JPS6246577B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vinyl chloride resin composition, and more specifically, it has excellent heat stability, weather resistance, coloring properties, plate-out properties, anti-fogging properties, etc., and is suitable for agricultural use without polluting the environment when discarded. The present invention relates to a vinyl chloride resin 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 significant deterioration of mechanical properties and color tone of processed products. cause a disadvantage. In addition, even when used outdoors for a long time, problems such as deterioration of color tone, decrease in strength, and decrease in transparency often occur, which greatly impairs its practicality. In order to overcome these drawbacks, various stabilizers have heretofore been used singly or in combination. Among these stabilizers, metal salts of organic acids are common and are used in almost all cases. Among these metal salts, cadmium,
Metal salts of lead have been highly prized for their effectiveness, but in recent years, the use of these toxic heavy metals has often been restricted, and harmless or low-toxicity metal salts such as zinc, alkali metals, and alkaline earth metals have been used. It is preferable to use However, these metal salts have weaker effects than cadmium and lead, and these metal salts alone cannot effectively stabilize vinyl chloride resin. 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 particular, the antifogging property of agricultural vinyl chloride resin is an important factor for crop growth, and the addition of an antifogging agent is necessary. Since it is known that the thermal stability of cadmium and lead decreases, conventional combinations are completely impractical, and there has been a strong demand for the development of highly effective stabilizers that do not use cadmium or lead. Conventionally used combinations, such as combinations of metal soaps, epoxy compounds, and organic triphosphites, have a relatively large effect on thermal stability and coloring properties, but have little effect on weather resistance; It has also been proposed to use diphenyl phosphite in addition to the combination, but although it is effective to some extent in preventing discoloration,
The long-term thermal stability and weather resistance were poor, and the plate-out property was also large, making it unsatisfactory for practical use. It has been proposed to add various other stabilizing aids, but none of them are practically sufficient, and further improvements have been desired. In view of the current situation, the present inventors have conducted intensive studies and found that (a) zinc organic acid salt, (b)
At least one type of organic acid salt of Group A or Group A metal, (c) At least one type of bisphenol type or novolak type epoxy resin, (d) At least one type of organic phosphite compound, (e) β having an aromatic nucleus. - diketone compounds or their metal salts and
(f) A vinyl chloride resin composition suitable for agricultural use that is excellent in all aspects of long-term thermal stability, anti-coloring properties, weather resistance, plate-out properties, and anti-fogging properties by incorporating at least one type of anti-fogging agent. The present invention was achieved by discovering that a product can be obtained. 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 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, satylylic 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, isoamylphenol, 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 lithium, sodium, potassium, 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. The epoxy resin used in the present invention includes bisphenol type and novolac type epoxy resins obtained by the reaction of polyhydric phenols with epichlorohydrin or methylepichlorohydrin. 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: 400-250).
455), Epicron 350 (Dainippon Ink Chemical; 184)
-194), Epicron 830 (same; 170-190), Epicort 828 (manufactured by Ciel; 184-194), Epicort
834 (same; 230-270), Sumiepoxy ELA128 (manufactured by Sumitomo Chemical; 184-194), EP-4100 (manufactured by Asahi Denka;
180-200), and examples of novolak type epoxy resins include DEM431 (manufactured by Dow; epoxy equivalent: 172-179), DEM438 (manufactured by Dow; epoxy equivalent: 175-182),
Epicron N-740 (Dainippon Ink Chemical; 170~
190), Epicron N-680 (same; 220-240),
CIBAEPN1139 (manufactured by Ciba Geigy; 172~
179) and CIBAECN1273 (same; approximately 225). The amount of these epoxy resins added is preferably 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin. The organic phosphite compounds used in the present invention include diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tributyl phosphite, tris( dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, tris(lauryl-
2-thioethyl) phosphite, tetratridecyl-1,1,3-tris(2'-methyl-5'-tertiary
Butyl-4'-oxyphenyl)butane diphosphite, tetra( _C12 - _C15 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
-Ethylhexyl diphenyl 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 pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4,4'-n- Butylidene bis(2-tert-butyl-5-methylphenol)
Diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, diphenyltridecyl phosphite, phenyl di(tridecyl) phosphite, tris(2-cyclohexyl phenyl) phosphite, Ditridecyl di(2-cyclohexylphenyl) hydrogenated bisphenonol A diphosphite, di(2.4
-di-tert-butylphenyl) cyclohexyl phosphite, 2,4-di-tert-butylphenyl diisodecyl phosphite, tris(butoxyethoxyethyl) phosphite, diphenyl acid phosphite, bis(2-cyclohexyl phenyl) acid phosphite , screw (2,4-G-t
-butylphenyl) acid phosphite and the like. The amount of these organic phosphite compounds added is
0.01 to 5 parts by weight per 100 parts by weight, preferably 0.1 to 5 parts by weight
It is 3 parts by weight. The β-diketone compound having an aromatic nucleus used in the present invention can be represented by the following general formula [] as an example. (In the formula, R ₁ and R ₂ are hydrogen atoms, halogen atoms,
represents an alkyl group or an alkoxy group, R ₃ represents a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or a cycloalkyl group; R ₄ represents a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group; arylalkyl group or

[Formula] is shown. ) To explain the above β-diketone compound in detail,
Alkyl groups in general formula [] include methyl, ethyl, propyl, isopropyl, butyl,
Isobutyl, t-butyl, amyl, isoamyl,
hexyl, heptyl, octyl, isooctyl,
Preferred examples include those having 1 to 18 carbon atoms such as nonyl, decyl, isodecyl, undecyl, tridecyl, pentadecyl, and hepdecyl groups; the aryl group is preferably a phenyl group; the alkylaryl group is preferably a group having 1 to 18 carbon atoms; 1~
An alkylphenyl group having 12 alkyl groups is preferable, and the arylalkyl group has 1 to 4 carbon atoms.
Phenylalkyl having an alkyl group of is preferred. Preferable examples of the cycloalkyl group include those having 6 to 8 carbon atoms, such as cyclohexyl and cyclooctyl groups. Further, this group may be substituted with an inert group such as an alkoxy group or a halogen atom. Typical compounds represented by the above general formula [] include benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylacetophenone, palmitoylacetophenone, lauroylacetophenone, heptanoylacetophenone, and dibenzoylmethane. , 1-octyl-1-benzoylacetone, 1-phenyl-3
-Benzoylacetone, p-methoxystearoylacetophenone, bis(4-chlorobenzoyl)methane, bis(4-t-butylbenzoyl)
Methane, ethylbenzoylacetylmethane, benzoyl phenylacetylmethane, benzoyl
Examples include nonylbenzoylmethane, 4-methoxybenzoyl benzoylmethane, bis(3,4-methylenedioxybenzoyl)methane, benzoyl trifluoroacetylmethane, and benzoyl formylmethane. Other examples include 2-benzoylcyclohexane-1,3-dione, benzoyltetralone, and 2-benzoylcyclohexanone. In addition, examples of metals constituting the metal salt of the β-diketone compound include lithium, sodium, potassium, magnesium, calcium, barium,
Examples include strontium, zinc, aluminum, zirconium, tin, and antimony. The amount of the β-diketone compound or its metal salt added is 0.001 to 5 parts by weight, preferably 0.005 to 1 part 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, pentaerythritol 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, laurylamide ethyl laurate phosphate, triethylcetylammonium iodide, oleyl aminodiethylamine Examples include basic pyridinium salts such as hydrochloride and dodecylpyridinium sulfate. The amount of these antifogging agents added is based on 100 parts by weight of resin.
The amount is 0.01 to 10 parts by weight, preferably 0.1 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, and cinnamic acid. 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. Agents, mold release agents, reinforcing agents, etc. can be included. 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- Isobrene 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 -Butadiene-styrene copolymer, acrylic ester-Butadiene-styrene copolymer, methacrylic ester-
Examples include blended products with butadiene-styrene copolymers. Examples of the present invention will be given below to clarify the effects of the present invention. In addition, the plate-out property in the table for each example is expressed in ppm of the plated-out dye by the watching plate method. Example 1 100 parts by weight of polyvinyl chloride (Vinica 37H), 45 parts by weight of di-2-ethylhexyl phthalate, 5 parts by weight of tricresyl phosphate, 0.8 parts by weight of Zn-stearate, 0.4 parts by weight of Ba-stearate, Ba
The additive components listed in Table 1 were added to a mixture of 0.5 parts by weight of nonylphenate, 3.0 parts by weight of sorbitan monopalmitate, and 0.3 parts by weight of methylene bisstearylamide, and a sheet with a thickness of 0.5 mm was prepared using a kneading roll. This sheet was tested for thermal stability, initial colorability, and plate-out property at 190°C. A weather resistance test using a weatherometer was also conducted. The results are shown in Table 1.

【table】

[Table] Example 2 The same test as in Example 1 was conducted by changing the type of triphosphite compound according to the following formulation. The results are shown in Table 2. Composition Part by weight Polyvinyl chloride (Vinicron 4000M-3) 100 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 mono Stearate 2.5 Benzoylstearoylmethane 0.2 Diphenyl acid phosphite 0.2 Organic triphosphite compounds 0.6

【table】

[Table] Example 3 A test similar to Example 1 was conducted using the following formulation. The results are shown in Table 3. Composition Part by weight Polyvinyl chloride (Vinica 37H) 100 Di-2-ethylhexyl phthalate 50 Epicote 828 2 Zn-stearate 0.6 Zn-toluate 0.2 Ba-stearate 0.3 Ba-nonyl phenate 0.5 Polyoxyethylene sorbitan monolaurate
1.5 Diphenyl acid phosphite 0.2 Diphenyl 2-ethylhexyl phosphite 0.3 β-diketone compound 0.05

【table】

【table】

Claims (1)

[Claims] 1 To the vinyl chloride resin, (a) zinc organic acid salt, (b) at least one group a or group a metal organic acid salt, (c) at least one bisphenol type or novolac type epoxy resin, ( An agricultural vinyl chloride resin composition comprising: d) at least one organic phosphite compound; (e) an aromatic β-diketone compound or a metal salt thereof; and (f) at least one antifogging agent.