JPH0345745B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vinyl chloride resin composition, specifically,
It is made by adding a plasticizer, a zinc salt of an organic acid, a Group A or Group A metal salt of an organic acid, an epoxy resin, and a liquid polybutadiene to a vinyl chloride resin, and has excellent heat stability, colorability, and weather resistance. The present invention relates to a vinyl chloride resin composition particularly suitable for agricultural use, which has improved roll staining and suppressed the occurrence of lumps. In general, vinyl chloride resins have poor stability against heat and light, and are prone to thermal decomposition mainly due to dehydrochlorination during thermoforming, resulting in decreased mechanical properties and color tone of processed products. It has the disadvantage of causing deterioration and causing significant disadvantages.
Moreover, when used outdoors for long periods of time, such as in agricultural applications, problems such as deterioration of color tone and decrease in strength often occur, impairing its practicality. In order to avoid such disadvantages, lead, barium,
By blending various combinations of metal soaps such as calcium, cadmium, magnesium, and zinc, organic tin compounds, organic phosphite compounds, epoxy compounds, etc., almost satisfactory results have been obtained in terms of thermal stability. However, cadmium, lead compounds, etc. are highly toxic, and their use is currently largely restricted. Therefore, methods have been considered in which a harmless or low-toxicity metal compound and a non-metal stabilizer are combined in a system that does not use cadmium or the like to achieve a synergistic effect.
However, although a certain degree of thermal stability can be obtained by such a method, it is not sufficient to satisfy the technical problems as a stabilizer. Epoxy compounds are known and widely used as stabilizing agents for vinyl chloride resin compositions, but to compensate for the lack of thermal stability of zinc soap, plasticizers such as epoxidized soybean oil and epoxidized linseed oil are used. If a large amount of epoxy compound is used, a bleeding phenomenon occurs and the surface of the molded product becomes sticky, making it impossible to obtain a practical product. Therefore,
It has been recognized that if a resin-type epoxy compound is used as an epoxy compound that does not have such drawbacks, it will be effective in improving the surface properties of products because it will not bleed even when used in large amounts. In addition, epoxy resin has better weather resistance than epoxidized vegetable oil.
It has excellent stain and mildew resistance, but due to the high temperature during molding and polycondensation of the epoxy compound due to the metal salt used as a stabilizer, plate-out phenomenon occurs on the breaker plate of the strainer and the take-off roll when calendering is performed. In the case of T-die machining, a plate-out phenomenon occurs as a die grain phenomenon, and in either case, long-run performance is significantly reduced. Moreover, when epoxy resin is used, it has a major drawback in that a lump phenomenon occurs several months after processing, which impairs its commercial value. In view of the current situation, the present inventors have made extensive studies to eliminate the drawbacks associated with the use of epoxy resins, and have found that 100 parts by weight of vinyl chloride resin, (a) 20 to 90 parts by weight of plasticizer, ( b) Zinc salt of organic acid 0.01 to 10 parts by weight, (c) Group a or group a metal salt of organic acid 0.01 to 10 parts by weight
10 parts by weight, (d) 0.01 to 10 parts by weight of epoxy resin, and (e)
By blending liquid polybutadiene with an average molecular weight of 500 to 10,000 or 0.005 to 3 parts by weight of its modified products, it has excellent long-term thermal stability, coloration prevention, and weather resistance.
In particular, it has been found that a vinyl chloride resin composition in which plate-out and lump formation are suppressed, particularly a vinyl chloride resin composition suitable for agricultural use, can be obtained, and the present invention has been achieved. Hereinafter, the vinyl chloride resin composition of the present invention having the above characteristics will be described in detail. Examples of plasticizers used in the present invention include phthalates such as dibutyl phthalate, diisononyl phthalate, butylbenzyl phthalate, dilauryl phthalate, diheptyl phthalate, dimethyl phthalate, diisodecyl phthalate, dioctyl phthalate, and dicyclohexyl phthalate, dioctyl adipate, and diisodecyl adipate. , diisononyl adipate, dibutyl diglycol adipate, and other adipates, tricresyl phosphate, tris(isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate , phosphates such as octyl diphenyl phosphate and tricylyl phosphate, other polyesters, tetrahydrophthalate, azelate, sebacate, stearic acid, citric acid, and trimellitate. The amount of these plasticizers added is 100% of vinyl chloride resin.
20 to 90 parts by weight, preferably 30 to 80 parts by weight
Parts by weight. Furthermore, among these plasticizers, phthalate plasticizers are particularly useful in the present invention, and when particularly high weather resistance is required, phthalate plasticizers and phosphate plasticizers may be used together. Preferably, in this case, 1 to 15 parts by weight of a phosphate plasticizer is used per 100 parts by weight of the vinyl chloride resin. Examples of the organic acids constituting the zinc salt of an organic acid and the group a or a 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, styrenic 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 naturally occurring mixtures of the above 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, xylicylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromo Examples include benzoic acid, monobutyl maleate, monodecyl phthalate, and cyclohexanecarboxylic acid. Phenols are also useful as organic acids. Examples of the phenols include cyclohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethylphenol, poly(di-penta)isopropylphenol, diisopropyl-m-cresol. , butylphenol, isoamylphenol,
Isooctylphenol, 2-ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-t-octyl Examples include phenol, di-t-nonylphenol, di-t-dodecylphenol, and the like. Group A metals of the metal component include lithium, sodium, potassium, etc., and Group A metals include barium, calcium, magnesium,
Examples include strotium. The amount of the zinc salt of the organic acid and the a or group a metal salt of the organic acid to be added is 0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight, respectively, per 100 parts by weight of the vinyl chloride resin.
It is 0.1 to 3 parts by weight. Epoxy resins used in the present invention include those obtained by reacting polyhydric phenols with epichlorohydrin or methylepichlorohydrin, with bisphenol type and novolac type epoxy resins being particularly preferred. Examples of bisphenol type epoxy resins include Araldite 502 (manufactured by Ciba Geigy; epoxy equivalent: 233-250), Araldite 508 (manufactured by Ciba Geigy; epoxy equivalent: 233-250),
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) etc. The amount of these epoxy resins added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The liquid polybutadiene or modified product thereof used in the present invention includes a butadiene homopolymer, a butadiene copolymer, a modified product thereof, and a mixture thereof. Furthermore, the term butadiene homopolymer is also used in a general sense, 1,
1, made by homopolymerization of 3-butadiene
Includes 2-atactic polybutadiene, 1,2-syndiotactic polybutadiene, 1,2-isotactic polybutadiene, 1,4-cis polybutadiene and 1,4-trans polybutadiene, or block polymers, graft polymers and mixtures thereof. . Similarly, butadiene copolymers include various copolymers made by copolymerizing 1,3-butadiene with olefinic monomers or conjugated diene monomers. It also includes partially modified polybutadiene. Modified polybutadienes include, for example, partially epoxidized products, those having a hydroxyl group and/or carboxyl group at the end, or partially maleated, halogenated, boiled, hydrogenated, acrylic modified,
Includes urethane-modified and ester-modified polybutadiene. In particular, for the purpose of the present invention, the amount of liquid polybutadiene containing 1,2-actactic polybutadiene as a main component or a modified product thereof is determined based on 100 parts by weight of vinyl chloride resin.
The amount is 0.005 to 3 parts by weight, preferably 0.01 to 1 part by weight. In order to obtain a particularly suitable agricultural vinyl chloride resin composition, it is preferable to further include an organic phosphite compound and an antifogging agent in the composition of the present invention. Such organic phosphite compounds include diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite,
Tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (dinonylphenyl) phosphite,
Trilauryltrithiophosphite, trilaurylphosphite, bis(neopentylglycol)-1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, tris(lauryl-2-thioethyl) Phosphite, tetratridecyl-1,1,
3-Tris(2'-methyl-5'-tert-butyl-4'-
oxyphenyl)butane diphosphite, tetra( _C12-15 mixed alkyl)4,4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert-butylphenyl)phosphite, tris(4 -oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4,
4'-isopropylidene diphenol polyphosphite, diphenyl bis[4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol)]thiodiethanol diphosphite, bis(octylphenyl) bis [4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol bentaerythritol diphosphite ,
Phenyl diisodecyl phosphite, tetratridecyl-4,4'-n-butylidene bis(2-tertiary)
Butyl-5-methylphenol) diphosphite, tris(2,4-di-tert-butylphenyl)
phosphite, trisstearyl phosphite,
Octyl diphenyl phosphite, diphenyl tridecyl phosphite, phenyl di(tridecyl) phosphite, tris(2-cyclohexyl phenyl) phosphite, di(tridecyl) di(2-cyclohexyl phenyl) hydrogenated bisphenol A diphosphite , di(2,4-di-third
butyphenyl) cyclohexyl phosphite,
2,4-di-tert-butylphenyl diisodecyl phosphite, tris(butoxyethoxyethyl) phosphite, diphenyl acid phosphite, bis(2-cyclohexyl phenyl) acid phosphite, bis(2,4-di-t- Examples thereof include butylphenyl) acid phosphite, bis(nonylphenyl) acid phosphite, dibenzyl acid phosphite, and the like. The amount of these organic phosphite compounds added is 0.01 to 10 parts by weight per 100 parts by weight of vinyl chloride resin.
Preferably it is 0.1 to 5 parts by weight. Nonionic, anionic, and cationic surfactants are used as antifogging agents, such as polyoxyalkylene ethers, partial esters of polyhydric alcohols, partial esters of alkylene oxide adducts of polyhydric alcohols, and higher alcohols. Examples include alkali metal sulfate ester 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, pentaerythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan distearate, diglycerin monooleate, triglycerin diolate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, butylnaphthalenesulfonic acid Examples include basic pyridinium salts of sodium, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, laurylamide ethyl laurate phosphate, triethylcetylammonium iodide, oleyl aminodiethylamine hydrochloride, and dodecylpyridinium sulfate. It will be done. The amount of these antifogging agents added is 100% of vinyl chloride resin.
0.01 to 10 parts by weight, preferably 0.1 parts by weight
~5 parts by weight. If an ultraviolet absorber is added to the composition of the present invention, the photostability can be improved, so it is possible to select and use these as appropriate depending on the purpose of use. These include benzophenone type, benzotriazole type, salicylate type, substituted acronitrile type, piperidine type and the like. Further, commonly used stabilizing aids can be added to the composition of the present invention. Such stabilizing aids include, for example, 2,6-di-t-butyl-
p-cresol, dilauryl thiodipropionate, diphenylthiourea, phenylindole,
Thiodiglycol bis(aminocrotonate),
Pentaerythritol, tris(hydroxyethyl)isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, dipentaerythritol, dipentaerythritol adipate, pt-butylbenzoic acid, dehydroacetic acid, zinc dehydroacetate, nonylphenoxy Examples include polyethoxyphosphoric acid, benzoic acid, cinnamic acid, dibenzoylmethane, stearoylbenzoylmethane, and benzoylpentanoylmethane. Others as necessary, such as pigments, fillers, surface treatment agents, lubricants, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, red deterioration agents, ultraviolet absorbers, processing aids, and mold release agents. , reinforcing agents, and the like. As the vinyl chloride resin used in the present invention,
Vinyl chloride homopolymer and vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene 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-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, chloride Vinyl chloride copolymers such as vinyl-methacrylic acid ester copolymers and vinyl chloride-acrylonitrile copolymers, and the above resins and α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, or ethylene-vinyl acetate. Copolymers, polyolefins such as ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile Blended products with -butadiene-styrene copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, etc. can be mentioned. Examples of the present invention will be given below to clarify the effects of the present invention. Example 1 The following formulation was also subjected to a kneading test using a two-roll mill, and the onset time of adhesion on the roll at 180°C and the staining of the roll 20 minutes after the mill test were measured. In addition, a film with a thickness of 0.1 mm was prepared using the same formulation, and was exposed outdoors for one year to evaluate its weather resistance.
In addition, the appearance of spots was observed when this film was stored at 70° C. and 90% relative humidity for 10 days. The results are shown in Table-1. Incidentally, the occurrence of bumps was evaluated on a 5-level scale, with 1 indicating no abnormality and the higher the number, the more bumps had occurred. In addition, roll dirt was evaluated on a scale of 1 to 1.
5 indicates that there is no abnormality, and as the number increases, the dirt becomes more severe. 5 indicates that a thin white film has been formed on the entire surface, and 10 indicates that a thick cloudy film has been formed. . Composition Part by weight Polyvinyl chloride 100 Di-2-ethylhexyl phthalate 50 Tricresyl phosphate 5 Zinc stearate 0.8 Barium stearate 0.4 Zinc octylate 0.3 Barium p-tert-butylbenzoate 0.3 Octyl diphenyl phosphite 0.6 Sorbitan mono Palmitate 2 Epoxy resin (manufactured by Asahi Denka; EP-13) 3 Liquid polybutadiene (Table 1) 0.1

【table】

[Table] Example 2 Using the following formulation, the onset time of adhesion onto the roll and the staining of the roll were measured in the same manner as in Example 1. Further, a film with a thickness of 0.1 mm was prepared using the same formulation, and the degree of haze of the film was measured after being exposed outdoors for 6 months. Since the degree of haze increases due to the attachment of fine dust to the film and reduces the transmittance of light rays, it is preferable that the degree of haze is small in agricultural films. The results are shown in Table-2. Mixture parts by weight Polyvinyl chloride 100 Di-2-ethylhexyl phthalate 50 Trixyl phosphate 7 Epoxy resin (manufactured by Ciel; Epicote 828) 3 Sorbitan monopalmitate 3 Ethylene bisstearylamide 0.5 Zinc octylate 0.3 Barium-pt -Butylbenzoate 0.3 Tetra(tridecyl)bisphenol 1.5 A.diphosphite Liquid polybutadiene (Table-
2) (Table-2)

【table】

[Table] Example 3 A film with a thickness of 0.1 mm was prepared from the following formulation, and its thermal stability at 190°C was measured. Further, regarding this film, the state of occurrence of spots was observed in the same manner as in Example 1. The results are shown in Table 3. Mixture parts by weight Polyvinyl chloride 100 Di-2-ethylhexyl phthalate 40 Triclidyl phosphate 3 Epoxy resin (manufactured by Asahi Denka; EP-13) 2 Stearic acid amide 1 Calcium stearate 1 Zinc stearate 1 Octyl diphenyl phosphite 0.5 Liquid Polybutadiene (Table-3) 0.1

【table】

【table】

Claims (1)

[Claims] 1 100 parts by weight of vinyl chloride resin, (a) 20 to 20 parts of plasticizer
90 parts by weight, (b) 0.01 to 10 parts by weight of zinc salt of organic acid, (c)
Adding 0.01 to 10 parts by weight of a Group A or Group A metal salt of an organic acid, (d) 0.01 to 10 parts by weight of an epoxy resin, and (e) 0.005 to 3 parts by weight of liquid polybutadiene or a modified product thereof having an average molecular weight of 500 to 10,000. A vinyl chloride resin composition.