JP2509949B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a vinyl chloride resin composition for agriculture, more specifically,
The present invention relates to a vinyl chloride resin composition which is excellent in heat stability, weather resistance, colorability and plate-out property and does not pollute the environment when it is discarded, and is particularly suitable for use as an agricultural film.

[Problems to be Solved by Prior Art and Invention]

Vinyl chloride resins are used for films, sheets, hoses and the like because they are excellent in transparency, strength, economy and the like, and are used in large amounts in agricultural films such as houses and tunnels. However, these vinyl chloride resin products are known to cause weathering deterioration such as curing and browning deterioration due to the effects of sunlight, dust, oxygen, etc., when used outdoors, and are particularly used as agricultural films. If so, it is most susceptible to deterioration due to weathering due to its usage form.

Conventionally, as a weather resistance improver for vinyl chloride resin products, metal salts of organic acids, ultraviolet absorbers, antioxidants, organic phosphorous acid esters, metal salts of organic phosphoric acid, hindered amines, etc. have been used. Several combinations have also been proposed and used.

The combination of conventionally used modifiers, for example, the combination of metal soap, epoxy compound and organic triphosphite, has a relatively large effect of improving thermal stability and colorability,
Although the effect of improving the weather resistance was small, and it was also proposed that diphenyl phosphite was used in combination with the combination of metal soap and organic triphosphite. The stability and weather resistance were inferior and the plate-out property was large, which was not practically sufficient. Recently, a combination of a metal salt of an organic phosphoric acid and a hindered amine has been proposed, but this combination has an adverse effect on the coloring property, the blooming property and the high frequency adhesion property, although the weather resistance is improved. Other various stabilizing aids have been proposed, but none of them is practically sufficient, and further improvement has been desired.

[Means for solving problems]

The present inventors have made diligent studies in view of the above situation, and as a result, (1) a phosphate ester-based plasticizer,
(2) Epoxy resin, (3) Organic phosphorous acid metal salt represented by the following general formula (I), (4) Organic phosphoric acid metal salt represented by the following general formula (II) and (5) Organic phosphorous acid ester are blended. By doing so, it is possible to obtain an agricultural vinyl chloride resin composition capable of forming an agricultural film excellent in weather resistance, colorability, high-frequency adhesiveness, bloomability, suppression of spots, heat stability, and crop productivity. And has reached the present invention.

[In the general formulas (I) and (II), R ₁ represents an alkyl group, an alkenyl group or an aryl group, and M represents Mg, Ca, Sr or Ba.
Or Zn, and R ₂ represents R ₁ or M _1/2 . ] The agricultural vinyl chloride resin composition of the present invention is described in detail below.

The vinyl chloride resin used in the present invention includes a vinyl chloride homopolymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene vinyl acetate copolymer, a vinyl chloride-ethylene copolymer, and a vinyl chloride-propylene copolymer. Copolymers, vinyl chloride-styrene copolymers, vinyl chloride-isobutylene copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-styrene-caleic anhydride terpolymers, vinyl chloride-styrene-acrylonitrile copolymers , 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, vinyl chloride-
Methacrylic acid ester copolymers, vinyl chloride copolymers such as 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, styrene and other monomers (eg maleic anhydride, butadiene, acrylonitrile, etc.)
And acrylonitrile-butadiene-styrene copolymer, acrylic acid ester-butadiene-butadiene-styrene copolymer blended products and the like.

Examples of the (1) phosphate ester-based plasticizer used in the present invention include tricresyl phosphate, trixylenyl phosphate, tristearyl phosphate, tris (nonylphenyl) phosphate, dicresyl stearyl phosphate, tris (cyclohexyl) phosphate,
Tribenzyl phosphate etc. are mentioned. The phosphate ester plasticizers may be used alone or in combination of two or more,
Further, the blending amount thereof is preferably 0.1 to 10 parts by weight, more preferably 1 part by weight with respect to 100 parts by weight of the vinyl chloride resin.
~ 6 parts by weight.

Examples of the (2) epoxy resin used in the present invention include bisphenol-type and novolac-type epoxy resins which are obtained by reacting a polyhydric phenol with epichlorohydrin or methylepichlorohydrin.

Examples of the above-mentioned bisphenol type epoxy resin include Araldite 502 (manufactured by Ciba Geigy; epoxy equivalent 233 to 250), Araldite 508 (the same; 400 to 455), Epicron 850 (Dainippon Ink and Chemicals; 184 to 194), Epicron 830 (same; 170-190), Epicote 828 (manufactured by Shell Co .;
184-194), Epicoat 834 (the same; 230-270), Sumiepoxy ELA128 (Sumitomo Chemical; 184-194), MARK EP-13 (Adeka Argus Chemical; 184-194), EP-4100 (Asahi Denka Kogyo) Commercially available products such as the product; 180-200) are used, and examples of the above-mentioned novolac type epoxy resin include DEN431 (manufactured by Dow; epoxy equivalent 172-179) and DEN438 (the same; 175-18).
2), Epicron N-740 (manufactured by Dainippon Ink and Chemicals; 170-19
0), Epiclon N-680 (same; 220-240), CIBAEPN1139
(Made by Iva Geigy; 172-179), CIBAECN1273 (same; about
225) and other commercially available products are used.

The compounding amount of the epoxy resin is the vinyl chloride resin 10
It is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 0 parts by weight.

Further, (3) the organic metal phosphite represented by the general formula (I) and (4) the general formula (II) used in the present invention.
In the organic phosphoric acid metal salt represented by, the alkyl group represented by R ₁ includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, sec-butyl, amyl, sec-
Amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, behenyl, benzyl, 1-phenylethyl, 2
-Phenylethyl, α, α-dimethylbenzyl and the like are mentioned, and an alkyl group having an ether bond is also useful. Examples of the alkyl group having an ether bond include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl and α-methylfurfuryl groups, or methyl-, ethyl-, isopropyl-, butyl-, isobutyl-, hexyl-, cyclohexyl- , A phenyl cellosolve residue;
Methyl-, ethyl-, isopropyl-, butyl-, isobutylcarbitol residues; triethylene glycol monomethyl ether, -monoethyl ether, -monobutyl ether residues; glycerin 1,2-dimethyl ether,-
1,3-dimethyl ether, -1,3-diethyl ether,-
1-ethyl-2-propyl ether residue; nonylphenoxypolyethoxyethyl, lauroxypolyethoxyethyl groups and the like.

Examples of the alkenyl group represented by R ₁ include octenyl, decenyl, dodecenyl, octadecenyl, etc., and examples of the aryl group include phenyl, tolyl, xylyl, tert-butylphenyl, di-tert-butylphenyl, octyl. Examples thereof include phenyl, nonylphenyl, dinonylphenyl, dodecylphenyl and the like.

Next, the following Table 3 shows typical compounds of the organic metal phosphite represented by the general formula (I) used in the present invention.
It is shown in FIG.

The compounding amount of the above organic metal phosphite is a vinyl chloride resin 10
It is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 0 parts by weight.

In addition, (4) representative compounds of the organophosphate metal salt represented by the general formula (II) used in the present invention are shown in Table 2 below.
Shown in

The blending amount of the above-mentioned organic metal phosphate is the vinyl chloride resin.
It is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight.

Examples of the (5) organic phosphite used in the present invention include diphenyldecylphosphite, triphenylphosphite, tris-nonylphenylphosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, tributylphosphite, Tris (dinonylphenyl) phosphite, trilauryltrithiophosphite, trilaurylphosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethylphosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite , Tris (lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris (2'-methyl-5'-tert-butyl-4'-oxyphenyl) butanediphosphite, tetra (C ₁₂ -C 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- 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, phenyldiisodecyl phosphite, tetratridecyl-4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, tris (2,4-diphenyl) -Tert-butylphenyl) phosphite, tristearylphosphite, octyldiphenylphosphite, diphenyltridecylphosphite, phenyldi (tridecyl) phosphite, tris (2-cyclohexylphenyl) phosphite, ditridecyldi (2-cyclohexylphenyl) (Hydrogenated bisphenol A diphosphite, di (2,4-di-tert-butylphenyl cyclohexylphosphite, 2,4-di-tert-butylphenyl diisodecylphosphite, tris (butoxyethoxyethyl Phosphite, diphenyl A Sid phosphite, bis (2-cyclohexyl-phenyl) A SID phosphite, bis (2,4-di -t-
Butylphenyl) acid phosphite and the like.

The blending amount of the organic phosphite ester is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin,
It is more preferably 0.1 to 3 parts by weight.

A metal salt of an organic acid can be further added to the composition of the present invention.

Examples of the organic acid component that constitutes the metal salt of the organic acid include the following carboxylic acids. 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, isodecanic acid, isostearic acid,
12-hydroxystearic acid, 12-ketostearic acid,
Chloro stearic acid, phenyl stearic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, and mixtures of the above naturally occurring acids such as tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean fatty acid and cottonseed oil fatty acid. , Benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, p-t-butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, xylyl acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, Bromobenzoic acid, monobutyl maleate, monodecyl phthalate,
Cyclohexanecarboxylic acid.

Phenols are also useful as the organic acid component. Examples of the phenols include 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-
Examples include nonylphenol and di-t-dodecylphenol.

As the metal component constituting the metal salt of the above organic acid,
Zinc and Group Ia metals such as lithium, sodium and potassium, and Group IIa metals such as barium, calcium, magnesium and strontium.

The amount of the metal salt of the organic acid added is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Further, an antifogging agent can be added to the composition of the present invention depending on the purpose. As such an antifogging agent, a nonionic type,
Anionic and cationic surfactants are used, for example, polyoxyalkylene ether, partial ester of polyhydric alcohol, partial ester of alkylene oxide adduct of polyhydric alcohol, higher alcohol sulfuric acid ester alkali metal salt, alkylaryl sulfonate. , 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 monbehenate, sorbitan distearate, diglycerin monooleate, triglycerin dioleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, butylnaphthalenesulfonate sodium,
Cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, laurylamidoethyl phosphate lauric acid, triethylcetylammonium iodide, oleylamide diethylamine hydrochloride, basic pyridinium salt of dodecylpyridinium sulfate, and the like. .

The amount of the antifogging agent added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Further, a phthalic acid ester-based plasticizer, a polyester-based plasticizer, other ester-based plasticizers, chlorine-based plasticizers and the like can be appropriately added to the composition of the present invention.

Further, if a light stabilizer is added to the composition of the present invention,
Since the light stability can be improved, it is possible to appropriately select and use these depending on the purpose of use. These light stabilizers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, piperidine-based, various metal salts or metal chelates, particularly nickel or chromium salts or chelates, triazine-based and the like. .

In addition, stabilizing aids commonly used in the composition of the present invention can be added. Examples of the stabilizing aid include 2,6-di-t-butyl-p-cresol, dilaurylthiodipropionate, diphenylthiourea, phenylindole, thiodiglycolbis (aminocrotonate), pentaerythritol. , Tris (hydroxyethyl) isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, pt-butylbenzoic acid, dehydroacetic acid, zinc dehydroacetate, dibezozoylmethane, benzoylacetone, stearoylbenzoylmethane, nonylphenoxypoly Ethoxyphosphoric acid,
Examples thereof include benzoic acid and cinnamic acid.

In the composition of the present invention, if necessary, for example,
Includes pigments, fillers, anti-plateout agents, surface treatment agents, lubricants, fluorescent agents, antifungal agents, bactericides, metal deactivators, infrared absorbers, processing aids, mold release agents, reinforcing agents, etc. be able to.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Polyvinyl chloride (= 1300) 100 parts by weight, di-2-ethylhexyl phthalate 50 parts by weight, tricresyl phosphate 5 parts by weight MARK EP-13 2 parts by weight, sorbitan monopalmitate 2 parts by weight, methylene bisstear Loamide
To a mixture of 0.5 parts by weight, tetra (C ₁₂ -C ₁₅ alkyl) bisphenol A / diphosphite 0.8 parts by weight and dibenzoylmethane 0.02 parts by weight, the additive components shown in Table 3 below were added, and the mixture was kneaded with a thickness of 0.5 mm. Created a sheet. The thermal stability of this sheet was measured. Further, a film having a thickness of 0.1 mm was prepared in the same manner and tested for adhesion, weather resistance and initial drop property. The results are shown in Table 3 below.
Shown in The thermal stability measurement method, the adhesion, weather resistance and initial drop property test methods and the evaluation criteria for the results are as follows.

-Thermal stability: Measures blackening time in a 190 ° C gear oven.

Weather resistance: Observe the surface condition one year after outdoor exposure.

-Adhesiveness: Adhesiveness is measured with a high frequency sewing machine after being left for 3 months at 50 ° C and 80% humidity.

・ Initial dripping property: After the film has been left for 2 weeks at 50 ° C and 80% humidity, put it in a beaker containing water and visually observe the state after left for 30 minutes in a refrigerator at 5 ° C.

Example 2 Polyvinyl chloride (= 1300) 100 parts by weight, di-2-ethylhexyl phthalate 50 parts by weight, tricresyl phosphate 5 parts by weight MARK EP-13 2 parts by weight, diphenyl.
To a mixture of 0.8 parts by weight of isodecyl phosphite, 0.5 parts by weight of methylenebisstearamide and 0.02 parts by weight of dibenzoylmethane, the additive components shown in Table 4 below were added, and a sheet having a thickness of 0.5 mm was prepared with a kneading roll. . The thermal stability of this sheet was measured in the same manner as in Example 1. Further, a film having a thickness of 0.1 mm was prepared in the same manner, and the adhesion and weather resistance tests were conducted in the same manner as in Example 1. The results are shown in Table 4 below.

Example 3 Polyvinyl chloride (= 1300) 100 parts by weight, di-2-ethylhexyl phthalate 45 parts by weight, trixylenyl phosphate 5 parts by weight Epicoat 828 2 parts by weight, methylenebis stearamide 0.3 parts by weight, polyoxyethylene sorbitan 1.5 parts by weight of monolaurate, tetra (C _{12 to} C ₁₅
To a mixture of 0.4 parts by weight of alkyl) bisphenol A.diphosphite and 0.4 parts by weight of diphenyl isodecyl phosphite, the additive components shown in Table 5 below were added, and a sheet having a thickness of 0.5 mm was prepared with a kneading roll. A thermal stability test was performed on this sheet in the same manner as in Example 1. Further, a film having a thickness of 0.1 mm was prepared in the same manner, and the adhesion, weather resistance and initial drop test were conducted in the same manner as in Example 1. The results are shown in Table 5 below.

[Effects of the Invention] According to the agricultural vinyl chloride resin composition of the present invention, weather resistance, colorability, high-frequency adhesiveness, blooming property, suppression of spots,
It is possible to form an agricultural film having excellent heat stability and the ability to grow agricultural products. Further, the film formed of the agricultural vinyl chloride resin composition of the present invention does not pollute the environment when it is discarded.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 63/00 NJN C08L 63/00 NJN (56) Reference JP-A-61-250045 (JP, A) ) JP-A-59-113046 (JP, A) JP-A-54-91553 (JP, A) JP-A-61-190543 (JP, A)

Claims (1)

(57) [Claims] 1. A vinyl chloride resin, (1) a phosphoric acid ester plasticizer, (2) an epoxy resin, (3) the following general formula (I):
An organic metal phosphite represented by (4) the following general formula (II)
A vinyl chloride resin composition for agriculture, which is prepared by blending the organic phosphoric acid metal salt shown in 1) and (5) organic phosphorous acid ester. [In the general formulas (I) and (II), R ₁ represents an alkyl group, an alkenyl group or an aryl group, and M represents Mg, Ca, Sr or Ba.
Or Zn, and R ₂ represents R ₁ or M _1/2 . ]