JPS6043860B2 - Polyvinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-toxic or low-toxic polyvinyl chloride resin composition.

More specifically, the present invention provides polyvinyl chloride resin with (
The present invention relates to a stabilized polyvinyl chloride resin composition containing a) a metal salt of an organic monocarboxylic acid, (b) an organic phosphite metal salt, and (c) an epoxy compound. In general, halogen-containing resins have poor stability against heat and light, and are prone to thermal decomposition mainly due to dehydrohalogenation during hot molding, resulting in a decrease in the mechanical properties of processed products. It has the disadvantage of causing deterioration of color tone and causing significant disadvantages.

In order to avoid such disadvantages, it is necessary to add one or more kinds of heat stabilizers to the synthetic resin to suppress deterioration during processing steps. Many metal soaps have been used for this purpose, and generally satisfactory results have been obtained in terms of thermal stability. However, the use of these metal soaps, especially cadmium soaps and lead soaps, poses serious toxicity problems. However, the thermal stability is still inferior to that obtained when using cadmium soap or lead soap, and at the same time there are certain drawbacks that do not satisfy the technical issues as a stabilizer. It cannot be said that it is sufficient to make this happen. For example, the combination of a metal soap such as calcium, zinc, magnesium or barium with a polyhydric alcohol, diphenylthiourea or trisnonylphenyl phosphite has an insufficient stabilizing effect and is not suitable for practical use. Although the combination of the metal soap and epoxidized soybean oil has a certain degree of heat stabilizing effect, it has the disadvantage of lowering the softening point during hard compounding.

Furthermore, aminocrotonic acid esters have very poor compatibility with halogen-containing resins, and their effects are particularly insufficient for vinyl chloride resins obtained by suspension polymerization. On the other hand, especially when the processed product is used as a food packaging material, various formulations of non-toxic stabilizers have been considered, and the resulting desirable properties have led to their wide use as food packaging materials, but they are still insufficient and cannot be utilized. There are quite a number of areas where there is no such thing.

In particular, with recent advances in processing technology for halogen-containing resins, many food packaging materials, food containers, etc. have appeared on the market, and at the same time, there is a demand for excellent non-toxic stabilizers that prevent thermal decomposition during molding processing at high temperatures. There is a need for something that is strong and can withstand the harsh working conditions of all types of molding processes. In order to meet this demand, less toxic dioctyltin stabilizers have been developed and put into practical use, but problems remain in long-term workability in molding processes. The properties that non-toxic stabilizers must have in the field of molding and processing food packaging materials include exhibiting sufficient stabilizing effects with a small amount of stabilizer, as well as having very good compatibility with resins and low migration. 、Ru.

Further, when using the calender roll method as an example, a blade-out phenomenon occurs on the surface of the calender roll, which impairs the shape of the surface of the molded product and significantly reduces processing efficiency.

This plate-out phenomenon is observed to a lesser extent in processing steps other than the calender roll method, and is a drawback when halogen-containing resins are stabilized using metal soaps. For this reason, the inventors of the present invention have conducted repeated research to solve the drawbacks associated with conventional stabilizers by using metal soaps other than cadmium and lead, and have found that they have excellent stability against deterioration due to light and heat. We have succeeded in developing a stabilizer with very low toxicity. That is, the present invention uses polyvinyl chloride; Stabilization characterized by adding (a) a zinc salt of an organic tetraorganic monocarboxylic acid, (b) an organic phosphite metal salt represented by the following general formula [1], and (c) an epoxy compound to the resin. The present invention provides a polyvinyl chloride resin composition.

(In the formula, R1 represents an alkyl or arylalkyl group, R2 and R3 represent an alkyl, arylalkyl, aryl or alkylaryl group, and R4 represents an aryl or alkylaryl group.

M is Ca. ．． Mg. Indicates a Ba or Sr metal atom. )
The composition of the present invention having the above characteristics will be described in detail below.

Examples of the carbonic acids constituting the zinc salt of organic monocarboxylic acid used in the present invention include hydrofuronic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid, linoleic acid, Linoleic acid, neoacid, oleic acid, stearic acid, isodecanoic acid, isostearic acid, 12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, brassic acid and Similar acids and mixtures of the above naturally occurring acids such as animal fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, p-
t-butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, xylylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid,
Examples include monobutyl maleate, monodecyl phthalate, and cyclohexane carboxylic acid.

The amount of zinc salt of these carboxylic acids added is as follows: resin 1 (4)
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
It is 1 to 3 parts by weight.

Further, examples of the alkyl group constituting the metal salt of the organic phosphite represented by the general formula [1] include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Sec-butyl, tertiary-butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, Cl.

~15 mixed alkyl, stearyl, cyclopentyl, 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, γ-phenylpropyl, β-phenylpropyl, and the like. Examples of alkylaryl groups include tolyl, xylyl, ethylphenyl, butylphenyl, tert-butylphenyl, octylphenyl, isooctylphenyl, tertiary-octylphenyl, nonylphenyl, and the like.

Typical examples of the metal salts of organic bossite represented by the general formula [1] are as follows.

Tris (tridecyl) phenyl diphosphite? salt,
Tris (tridecyl) ◆ Phenyl diphosphite Ca salt, Tris (tridecyl) ● Phenyl diphosphite Mg
Salt, bis(tridecyl◆phenylphosphite)? salt,
Bis(2-ethylhexyl phenylphosphite) B
a salt, tris (isodecyl) ● phenyl diphosphite? Salt, bis(2-ethylhexyl◆phenylphosphite) Ca salt, tris(tridecyl)●phenyldiphosphite Sr salt, butyl◆triphenyldisphite? salt, butyl triphenyl diphosphite Mg salt, bis(
benzyl, phenyl phosphite) Ba salt, bis(cyclohexyl ◆ phenyl phosphite) Ba salt, bis (isooctyl ◆ nonylphenyl phosphite) Ba salt, bis (lauryl ◆ octylphenyl phosphite) Ba salt, bis (isodecyl ● isopropylphenyl) ) Mg salt,
Bis(isodecyl phenylphosphite) S lie, tridecyl triphenyl diphosphite Sr salt, bis(2
-Ethylhexyl●Phenylphosphite) S Lie.

The organic phosphite metal salt in the present invention as described above is, for example, an alkali metal salt of an alkyl aryl acid phosphite and a Ca. ．． Mg. ．． By reaction with halides or fatty acid salts of Bai or Sr, dialkyl◆
Monoarylphosphite and Ca,. Mg. ．． It can also be easily produced by reacting a fatty acid salt of Ba or Sr.

The amount of these organic phosphite metal salts added is 0.01 to 3 parts by weight, preferably 0.1 to 1 part by weight, per 10 parts by weight of the resin.
．． 5 parts by weight. Further, the epoxy compound that can be used in the present invention is an organic compound containing at least one epoxy group, and any epoxy compound can be used.

Such compounds may also include those of aliphatic, aromatic or alicyclic nature, and therefore those having aromatic, heterocyclic and alicyclic groups may also be present.

Typical epoxy compounds include epoxy carboxylic acids such as epoxy stearic acid, triglycidyl glycerin, diglycidyl ether of diethylene glycol, glycidyl epoxy stearyl ether, and 1,4-bis(2◆3
-epoxypropoxy)benzene, 4●4″-bis(
2●3-epoxypropoxy)diphenyl ether,
1●8-vinos(2●3-epoxypropoxy)octane, 1,4-bis(2●3-epoxypropoxy)cyclohexane and 1●3-bis(4●5-epoxybentoxy)-5-chlorobenzene Gly, cidyl ethers of polyhydric alcohols and polyhydric phenols such as, and polyhydric phenols such as resorcinol, catechol, hydroquinone, methylresorcinol or 2●
2-bis(4″-hydroxyphenyl)propane [bisphenol A], 2,2″-bis(4″-hydroxyphenynol)butane, 4●4′-dihydroxybenzophenone and 1●5-dihydroxy Epoxy ethers of polyhydric phenols obtained by the reaction of polynuclear phenols such as naphthalene with halogen-containing epoxides or dihalohydrins such as 3-chloro-1,2-epoxybutane, 3-chloro-1,2-epoxyoctane and epichlorohydrin. Epoxy esters can also be used as the epoxy compound of the present invention, but such epoxy esters are initially unsaturated in the alcohol or acid part of the molecule, and epoxy groups are formed in this part, resulting in saturation. It is what was done.

Representative unsaturated acids include acrylic acid, oleic acid, linoleic acid, linolenic acid, euricic acid, ricinoleic acid, and brassic acid, and these acids can be esterified with organic monohydric or polyhydric alcohols. Representative monohydric alcohols include butyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, octyl alcohol, isooctyl alcohol, stearyl alcohol and oleyl alcohol, with octyl alcohol being particularly preferred. Typical polyhydric alcohols include pentaerythritol, glycerol, ethylene glycol, 1●2-propylene glycol, 1●4-butylene glycol, neopentyl glycol, ricinoleyl alcohol, erythritol, mannitol, and sorbitol. is particularly preferred. Some or all of the hydroxyl groups of these alcohols form epoxidized acids and esters. Examples of these epoxidized esters include epoxidized 1,4-butylene glycol diacrylate and epoxidized pentaerythritol tetratolate. Epoxidized mixtures of higher fatty acid esters of naturally occurring oils can also be used, such as epoxidized soybean oil, epoxidized cottonseed oil, epoxidized tall oil fatty acid esters, epoxidized coconut oil, and epoxidized tallow oil. Among these, epoxidized soybean oil is preferred. In the epoxy ester used in the present invention, the alcohol may contain an epoxy group, and the alcohol may have a long or short chain, and the acid may have a correspondingly short or long chain, such as epoxy stearyl acetate, stearin, etc. Acid epoxy stearyl, glycidyl stearate and glycidyl methacrylate can be esters.

. Other epoxy compounds of the present invention include tris(epoxypropyl)isocyanurate and epoxidized polybutadiene. The amount of these epoxy compounds added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 10 parts by weight of the resin.

In carrying out the present invention, these stabilizers used for stabilizing polyvinyl chloride resin ((a) to (c)
The total amount of components) added is 1 to 100 parts by weight of the resin.
1 part by volume, preferably 2 to 6 parts by weight.

The polyvinyl chloride resin composition of the present invention may contain a phthalate ester plasticizer, other ester plasticizer, polyester plasticizer, phosphate ester plasticizer, chlorine plasticizer, or other plasticizer depending on the use. It can be used as appropriate.

Adding an antioxidant to the polyvinyl chloride resin composition of the present invention can increase the oxidative deterioration prevention properties of the polymer composition, so it can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, sulfur compounds, and the like. If an ultraviolet absorber is added to the polyvinyl chloride resin composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates, especially nickel or chromium salts or xylates, triazine types, and the like. Furthermore, in order to obtain a non-toxic polyvinyl chloride resin, a non-toxic polyvinyl chloride resin composition which is non-toxic and has good thermal stability can be obtained by selecting and using a non-toxic one from among the above-mentioned commonly used metal soaps. Others as necessary, such as organic chelators, keto acid compounds, pigments,
Fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, anti-mold agents,
Bactericides, metal deactivators, photodegradants, non-metal stabilizers,
Borate esters, thiourea derivatives, processing aids, mold release agents, reinforcing agents, and the like can be included. Examples of the polyvinyl chloride resin stabilized in the present invention include polyvinyl chloride resin, and polyvinyl chloride resin and α-
Olefin polymers or polyolefins such as ethyne-vinyl acetate copolymer, ethylene-propylene copolymer and their copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene,
Examples include copolymers with acrylonitrile (such as acrylonitrile), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and blends with methacrylic ester-butadiene-styrene copolymers.

The following Examples show the effects of the polyvinyl chloride resin composition of the present invention, but the present invention is not limited by these Examples.

Example 1 In order to see the effect of the stabilizer system of the present invention, a sheet with a thickness of 1 Tr$L was prepared using a kneading roll according to the following formulation.
We conducted a performance test.

The results are shown in Table 1 below. Blend> PVC (GeOnlO3EP) 10 parts DOP2O stearic acid
0.2 Stabilizer (Table 1) Table 1 Example 2? In the -Zn system, performance tests were conducted in the same manner as in Example 1, using the following formulations and changing the types of Ba salts.

The results are shown in Table 2 below. <Composition> PVC (GeOnlO3EP) 10 parts DOP5O hostearic acid
0.3 epoxidized soybean oil
2.0 Toluic acid ZnO. 7omi salt (Table 2) Nonylphenol? The metal content was adjusted to 1.1 parts by weight of salt.

Example 3 Various epoxy compounds were used with different types according to the following formulation.
A performance test was conducted in the same manner as in Example 1.

The results are shown in Table 3 below. <Composition> PVC (GeOnlO3EP) 10 parts DOP5O stearic acid
0.3 toluic acid ZnO. 7 Tris(isooctyl)phenyl diphosphite Ca salt 1.4 Epoxy compound (Table 3) 0.5 Example 4
In order to examine the effect of using other stabilizing aids in combination with the composition of the present invention, a performance test was conducted in the same manner as in Example 1 using the following formulation.

The results are shown in Table 4. <Composition> PVC (GeOnlO3EP) 10 parts DOP48 epoxidized soybean oil
2.0.Octylic acid ZnO. 2 Tris (tridecyl)
Phenyl Jiho

Claims (1)

[Claims] 1. Adding (a) a zinc salt of an organic monocarboxylic acid, (b) an organic phosphite metal salt represented by the following general formula [I], and (c) an epoxy compound to a polyvinyl chloride resin. A stabilized polyvinyl chloride resin composition comprising: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R
_1 represents an alkyl or arylalkyl group, R_
2 and R_3 represent an alkyl, arylalkyl, aryl or alkylaryl group, and R_4 represents an aryl or alkylaryl group. M represents a Ca, Mg, Ba or Sr metal atom. )