ) ₂ , Mg (OH) ₂ · MgHPO ₃ , Mg (OH) ₂ · Mg ₂ SiO ₄ , 2MgO · Mg ₂ SiO ₃ , CaO · Ca. ₃ (PO ₄ ) ₂ , Ca (OH) ₂ · Ca ₃ (PO ₄ ) ₂ , 2CaO · CaHPO ₃ · CaO · Ca ₂ SiO ₄ , 2ZnO · Zn ₃ (PO ₄ ) ₂ , ZnO · ZnHPO ₃ etc. To be

The hydrotalcite-like compound means the above-mentioned general formula (I).
Indicates a compound as it is, which is not treated with perchloric acid.

Examples of organic phosphite compounds include isooctyl phosphite, distearyl phosphite, triisodecyl phosphite, triisoactyl phosphite, trilauryl phosphite, tristearyl phosphite, tridipropylene glycol phosphite, diphenyl phosphite, Triisononyl phenyl phosphite, triphenyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, phenyl diisooctyl phosphite, diisodecyl pentaerythritol-diphosphite, tetraphenyl dipropylene glycol diphosphite, polydipropylene glycol phenyl Phosphite, trilauryl trithiophosphite, trisnonylphenyl phosphite, distearyl penta Lithritol-diphosphite, bis (2,4-ditertiary-butylphenyl) -pentaerythritol diphosphite, dilauryl phosphite, ditridecyl phosphite, ethylhexyl diphenyl phosphite, phenyl neopentylene glycol phosphite, peptakis tripropylene glycol Triphosphite, diphenyldidecyl (2,2,4-trimethyl-1,3-pentanediol) -diphosphite, diisooctyloctylphenylphosphite, poly 4,
4'-isopropylidene diphenol neodol 25 alcohol phosphite and the like can be mentioned.

Examples of the organic phosphoric acid metal salts are represented by the following general formula (IV) or (V).

Examples include either the monoorganophosphoric acid metal salt of (IV) or the diorganophosphoric acid metal salt of (V), or a mixture of both.

In the formula, R ₁ , R ₂ and R ₃ each represent alkyl, aryl, arylalkyl, alkylaryl or an alkyl group having an ether bond, and M represents two alkali metal atoms, alkaline earth metal atoms or zinc. , M'represents an alkali metal atom, an alkaline earth metal atom or zinc. a represents 1 or 2.

Examples of such metal components of the organic metal phosphates include:
Examples thereof include alkali metals such as Li, Na and K, alkaline earth metals such as Mg, Ca, Sr and Ba, and Zn.

Examples of alkyl groups include methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, secondary butyl, tertiary
Butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, _{tridecyl, C 1 2 - 1 3} mixed alkyl, stearyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl , 4-methylcyclohexyl and the like.

Examples of aryl groups include phenyl, naphthyl and the like. Examples of arylalkyl groups are benzyl, β-phenylethyl, γ-phenylpropyl, β-
Examples include phenylpropyl.

Examples of alkylaryl groups include tolyl, xylyl, ethylphenyl, butylphenyl, tert-butylphenyl,
Examples thereof include octylphenyl, isooctylphenyl, tert-octylphenyl, nonylphenyl, 2,4-di-tert-butylphenyl and the like.

Examples of the alkyl group having an ether bond include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl and α-methylfurfuryl groups, or methyl-, ethyl-,
Isopropyl-, butyl-, isobutyl-, hexyl-, cyclohexyl-, phenylcellosolve residues; methyl-, ethyl-, isopropyl-, butyl-, isobutylcarbitol residues; triethylene glycol monomethyl ether, -monoethyl ether, -Monobutyl ether residue; glycerin 1,2-dimethyl ether, -1,3-
Dimethyl ether, -1,3-diethyl ether, -1-
Ethyl-2-propyl ether residue; nonylpheninoxypolyethoxyethyl, lauroxypolyethoxyethyl groups and the like.

Examples of polyols include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, mannitol, sorbitol, polyethylene glycol, ditrimethylolpropane, tris- (2-hydroxyethyl) isocyanurate and the like. And further,
Partial esterification products with these monobasic acids and / or polybasic acids may be used.

Examples of nitrogen-containing non-metal stabilizers include urea, melamine, α
-Phenylindole, diphenylthiourea, 1,4-butanediol aminocrotonic acid ester and the like can be mentioned.

Examples of antioxidants are 2,6-di-t-butyl-p-cresol, 2,5-di-t-butylhydroquinone, 2,2 '.
-Methylene-bis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (6-t-butylphenol), 4,4'-thiobis- (6-t-butyl-m-cresol) Octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenol) propionate,
Pentaerythrityl-tetrakis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate)] and the like can be mentioned.

Examples of light stabilizers are 2-hydroxy-4-octoxybenzophenone, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenylacrylate, bis (2 2,2,6,6-tetramethyl-4-piperidine) sebacate, 2,4-di-tertiarybutylphenyl-3 ′, 5′-ditertiarybutyl, 4′-hydroxybenzoate and the like can be mentioned.

Examples of β-diketone compounds include dibenzoylmethane, stearoyl, balmitoylbenzoylmethane, dehydroacetic acid, and metal salts of these β-diketone compounds.

Examples of the epoxy compound, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized polybutadiene, epoxy methyl stearate, -butyl,-
2-ethylhexyl, -stepril, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, 3- (2-xenoxy) -1,2-epoxypropane, bisphenol- A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-
Methylepoxycyclohexanecarboxylate and the like can be mentioned.

Examples of the organic tin compound, dibutyltin laurate, dioctyltin laurate, dibutyltin maleate, dioctyltin maleate, dibutyltin mercaptoacetate, monobutyltin mercaptoacetate,
Dibutyl tin isoactyl thioglycolate, monobutyl tin isooctyl thioglycolate, dioctyl tin mercapto acetate, monooctyl tin mercapto acetate, dioctyl tin isooctyl thioglycolate, monooctyl tin isooctyl thioglycolate,
Etc.

In addition to the above-mentioned conventional additives, if necessary, a plasticizer, a pigment, a filler, a foaming agent, an antistatic agent, an antifogging agent, an anti-flate agent, a surface treatment agent, a lubricant, a flame retardant, etc. may be added. It doesn't matter what you add.

(E) Synthetic example Synthetic example 1 Synthetic example of hydrotalcite-like compound having zinc, Mg (NO ₃ ) _{2 in} a beaker equipped with stirrer and pH electrode
· 6H ₂ O, 25.6g (0.1 mol) and _{Zn (NO 3) 2 · 6H} 2 O, 6.95
g (0.02 mol), further _{Al (NO 3) 3 · 9H} 2 O, 15.0g (0.04
Acid solution of 200 ml of pure water and 2.1 g of Na ₂ CO ₃
(0.0198 mol) and NaOH 12.8 g (0.32 mol) in pure water 200
The alkaline liquid dissolved in ml is added dropwise while controlling the flow rate of both so that the pH of the liquid is maintained between 10.0 and 11.0.

After completion of the reaction, the precipitate was filtered off and dried at 80 ° C for 10 hours.
The resulting samples by metal analysis such as was _{Mg 5 ZnAl 2 (OH) 1} 6 · CO 3 · 4H 2 O.

Similarly operated by _{Zn 6 Al 2 (OH) 1} 6 · CO 3 · 4H 2 O, Mg
_4.0 was synthesized ones _{Zn 0.5 Al 2 (OH) 1} 3 · CO 3 · 3.5H 2 O and the like various molar ratios.

Synthesis Example hydrotalcite like compounds containing zinc adjusted by adjusting the above Synthesis Example 1 of the mixed product of the hydrotalcite-like compound and perchloric acid containing 2 zinc _{Mg 5 ZnAl 2 (OH) 1} 6 · CO ₃ · 4H ₂ O64.
While stirring 5 g (0.1 mol) in a beaker, perchloric acid 1
5.1 g (0.15 mol) diluted with 200 ml of water was added dropwise and mixed well. The product was dehydrated by a dehydrator equipped with a vacuum pump and dried at 80 ° C. for 10 hours.

The same operation was performed to prepare mixed products having different Zn / Mg ratios and different molar ratios of perchloric acid to obtain mixed product evaluation samples shown in Table 1.

(F) Examples The gist of the present invention will be specifically described below with reference to Examples. However, the invention is not limited to these examples.

Example 1 To see the effect of the halogen-containing resin composition according to the present invention,
The mixture shown below was made into a test sheet having a thickness of 0.5 mm by a kneading roll. Gear-Aging tester 180 ℃
The thermal stability and colorability of the were investigated. The evaluation of thermal stability was expressed by the time when the test piece turned black. The colorability was determined by visually observing the degree of coloration after 20 minutes from the gear-aging tester. The results are shown in Table 2. Further, deterioration due to light was measured using a sunshine weather meter. The degree of deterioration was expressed as the residual elongation percentage after 500 hours, and the degree of coloration of the test piece at the same time was visually observed and the color tone thereof is also shown. The closer the residual elongation rate is to 100%, the smaller the deterioration due to light.

For comparison, the same test was conducted without the sample, and the results are also shown in Table 2.

Blended polyvinyl chloride 100 parts by weight DOP 40 〃 Epoxidized soybean oil 1.0 〃 Barium nonylphenate 0.8 〃 Zinc stearate 0.2 〃 Sample As shown Example 2 When the composition of the present invention was used in combination with one or more conventional additives usually used as a stabilizer component, a further improvement effect was obtained. The synergistic effect with the combined stabilizer was examined by the same method as in Example 1 using the formulations shown below. The results are shown in Table 3.

Blend Polyvinyl chloride 100 parts by weight ABS 20 〃 calcium carbonate 5 〃 DOP 50 〃 barium stearate 0.6 〃 zinc octoate 0.3 〃 sample B 0.5 〃 In Table 3, ST-210 Ajinomoto Co. dipentaerythritol partial esterified product THEIC Shows Tris (2-hydroxyethyl) isocyanurate manufactured by Nissan Chemical Industries, Ltd.

(G) Effect of the Invention As is clear from the results of Example 1, by adding the mixed product of the present invention to the halogen-containing resin, the halogen-containing resin composition is significantly improved in coloration-preventing property and long-term thermal stability. I was seen. Further, the effect of improving physical properties such as prevention of deterioration due to light was also observed.

In Example 2, by using the mixed product of the present invention in combination with one or more of the conventional additives, excellent synergistic effects on the coloration-preventing property and long-term thermal stability can be obtained. Between the composition. Therefore, the present invention provides a halogen-containing resin composition having extremely high commercial value.

Continuation of the front page (56) References JP-A-60-104141 (JP, A) JP-A-59-140261 (JP, A) JP-A-58-222128 (JP, A)

Claims (1)

[Claims] 1. A mixed product obtained by mixing perchloric acid in a molar ratio of 1.50 to 0.30 mol with respect to 1 mol of a hydrotalcite-like compound containing zinc in a Zn / Mg ratio of 0.09 to 0.25. A stabilized halogen-containing resin composition, which is added to a halogen-containing resin.