JPS6320263B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to non-toxic and low toxicity chlorine-containing resin compositions. More specifically, the present invention provides a stabilized chlorine-containing resin obtained by adding an organic phosphite compound derived from a 2,6-di-tertyabutylphenol and an aliphatic alcohol having an ether group to a chlorine-containing resin. Regarding the composition. In general, vinyl chloride resins have poor stability against heat and light, and are susceptible to thermal decomposition mainly due to dehydrochlorination during hot molding, resulting in decreased mechanical properties and color tone of processed products. It has drawbacks that cause 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. Although a certain degree of thermal stability has been achieved, the thermal stability is still inferior to that when using cadmium soap or lead soap, and at the same time it has certain drawbacks and does not satisfy the technical issues as a stabilizer. It's not enough to make it happen.
For example, when agricultural vinyl chloride resin is formulated with a non-Cd and non-Pb system, it is usually used in combination with an organic phosphite compound because its thermal stability and weather resistance are extremely poor. phosphite, diphenyl phosphite, diisodecyl monophenyl phosphite, tridecyl phosphite, tetraalkyl phosphite,
Organic phosphites such as bisphenol A diphosphite are effective in improving initial coloration, but their effects on improving thermal coloration and weather resistance are small, and their water resistance is poor, making them insufficient for practical use. Further, a combination of a metal soap and an epoxy compound has a certain degree of heat stabilizing effect when added in a large amount, but has the disadvantage of causing a whitening phenomenon. In particular, recently, with advances in processing technology for chlorine-containing resins, many food packaging materials, food containers, etc. have appeared on the market. There is a strong demand for products that can withstand the harsh working conditions of all types of molding processes. In order to meet this demand, a less toxic dioctyltin stabilizer has been developed and put into practical use, but problems remain in long-term workability during molding. For this reason, it has been proposed to use a combination of various stabilizing aids, but the combinations proposed so far still have insufficient effects and require further improvement. In other words, the combinations conventionally used, such as the combination of metal soap, epoxy compound, and organic triphosphite, have a relatively large effect on thermal stability and coloring properties, but have a small effect on weather resistance; It has also been proposed to use diphenyl phosphite in combination, but this is effective to some extent in preventing discoloration, but it has poor long-term thermal stability and weather resistance, and is highly susceptible to plate-out, making it insufficient for practical use. It was hot. As a result of repeated research to solve the above-mentioned drawbacks associated with conventional stabilizers, the present inventors have developed a stabilizer system that has excellent stability against deterioration due to light and heat and has very low toxicity. succeeded in developing. That is, in the present invention, an organic phosphite compound represented by the following general formula [] is added to a chlorine-containing resin. A chlorine-containing resin composition is provided. (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms,
R ₂ represents a divalent hydrocarbon group, R ₃ represents alkyl,
It represents an aryl, alkylaryl or arylalkyl group, R ₄ represents R ₃ (-OR ₂ --) _n , an alkyl, aryl, alkylaryl or arylalkyl group, and m represents a positive integer. ) Specific examples of the alkyl group represented by R ₁ in the above general formula [] include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec
-butyl and t-butyl. Examples of the divalent hydrocarbon group represented by _R2 include ethylene, 1,2-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene,
Examples include 1,4-butylene, pentylene, and 1,2-dodecene. Examples of the alkyl group represented by R ₃ or R ₄ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl. , isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, _C12-15 mixed alkyl, stearyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl, and the like. Examples of the aryl group represented by R ₃ or R ₄ include phenyl, naphthyl, and the like. Examples of the arylalkyl group represented by R ₃ or R ₄ include benzyl, β-phenylethyl,
Examples include γ-phenylpropyl and β-phenylpropyl. Examples of the alkylaryl group represented by R ₃ or R ₄ include tolyl, xylyl, ethyl phenyl, butylphenyl, tert-butylphenyl, octylphenyl, isooctyl phenyl, tertiary octylphenyl, nonylphenyl, dinonylphenyl, 2 , 4-di-tert-butyl phenyl, 2,6-di-tert-butyl-4-methylphenyl, and the like. Although m is not particularly limited, m is particularly preferably from 1 to 5. Next, specific examples of the organic phosphite compounds represented by the general formula [] are shown in Table 1 below. However, the organic phosphite compound used in the present invention is not limited to the following compounds. The amount of the organic phosphite compound added is not limited, but preferably chlorine-containing resin
0.001 to 10 parts by weight can be used per 100 parts by weight,
More preferably, 0.05 to 5 parts by weight can be used. The organic phosphite compounds represented by the above general [] used in the present invention are, for example, React the phenol shown by with phosphorus trichloride,
Next, a compound represented by R ₃ (-OR ₂ -) _n OH and
Compounds represented by R ₄ OH (provided that R ₄ is

[Formula]) or by reacting triphenyl phosphite or trimethyl phosphite in place of phosphorus trichloride. Also,

[Formula] or X ₂ P―O― ₍ ―R ₂ O―) _n R ₃ (However,

[Formula] is shown, and R ₄ is

[Formula] (not) and R ₄ OH. Next, a specific example of synthesis of an organic phosphite compound will be shown. Synthesis example: 2,6-di-t-butyl-4-methylphenyl bis(butoxyethoxyethyl) phosphite (Compound No. 1 in Table 1). 2,6-di-t-butyl-4-methylphenol 11.02g (0.05mol) and triethylamine 6.10g
(0.06 mol) was dissolved in 50 ml of chloroform.
Add 6.88 g (0.05 mol) of phosphorus trichloride to this solution at room temperature.
After dropwise addition, the mixture was reacted at 50° C. for 9 hours under a N ₂ stream. Then, 16.2 g (0.1 mol) of butyl carbitol
A mixed solution of 10.17 g (0.1 mol) of triethylamine and 10.17 g (0.1 mol) of triethylamine was added dropwise, and the mixture was reacted at 50° C. for 3 hours under a N ₂ stream.
After the reaction, chloroform was distilled off and the generated N
(C ₂ H ₅ ) ₃ HC1 was removed by dispersing it in toluene and then filtering it. Next, 2,6-di-
t-Butyl-4-methylphenyl bis(butoxyethoxyethyl) phosphite was obtained as a pale yellow viscous liquid. Examples of chlorine-containing resins used in the present invention include the following. For example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer,
Vinyl chloride - propylene copolymer, vinyl chloride -
Styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer,
Vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-
Chlorine-containing synthetic resins such as acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, or these resins and α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and their copolymers, polystyrene, Vinyl acetate, acrylic resin, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile, butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, Examples include blends with methacrylic acid ester-butadiene-styrene copolymers, block copolymers, and graft copolymers. The composition according to the invention usually contains a zinc organic acid salt and a group a metal organic acid salt. Carboxylic acids constituting the metal salt of an organic acid to be blended into the composition of the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid, linoleic acid, and linoleic acid. acids, neodecanoic acid, 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 tallow 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, pt-butylbenzoic acid ,5
-t-octylsalicylic acid, naphthenic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid,
Examples include di-t-butylbenzoic acid, bromobenzoic acid, monobutyl maleate, monodecyl phthalate, and cyclohexanecarboxylic acid. Phenols are also useful as organic acids.
For example, phenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, cyclohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethylphenol, poly(di-
penta)isopropylphenol, diisopropyl-m-cresol, butylphenol, isoaluminphenol, isooctylphenol, 2-
Ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-t-octylphenol, di-t-nonyl Examples include phenol and di-t-dodecylphenol. Metal components include zinc and Group A metals such as barium, calcium, magnesium and strontium. The amount of these metal salts added is 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the resin. When the composition of the present invention is further combined with an epoxy compound, an excellent synergistic effect is exhibited. The epoxy compound used in the present invention is Araldite 502 (manufactured by Ciba Gaiki Co., Ltd.; epoxy equivalent
233-250), Araldite 508 (400-455), Epicron 850 (Dainippon Ink Chemical; 184-194),
Epicron 830 (same; 170-190), Epicort 828
(manufactured by Ciel; 181-194), Epicote 834 (manufactured by Ciel;
230-270), Sumiepoxy ELA128 (manufactured by Sumitomo Chemical;
184-194), EP-4100 (Asahi Denka; 180-200), bisphenol type epoxy resin DEN431 (Dow; epoxy equivalent 172-179), DEN438 (Asahi Denka;
175-182), Epiclon N-740 (Dainippon Ink Chemical; 170-190), Epiclon N-680 (Dainippon Ink Chemical; 220-
240), CIBA EPN 1139 (Ciba Geigy: 172~
179), (Novolac type epoxy resin such as IBA ECN 1273 (same = about 225), 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, -stearyl, 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,
Examples include epoxy compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate. The amount of these epoxy compounds added is 100% of the resin.
0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight
It is 5 parts by weight. It goes without saying that other additives may be added to the composition of the present invention to further improve its performance; examples of these other additives include other metal soaps, plasticizers, and antioxidants. , light stabilizer, crosslinking agent, filler, epoxy stabilizer, infrared absorber,
Pigments, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, fungicides, photodegradants, nonmetallic stabilizers, processing aids, mold release agents Agents and the like can be included. Next, the effects of the present invention will be specifically explained with reference to Examples. However, the invention is not limited to the examples listed below. In addition, the plate-out property in the table for each example is determined by the watching-red method.
Shown in ppm. Example 1 In order to examine the stabilizing effect of the composition of the present invention, the organic phosphite compounds listed in Table 2 were added to the following formulation, and a sheet with a thickness of 1 mm was prepared using a kneading roll.
A thermal stability test at 190°C, transparency, initial coloring, plate-out property, and lead property were tested. At the same time, a weather resistance test was conducted using a weather meter. The results are shown in Table 2 below. <Formulation> Polyvinyl chloride (Vinica 37H) 100 parts by weight Di-2-ethylhexyl phthalate 45 Tricresyl phosphate 3 Epoxidized soybean oil 2.0 Zn-stearate 0.8 Ba-stearate 0.4 Ba-nonyl phenate 0.5 Sorbitan monopalmitate 3.0 Methylenebisstearylamide 0.3 Organic phosphite compounds (Table 2) 0.3

【table】

[Table] * + With bleed - Without bleed Example 2 Next, the same test as in Example 1 was conducted by changing the type of organic phosphite compound according to the formulation. The results are shown in Table 3. <Formulation> Polyvinyl chloride (Vinicron 400M-3)
100 parts by weight Di-2-ethylhexyl phthalate 45 Trixylinyl phosphate 5 Epicote 828 3 Zn-laurate 0.5 Ca-stearate 1.0 Mg-octoate 0.3 Ethylene bisstearylamide 0.3 Sorbitan monostearate 2.5 Organic phosphite compounds (Table 3) 0.4

[Table] Example 3 In order to examine the stabilizing effect of the combination of the present invention, a sheet with a thickness of 1 mm was prepared using a kneading roll using the following formulation, and a heat deterioration test and an initial coloring test were conducted at 190°C. Ta. The results are shown in Table 4 below. <Composition> PVC (Geon 103 EP) 100 parts by weight Dioctyl phthalate 48 Epoxy compound (Table 4) 2 Ca-stearate 1.0 Zn-stearate 0.2 Organic phosphite compound No. 1 (Table 1)
0.4 * However, initial coloring and thermal coloring indicate yellowness measured by Hunter colorimeter.

[Table] Example 4 A test was conducted in the same manner as in Example 3 using the following hard formulation. A plate-out property test was also conducted. The results are shown in Table 5. <Composition> PVC (Geon 103EP-8) 100 parts by weight Epoxidized linseed oil 1.0 Organic phosphite compound (Table 5) 0.5 Mg-stearate 0.2 Ca-stearate 1.0 Zn-stearate 0.4

【table】

[Table] Example 5 In order to see the effect of PVC-MBS primer blend, a sheet was made by blending, and 190
A thermal stability test at ℃ and an initial coloring test were conducted. The results are shown in Table 6. <Composition> PVC (Geon 103 EP-8) 100 parts by weight MBS (methyl methacrylate-butadiene-styrene polymer) 10 Epoxidized soybean oil 1.0 Stearic acid 0.3 Zn-toluate 0.4 Ba-nonyl phenolate 0.7 Organic phosphite compound (No. 6 Table) 0.3

【table】

【table】

Claims (1)

[Scope of Claims] 1. A chlorine-containing resin composition obtained by adding an organic phosphite compound represented by the following general formula [] to a chlorine-containing resin. (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms,
R ₂ represents a divalent hydrocarbon group, R ₃ represents alkyl,
It represents an aryl, alkylaryl or arylalkyl group, R ₄ represents R ₃ (-OR ₂ --) _n , an alkyl, aryl, alkylaryl or arylalkyl group, and m represents a positive integer. )