JPS62267347A - Chlorine-containing urethane resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition markedly improved in both thermal stability and heat discoloration-proofness, by incorporating a blend of chlorine-contg. resin and urethane resin with a blend product from specific hydrotalcite compound(s) and perchloric acid. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of either polymer blend of chlorine-contg. resin and urethane resin or copolymer resin therefrom with (B) 0.001-10pts.wt. of a blend product from B1: one or two kinds of hydrotalcite compounds selected from hydrotalcite compounds with their metal components being Mg and Al and those compounds with their metal components being Mg, Zn and Al and B2: perchloric acid. For the component A, 30-80wt% of the chlorine-contg. resin and 70-20wt% of the polyurethane resin are used.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a chlorine-containing urethane resin composition, specifically a polymer blend consisting of a chlorine-containing resin and a urethane resin, or a copolymer of a chlorine-containing resin and a urethane resin. The present invention relates to a stabilizer for a resin composition.

(b) Problems to be solved by the prior art and the invention Chlorine-containing resins are widely used as thermoplastic resins, and by selecting the amount of plasticizer such as dioctyl phthalate, they can be used to create films, which are molded products. The hardness of sheets and profile extrusions can be adjusted as desired. However, since plasticizers are low molecular weight compounds, they are prone to leaching out of resin compositions, a so-called blooming phenomenon, which causes problems such as surface staining and deterioration of physical properties.

Furthermore, in recent years, demands regarding the physical properties of molded products have diversified, and in order to impart rubber elasticity to chlorine-containing resins, elastic resin compositions have been developed by blending plasticizers with highly polymerized chlorine-containing resins. ing.

In order to prevent such leaching of plasticizers and to impart rubber elasticity, urethane resins are mixed in place of plasticizers. Examples of blending methods include using a so-called polymer blend in which a urethane resin is blended with a chlorine-containing resin, and a chlorine-urethane copolymer resin obtained by copolymerizing a chlorine-containing resin and a urethane resin.

However, compared to the case where a chlorine-containing resin is plasticized with a plasticizer, when a urethane resin is blended by the above-mentioned method, the thermal stability and discoloration prevention property of the resin composition during heat molding are not sufficient. Improvements were requested.

The chlorine-containing resin, which is one of these components, easily undergoes a dehydrochloric acid reaction when heated, and the stabilizers include metal organic acid salts such as Ca, Ba, Zn, and Sn, and the produced gold as a so-called hydrochloric acid catcher. Various compounds such as phosphite compounds, polyols, and nitrogen-containing compounds are used in combination as chloride scavengers.

On the other hand, as stabilizers for urethane resins, for example, when aromatic isocyanates are used as the isocyanate component, azo compounds and phenolic compounds are used as antioxidants to prevent oxidation of benzene nuclei present in urethane.

As described above, since the stabilization mechanisms of chlorine-containing resins and urethane resins are different, it is currently difficult to find a stabilizer that has a common improvement effect, except for antioxidants that commonly have a certain degree of stabilizing effect. there were.

(c) Means for Solving the Problems The present inventors have repeatedly investigated various causes of decomposition due to heating of chlorine-containing urethane resin systems. As a result, the residual aroma of catalysts such as tertiary amines such as triethylene amine, sulfonic acid, and phosphoric acid catalysts used during the polymerization of urethane resins has a negative effect on the thermal stability and thermal coloring prevention properties of chlorine-containing resins. We found that this is a major inhibiting factor.

The present inventors previously disclosed the use of a mixed product of hydrotalcite compounds and perchloric acid as a stabilizer for halogen-containing resins in JP-A-59-140261.
By adding this mixed product of hydrotalcite and perchloric acid to a chlorine-containing urethane resin system, it is possible to significantly alleviate the above-mentioned inhibitory factor of catalyst residual smell, improve thermal stability, and prevent thermal discoloration. The present inventors have discovered that a resin composition with significantly improved properties can be obtained, and have completed the present invention.

That is, the present invention provides a polymer blend of a chlorine-containing resin and a urethane resin, or a copolymer resin of a chlorine-containing resin and a urethane resin, and a hydrotalcite I compound in which the metal component is Mg, 1, or a metal component force <Mg. Zn, AI
The method is characterized in that a mixed product of one or two hydrotalcite compounds selected from the hydrotalcite compounds represented by I and perchloric acid is added. thermal stability,
The object of the present invention is to provide a chlorine-containing urethane resin composition that has excellent thermal coloring prevention properties.

The chlorine-containing resin used in the present invention includes a homopolymer or copolymer of vinyl chloride or vinylidene chloride.

A copolymer is a copolymer of vinyl chloride or vinylidene chloride and other ethylenically unsaturated monomers, and these ethylenically unsaturated monomers include acrylic acid, ethyl acrylate, acrylonitrile, etc. Examples include acrylates: vinyl monomers such as styrene, vinyl acetate, and alkyl vinyl ethers; maleates such as maleic acid, maleic anhydride, and maleic esters; and olefinic monomers such as ethylene, propylene, and butadiene.

The polyurethane resin used in the present invention is a polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, etc., a high molecular weight polyester polyol or polyether polyol having hydroxyl groups at both ends, and, if necessary, glycol, diamine, hydrazine, etc. and a chain extender by a conventional method.

The copolymer resin of a chlorine-containing resin and a urethane resin used in the present invention is, for example, an unsaturated polyurethane produced from a polyester polyol and polyisocyanate containing an unsaturated aliphatic dibasic acid as part or all of the acid component. Examples include vinyl chloride-urethane copolymer resins in which vinyl chloride is graft-polymerized.

In the polymer blend consisting of a chlorine-containing resin and a polyurethane resin in the present invention, the ratio of both resins is not particularly limited, but the chlorine-containing resin is 30 to 80% by weight and the polyurethane resin is 70 to 20% by weight. preferable.

In the copolymer resin of chlorine-containing resin and urethane in the present invention, the ratio of both components is not particularly limited, but it is preferable that the chlorine-containing resin component is 30 to 80% by weight and the urethane component is 70 to 20% by weight. .

To obtain a mixed product of the hydrotalcite compound and perchloric acid used in the present invention, it can be prepared by stirring and mixing the hydrotalcite compound with perchloric acid in a solvent or the like. . The hydrotalcite compound used for mixing adjustment is, for example, a composite metal hydroxide of a divalent metal and a trivalent metal represented by the following general formula (1), and may be a natural product or a synthetic product.

General formula M”+-XA (l X(OH)z AX/
2 ・mH2O...(1) Here, X is a positive number in the range of O<x≦0.5, and H2O represents a divalent metal cation. For example, from M g 2" + Zn", etc. Represents one or two selected types.

, represents the anion CO3.

A method for producing a synthetic product having a divalent metal cation power of N M g 2 + is disclosed in Japanese Patent Publication No. 1983-2280, Method for Producing Hydrotalcite. Bivalent metal positive, t
77><Mg'' and Zn''
It is disclosed in Publication No. 29.

The preparation of the mixed product of the above-mentioned hydrotalcite compound and perchloric acid can be carried out, for example, in JP-A-59-1 filed by the same applicant.
This can be carried out by the method disclosed in Japanese Patent No. 40261.

The amount of the adjusted mixed product of the present invention added is 0.001 to 100 parts by weight of the total amount of chlorine-containing resin and polyurethane resin in the case of a polymer blend, or 100 parts by weight of copolymer resin. 10 parts by weight is preferred. When the amount of O, OO added is less than 1 part by weight, no improvement effect is observed;
Even if it is added in an amount of 0 parts by weight or more, no further effect will be obtained, and it will no longer be appropriate from an economic standpoint.

(d) Scope of Application of the Invention When carrying out the present invention, in addition to the addition of the mixed product of the present invention, one or more conventional additives may be added to the resin, thereby making it possible to combine the composition with the present invention. Excellent synergistic effects can be obtained between them.

Examples of such additives include metal salts of organic acids, metal oxides, hydroxides, basic inorganic acid salts, hydrotalcite compounds, organic phosphite compounds, metal organic phosphates, polyols, Nitrogen-containing nonmetallic compounds, antioxidants, light stabilizers, β-diketone compounds, epoxy compounds,
Examples include organic tin compounds.

The above-mentioned commonly used additives are illustrated below by type.

Examples of metal salts of organic acids that are metal components of organic acids include Li, Na, K, Mg, Ca, and S.
r, Ba.

There are Zn, Cd, Pb, etc.

Examples of organic acid residues include carboxylic acid or haphenol residues as shown below. Examples of carboxylic acids include acetic acid, propionic acid, caprylic acid, 2-ethylhexoic acid, lauric acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, lyluic acid, and glycolic acid. , lactic acid, hydroacrylic acid, alpha-oxybutyric acid, glyceric acid, malic acid, tartaric acid, citric acid, thioglycolic acid, mercaptopropionic acid, laurylmercaptopropionic acid, benzoic acid, paratertiary butylbenzoic acid, dimethylbenzoic acid, amino benzoic acid,
Examples include salicylic acid, aminoacetic acid, glutamic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, maleic acid, and thiodipropionic acid.

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

Metal oxidation 'tlJ rD Example Toshi''Cha MgO,C
ab, BaO,'A l 203.

As hydroxides, Mg(OH)z, Ca(OH)z,
Ba(0)l)zlAβ(OH), and the like.

Examples of basic inorganic acid salts include MgO・Mgx(PO4)z, Mg(OH)z・M
g1iPOff.

Gate (OH) 2 ・MgzSiOn, 2
Mg0・Mg25i(h +CaOHca(pot)
z + Ca(OH)z HCa5(PO4)z.

2Ca(lCaHPO,, CaO-Ca2Si04
.

2ZnO・Zn*(PO4)2. ZnO・ZnHPO
3rd prize is given.

The hydrotalcite compound refers to a compound represented by the above general formula (1) as it is without being subjected to perchloric acid treatment.

Examples of organic phosphite compounds include inoctyl phosphite, distearyl phosphite, triisodecyl phosphite, triisooctyl phosphite, trilauryl phosphite, tristearyl phosphite, tridipropylene glycol phosphite, diphenyl phosphite, Triisononylphenyl 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 pentaerythritol-diphosphite, bis(2,4-ditertiary-butylphenyl)-pentaerythritol diphosphite, diuralyl phosphite, ditridecyl phosphite, Ethylhexyl diphenyl phosphite, phenylneopentylene gelicol phosphite, peptakistripropylene glycol phosphite, diphenyldidecyl (2,2,4-trimethyl-1,3-pentadiol)-diphosphite, diisooctyloctyl phenyl phosphite, poly 4,
Examples include 4'-isopropylidene diphenol neodol 25 alcohol phosphite.

Examples of organic phosphate metal salts include the following general formula (n) or (
I[[).

○ Either the monoorganic metal phosphate of (If) or the diorganic metal phosphate of (III), or a mixture of both can be mentioned.

In the formula, R+, Rz and -R3 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. and M' represents an alkali metal atom, an alkaline earth metal atom, or zinc. a represents 1 or 2.

Examples of metal components of such organophosphate metal salts include:
Alkali metals such as Li, Na, and Mg.

Examples include alkaline earth metals such as Ca, Sr, and Ba, and Zn.

Examples of alkyl groups include methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, sec-butyl, tertiary
Butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl,
2-Catylhexyl, decyl, isodecyl, lauryl,
Tridecyl, 0 + z-+ x /l alkyltyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl and the like can be mentioned.

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

Examples of alkylaryl groups include tolyl, xylyl, ethylphenyl, butylphenyl, tert-butylphenyl,
Examples include octylphenyl, isooctylphenyl, tertiary 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, or methyl, ethyl, isopropyl, butyl, isobutyl, hexyl,
Cyclohexyl-, phenyl cellosolve residue M: methyl-, ethyl-, isopropyl-, butyl-, isobutylcarpitol residue-i;) Liethylene glycol monomethyl ether, -monoethyl ether, -motsbutyl ether residue; glycerin 1,2 -dimethyl ether, -1,
3-dimethyl ether, -113-diethyl ether,
-1-ethyl-2-propyl ether residue; examples include nonylphenoxypolyethoxyethyl and lauroxypolyethoxyethyl groups.

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

Examples of nitrogen-containing nonmetallic stabilizers include urea, melamine, α
-phenylindole, diphenylthiourea, 1,4-
Examples include butanediol aminocrotonic acid ester.

Examples of antioxidants include 2,6-di-t-butyl-p-
Cresol, 2,5-di-t-butylhydroquinone,
2.2'-methylene-bis-(4-methyl-5-t-butylphenol), 4.4'-thiobis-(6-t-butylphenol), 4.4'-thiobis-(6-L-butyl- m-cresol), octadecyl 3-(3',5
'-di-t-butyl-4'-bitroxyphenol) propionate, pentaerythrityl-tetrakis (3-
(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate] and the like.

Examples of light stabilizers include 2-hydroxy-4-octoxybenzophenone, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, ethyl-2-cyano-3,3-diphenylacrylate, bis(2'-hydroxy-5-methylphenyl)benzotriazole, ,2,6
, 6-tetramethyl-4-piperidine) sebacate, 2
, 4-di-tert-butylphenyl-3', 5'-diter-butyl, 4'-hydroxyhenzoate, and the like.

Examples of the β-diketone compound include dibenzoylmethane, steacylbenzoylmethane, balmitoylbenzoylmethane, and metal salts of these β-diketone compounds.

Examples of epoxy compounds include 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 flower oil, epoxidized linseed oil fatty acid butyl, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexane diepoxide, dicyclopentadiene dieboxide, 3,4-epoxycyclohexyl-6-
Examples include methylnipoxycyclohexanecarpoxylate.

Examples of organotin compounds include dibutyltin laurate, dioctyltin laurate, dibutyltin maleate, dioctyltin maleate, dibutyltin mercaptoacetate, monobutyltin mercaptoacetate, dibutyltin isooctylthioglycolate, and monobutyltin isooctylthioglycolate. , dioctyltin mercaptoacetate, monooctyltin mercaptoacetate, dioctyltin isooctylthioglycolate, monooctyltin isothioglycolate, and the like. In addition to the above-mentioned conventional additives, plasticizers, pigments, fillers, foaming agents, antistatic agents, antifogging agents, anti-flate-out agents, surface treatment agents, lubricants, flame retardants, etc. may be added as necessary. It doesn't matter what you add.

(e) Synthesis Examples-Examples The gist of the present invention will be specifically explained below using synthesis examples and examples. However, the present invention is not limited to these synthesis examples and examples.

Synthesis Example-1 Hydrotalcite Compound Chemical Formula % Formula % -4A Kyowa Chemical Industry Co., Ltd.) 50.7 g (0
, 1 mol) into a beaker equipped with a stirrer, and while stirring, add 200 ml of an aqueous solution of 10 g (0.1 mol) perchloric acid.
l (add several drops of nonionic surfactant in advance)
Drip. After the addition is complete, stirring is continued for approximately 1 hour until no carbon dioxide gas is generated. After drying the product under reduced pressure to remove most of the moisture, it is further dried at 80° C. for 10 hours. Chemical analysis etc. revealed that the composition of the obtained product was approximately M
ga, 5A1z(OH>rzccOs). , s(C10
4)・It was 3.5H20.

Synthesis Example-2 Synthesis example of hydrotalcite compound containing Mg h Zn and adjustment of mixed product with perchloric acid Mg (NO3) z into a beaker equipped with a stirrer and a pH electrode
・6Hz0 25.6 g (0.1 mol) and Zn(N
O□)z ・68zO6,95g (0,02 mol)
, further A l (N(h)i・9H2015,Og (
0.04 mol) dissolved in 200 mN of pure water,
2.1 g (0.0198 mol) of NazCO+ and 12.8 g (0.32 mol) of NaOH were added to 20 g (0.32 mol) of pure water.
When the pi of the liquid is 10.
Drop the mixture while adjusting the flow rates of both so as to maintain the flow rate between 0 and I1.0.

After the reaction was completed, the precipitate was filtered off and dried at 80°C for 10 hours. The obtained sample was found to be Mg5ZnA by metal analysis etc.
It was l 2 (OH) lb .CO3.48zO.

While stirring 64.5 g (0.1 mol) of the above product in a beaker, 15.1 g (0.15 mol) of perchloric acid was added to 2
00m/! , diluted with water, was added dropwise and mixed thoroughly. The product was dried under reduced pressure to remove most of the moisture, and then further dried at 80° C. for 10 hours.

The obtained product had approximately the following composition.

Mg5ZnAI! 2(OH)+6・(CO3)o,zs
(Cj!Oa) +, s ・4HzO By the same operation, samples of mixed products with different molar ratios of perchloric acid were prepared, and trial samples of mixed products as shown in Table 1 were obtained. Ta. For comparison, the composition of a sample of a hydrotalcite compound that was not treated with perchloric acid is also shown in Table 1.

Example 1 In order to examine the effect of the resin composition according to the present invention, a test sheet having a thickness of 0.5*s was prepared using a blend 1 and a blend 2 shown below using a kneading roll at 170°C. Thermal stability at 180°C was investigated using a gear set aging tester. Evaluation of thermal stability was expressed by the time taken for the test piece to turn black. Thermal colorability evaluation was 5 from the test sheet.
A test piece with a size of cm x 5 cm was cut out, several pieces were stacked on top of each other, and the degree of coloring was visually determined after press molding at 190°C for 5 minutes. The results are shown in Table 2.

However, the evaluation numbers for thermal colorability are 1: White 2; light yellow 3: Yellow, 4: Yellowish brown to reddish brown 5: Black represents.

Blend 1 Vinyl chloride resin 60 parts by weight Polyurethane resin 40 parts by weight Ba-lysyllate 0.5 parts by weight Zn-stearate 0.5 parts by weight Sample (Table 2) Blend 2 Vinyl chloride urethane 100 parts by weight Copolymer resin Ba-stearate 1.0 parts by weight Zn-octoate 0.5 parts by weight
(Table 2) Example-2 When the composition of the present invention is used in combination with one or more conventional additives that are normally used as stabilizer components for chlorine-containing resins, further improvement effects can be obtained. was gotten. Using the following formulations 3 and 4, the synergistic effect with the combined stabilizer was investigated in the same manner as in Example 1. The results are shown in Table 3.

Blend 3 Vinyl chloride resin 50 parts by weight Polyurethane resin 50 parts by weight Ba-phenate 0.5 parts by weight Zn-stearate 1.0 parts by weight Material B 005 parts by weight Concomitant stabilizer Table 3 Blend 4 Vinyl chloride urethane Polymer resin 100 parts by weight Ca-stearate 0.5 parts by weight Zn-stearate 1,0 parts by weight Method Material D
0.5 parts by weight stabilizer
Table 3 (f) Effects of the Invention As is clear from the results of Example 1, by blending the mixed product of the present invention, thermal Significant improvements in stability and heat coloring prevention were observed.

In Example 2, by using the mixed product of the present invention and one or more types of conventional additives, an excellent synergistic effect was obtained in the composition of the present invention in terms of long-term thermal stability and heat discoloration prevention properties. recognized between things. Therefore, the present invention provides a resin composition with extremely high commercial value.

Claims (1)

[Claims] A polymer blend of a chlorine-containing resin and a urethane resin or a copolymer resin of a chlorine-containing resin and a urethane resin, and a hydrotalcite compound whose metal component is Mg or Al, or a hydrotalcite compound whose metal component is Mg, Zn, or Al. A chlorine-containing urethane resin composition, characterized in that a mixed product of one or two hydrotalcite compounds selected from site compounds and perchloric acid is added.