JPS6411065B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a halogen-containing resin composition in which the generation of spots is suppressed, and more specifically, an organic acid metal salt, an epoxy resin, a specific organic phosphite compound, an antifogging agent, and an alkanolamine are added to the halogen-containing resin. The present invention relates to a halogen-containing resin composition that has excellent thermal stability, thermal colorability, and transparency, and in particular suppresses the occurrence of lumps. In general, halogen-containing resins have poor stability against heat and light, and are prone to thermal decomposition mainly due to dehydrohalogenation during thermoforming processing, resulting in decreased mechanical properties and color tone of processed products. It has the disadvantage of causing deterioration of the environment and causing significant disadvantages. In order to avoid such disadvantages, lead, barium, calcium, cadmium, magnesium,
Almost satisfactory results in terms of thermal stability have been obtained by blending various combinations of combination soaps such as zinc, organic tin compounds, organic phosphite compounds, epoxy compounds, etc. However, cadmium, lead compounds, etc. are highly toxic, and their use is currently largely restricted. Therefore, methods have been considered in which a non-toxic or low-toxic metal compound and a non-metal stabilizer are combined in a system that does not use cadmium or the like in order to achieve a synergistic effect. However, although such a method provides a certain degree of thermal stability, the effect is insufficient. In particular, for agricultural vinyl chloride resin, its antifogging property is an important factor for crop growth, and the addition of an antifogging agent is required. Since it is known that the stability of the stabilizer is reduced, there has been a strong demand for the development of a more effective stabilizer. In conventionally used combinations, such as combinations of organic acid metal salts, epoxy compounds and organic phosphite compounds, epoxidized soybean oil,
If a large amount of epoxidized vegetable oil such as epoxidized linseed oil is used, a bleeding phenomenon occurs and the surface of the molded product becomes sticky, making it impossible to obtain a substantial product. Therefore, if a bisphenol A/glycidyl ether type epoxy resin is used, a product with less bleeding and good heat resistance even if used in a large amount can be obtained. However, there was a major drawback in that a lump phenomenon occurred several months after the molding process, which impaired the commercial value of the molded product. In addition, as organic phosphite compounds, phosphite compounds and pentaerythritol diphosphite compounds that have an ether group in their molecules have good thermal stability and coloring properties, but when used together with epoxy resins, the above-mentioned problems occur. In practice, it could not be used in combination with epoxy resin because it promotes generation. The present inventors investigated additives to prevent the formation of these lumps, and found that the addition of alkanolamines significantly suppressed the formation of lumps, and also significantly improved thermal stability, coloring properties, etc. It has been found that a significantly improved halogen-containing resin composition can be obtained. That is, in the present invention, based on 100 parts by weight of the halogen-containing resin, (a) at least one kind of organic acid metal salt, 0.1
~5 parts by weight, (b) 0.1 to 5 parts by weight of epoxy resin, (c)
Contains 0.005 to 1.5 parts by weight of alkanolamines, (d) 0.01 to 5 parts by weight of at least one antifogging agent, and (e) 0.01 to 5 parts by weight of at least one phosphite compound or pentaerythritol diphosphite compound having an ether group. The object of the present invention is to provide a halogen-containing resin composition that has excellent thermal stability, thermal colorability, and transparency, and is particularly inhibited from generating lumps. The composition of the present invention having the above characteristics will be described in detail below. Examples of the carboxylic acids constituting the metal salt of an organic acid used in the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid, linoleic acid, linoleic acid, 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, pracidic acid and similar acids and naturally occurring mixtures of the above 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 −
Examples include t-octylsalicylic acid, naphthenic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid, monobutyl maleate, monodecyl phthalate, cyclohexane carboxylic acid, and the like. 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-venta) Isopropylphenol, diisopropyl-m-cresol, butylphenol, isoamylphenol, isooctylphenol, 2
-Ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-t-octylphenol, di-t- Examples include nonylphenol and di-t-dodecylphenol. Metal components include zinc and Group A metals such as lithium, sodium, potassium, and Group A metals such as barium, calcium, magnesium, and strontium. The amount of these metal salts added is 0.1 to 5 parts by weight per 100 parts by weight of the resin. The epoxy resin used in the present invention is obtained by the reaction of polyhydric phenols with epichlorohydrin or methylepichlorohydrin, and bisphenol type and novolac type epoxy resins are particularly preferred. Examples of bisphenol type epoxy resins include Araldite 502 (manufactured by Ciba Geigy; epoxy equivalent: 233 to 250), Araldite 508 (manufactured by Ciba Geigy; epoxy equivalent: 233 to 250),
Epicron 850 (Dainippon Ink Chemical; 184-194),
Epicron 830 (same; 170-190), Epicort 828
(manufactured by Ciel; 184-194), Epicote 834 (manufactured by Ciel;
230-270), Sumiepoxy ELA128 (manufactured by Sumitomo Chemical;
184-194), EP-4100 (manufactured by Asahi Denka; 180-200), and examples of novolak type epoxy resin include DEN431 (manufactured by Dow Corporation; epoxy equivalent 172-200).
179), DEN438 (same; 175-182), Epicron N-
740 (manufactured by Dainippon Ink Chemical; 170-190), Epicron N-680 (manufactured by Dainippon Ink Chemical; 220-240), CIBAEPN1139 (manufactured by Ciba Geigy; 172-179), CIBAECN1273 (manufactured by Ciba Geigy;
Approximately 225). The amount of these epoxy resins added is 0.1 to 5 parts by weight per 100 parts by weight of the resin. As the antifogging agent used in the present invention, nonionic, anionic and cationic surfactants are used, such as polyoxyalkylene ether,
Partial ester of polyhydric alcohol, partial ester of alkylene oxide adduct of polyhydric alcohol,
Examples include higher alcohol sulfate ester alkali metal salts, alkylaryl sulfonates, quaternary ammonium salts, and aliphatic amine derivatives. Specifically, polyoxyethylene lauryl ether, -stearyl ether, -nonyl phenyl ether,
Polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, penta Erythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan distearate,
Diglycerin monooleate, triglycerin diolate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalene sulfonate, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, lauric acid laurylamide ethyl phosphate ,
Examples include triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, and basic pyridinium salts of dodecylpyridinium sulfate. The amount of these antifogging agents added is based on 100 parts by weight of resin.
It is 0.01 to 5 parts by weight. The alkanolamines used in the present invention include alkanolamines such as triethanolamine, triisopropanolamine, tri-n-propanolamine, diethanol/aliphatic amine, diisopropanol/aliphatic amine, and di-n-propanol/fatty amine. Dialkanols and aliphatic amines such as group amines, diethanol and 2-hydroxyoctylamine, diethanol and 2-hydroxydecylamine, diethanol and 2-hydroxy C _8-12 alkylamines, diisopropanol and 2-hydroxyoctadecylamine, etc. Examples include alkanolamine/long chain α-olefin oxide adducts. The amount of these alkanolamines added is
The amount is 0.005 to 1.5 parts by weight per 100 parts by weight. The use of 1.5 parts by weight or more is not practical because it worsens the thermal stability. Examples of the ether group-containing phosphite compounds used in the present invention include tris(butoxyethyl) phosphite, tris(butoxyethoxyethyl) phosphite, phenyl bis(butoxyethoxyethyl) phosphite, diphenyl butoxyethoxyethyl phosphite, Nonylphenyl bis(butoxyethoxyethyl) phosphite, phenyl octyl butoxyethoxyethyl phosphite, diphenyl nonylphenoxypolyethoxyethyl phosphite, diphenyl lauroxypolyethoxyethyl phosphite, tetraphenyl (diethylene glycol),
Diphosphite, tetraphenyl (dipropylene glycol) diphosphite, penta (dipropylene glycol) diphosphite, diphenyl bis (butoxyethoxyethyl) bisphenol A diphosphite, tetra (ethoxyethoxyethyl) bisphenol A diphosphite, bis (cyclohexyl ph) enyl)/bis(butoxyethoxyethyl)/hydrogenated bisphenol A/diphosphite, diphenyl/bis(methoxyethyl)/hydrogenated bisphenol A/diphosphite, bis(nonylphenyl)/bis(butoxyethoxyethyl)/cyclohexanedimethanol/ Examples of pentaerythritol diphosphite compounds used in the present invention include diphosphite, tetra(butoxyethoxyethyl)・1,6-hexanediol diphosphite, and examples of pentaerythritol diphosphite compounds used in the present invention include diphenylpentaerythritol diphosphite, bis( Nonyl phenyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(butoxyethoxyethyl) pentaerythritol diphosphite, phenyl 4,4'-isopropylidene diphenol pentaerythritol diphosphite Examples include phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and the like. The amount of these phosphite compounds added is 100% of the resin.
The amount is 0.01 to 5 parts by weight. Phthalate plasticizers, polyester plasticizers, other ester plasticizers, phosphate plasticizers, chlorine plasticizers, and the like can be appropriately used in the composition of the present invention. If an ultraviolet absorber is added to the polymer 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 benzophenone, benzotriazole, salicylate, substituted acrylonitrile, piperidine, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, and the like. It is also possible to add stabilizing aids commonly used in the compositions of the invention. For example, 2,6-
Di-t-butyl-p-cresol, dilauryl thiodipropionate, diphenylthiourea, phenylindole, thiodiglycol bis(aminocrotonate), pentaerythritol, tris(hydroxyethyl)isocyanurate, sorbitol, mannitol, ani Examples include linodithiotriazine, melamine, pt-butylbenzoic acid, dehydroacetic acid, zinc dehydroacetate, nonylphenoxypolyethoxyphosphoric acid, benzoic acid, cinnamic acid, dibenzoylmethane, benzoylacetone, and stearoylbenzoylmethane. Other materials may be added as necessary, such as pigments, fillers, plate-out inhibitors, surface treatment agents, lubricants, fluorescent agents, antifungal agents, fungicides, metal deactivators, photodegradants, infrared absorbers, processing aids, etc. agent, mold release agent, etc. can be used in combination. Examples of the halogen-containing polymer used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer Coalescence, 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-acrylic acid ester copolymer, vinyl chloride- Halogen-containing synthetic resins such as maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polybutene, polyester, etc. -α-olefin polymers such as 3-methylbutene or ethylene-
Polyolefins and their copolymers such as vinyl acetate copolymers, ethylene-propylene 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-butaedine-styrene copolymers. The following examples show the effects of the halogen-containing resin composition according to the present invention, but the present invention is not limited to these examples. Example 1 100 parts by weight of polyvinyl chloride (Vinica 37H), 50 parts by weight of di-2-ethylhexyl phthalate, 3 parts by weight of epoxy resin (Epicote 828), 0.6 parts by weight of zinc stearate, 0.4 parts by weight of barium stearate, barium nonyl 0.5 parts by weight of phenate, distearyl pentaerythritol diphosphite
0.5 parts by weight of sorbitan monopalmitate, 2.0 parts by weight of methylene bisstearylamide, and 0.3 parts by weight of the alkanolamines shown in Table 1 were kneaded using a kneading roll to prepare a film with a thickness of 0.1 mm. This film was tested in an accelerated test (70°C, 90°C).
% relative humidity for 10 days) and when left as is indoors for 2 years, the surface condition (state of occurrence of lumps) was observed. The results are shown in Table 1.

[Table] Example 2 Films with a thickness of 0.1 mm were prepared using the following formulations with varying amounts of alkanolamines added, and the same tests as in Example 1 were conducted on these films. The results are shown in Table 2. <Composition> Polyvinyl chloride (Vinicron 4000M-3) 100 parts by weight Di-2-ethylhexyl phthalate 50 Epicote 828 3 Zn-stearate 0.6 Zn-toluate 0.2 Ba-stearate 0.3 Ba-nonyl phenolate 0.5 Distearyl pentaerythritol di Phosphite 0.5 parts by weight Diphenyl acid phosphite 0.3 Diphenyl-2-ethylhexyl phosphite
0.2 Sorbitan Monostearate 2.0 Alkanolamines (Table 2)Table 2

[Table] Example 3 Films with a thickness of 0.1 mm were made using different types of organic phosphite compounds according to the following formulations.
This film was subjected to the same tests as in Example 1, as well as thermal stability and initial colorability tests. The results are shown in Table 3. <Formulation> Part by weight Polyvinyl chloride (Vinicron 4000M-3)
100 Di-2-ethylhexyl phthalate 45 Trixylinyl phosphate 5 Bisphenol A diglycidyl ether
3 Zn-laurate 0.5 Ca-stearate 1.0 Mg-octoate 0.3 Ethylene bisstearylamide 0.3 Sorbitan monostearate 2.5 Triisopropanolamine 0.2 Diphenyl acid phosphite 0.2 Organic phosphite compounds (Table 3) 0.8

【table】

Claims (1)

[Claims] 1 For 100 parts by weight of halogen-containing resin, (a) 0.1 to 5 parts by weight of at least one organic acid metal salt, (b)
0.1 to 5 parts by weight of epoxy resin, (c) 0.005 to 1.5 parts by weight of alkanolamines, (d) 0.01 to 5 parts by weight of at least one antifogging agent, and (e) phosphite compound or pentaerythritol diphosphite having an ether group. A halogen-containing resin composition containing 0.01 to 5 parts by weight of at least one type of compound.