JPH0270711A - Vinyl chloride resin composition for agricultural use - Google Patents

Abstract

PURPOSE:To make it possible to form a vinyl chloride resin composition for agricultural use having a good weathering resistance over a long period of time by using a vinyl chloride resin produced by copolymerizing vinyl chloride with a specific ultraviolet absorptive compound as essential components. CONSTITUTION:The title vinyl chloride resin composition is obtained by mixing a vinyl chloride resin with a plastisizer, stabilizer, and if desired, other additive(s). That is, the composition is produced by using a monomer mixture comprising as essential components vinyl chloride and an ultraviolet absorptive compound of formula I in an amount of 0.01-10wt.% for vinyl chloride. In formula I, X is a group of formula II or III; R3 and R4 are independently a hydrogen atom, an alkyl group or an alkoxy group; B is a 2C or higher alkylene group or -CH2CH(OH)-CH2-; n is 0 or 1; Y is a hydrogen atom, a halogen atom or an alkyl group; R5 is a hydrogen atom or an alkyl group; R1 is a hydrogen atom or a methyl group; R2 is a hydrogen or -A-X; and A is -CO-, -CH2-, a direct bond or a group of formula IV.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to agricultural vinyl chloride resin compositions, and more specifically, the present invention relates to vinyl chloride resin compositions for agricultural use, and more specifically, the present invention relates to agricultural vinyl chloride resin compositions. The present invention relates to an agricultural heenyl chloride resin composition comprising a vinyl resin containing a plasticizer, a stabilizer, and other additives as necessary.

[Conventional technology and its problems]

Vinyl chloride resins have characteristics such as excellent weather resistance, high strength, and good transparency, and are used in a wide range of applications. In particular, soft products containing plasticizers are easy to process and are widely used as agricultural films, sheets, etc.

However, vinyl chloride resins have poor stability against heat and light, and have the drawback of being susceptible to thermal decomposition, mainly due to dehydrochlorination, during thermoforming processing, resulting in poor mechanical properties of processed products. Significant inconveniences such as deterioration and deterioration of color tone were often caused. In order to overcome these drawbacks, various heat stabilizers have been used singly or in combination, and almost satisfactory results have been obtained regarding stabilization during thermoforming.

Furthermore, although vinyl chloride resins have relatively good weather resistance, agricultural vinyl chloride resin compositions that are used outdoors for long periods of time suffer from problems such as deterioration of color tone, decrease in strength, and decrease in transparency. This often resulted in a significant loss of practicality.

For this reason, it is essential to use light stabilizers in agricultural vinyl chloride resin compositions, and conventionally, benzophenone-based,
UV absorbers such as benzotriazole or 2,2
．． A hindered amine light stabilizer typified by a 6,6-titramethylpiperidine derivative was added. By using these additive-type light stabilizers, the initial weather resistance can be improved to a relatively satisfactory degree. In particular, benzophenone-based and benzotriazole-based ultraviolet absorbers have a large effect, and they also suppress harmful wavelengths. It has also been reported that cutting out ultraviolet rays is effective in preventing the occurrence of diseases, and relatively large amounts of ultraviolet absorbers are added.

However, these additive-type light stabilizers tend to bleed or plume onto the resin surface, and are also extracted by rainwater, so they cannot function effectively over a long period of time.

Therefore, it has been strongly desired to develop a vinyl chloride resin composition that has good weather resistance over a long period of time.

[Means for solving the problem] As a result of extensive studies in view of the above-mentioned current situation, the present inventors have found that
In an agricultural vinyl chloride resin composition comprising a vinyl chloride resin containing a plasticizer, a stabilizer, and other additives as necessary, the vinyl chloride resin contains a By using a vinyl chloride resin produced from a monomer mixture containing 0.01 to 10% by weight of a compound represented by the following general formula (1) as an essential component, the above drawbacks can be overcome. I discovered that.

Indicates a hydrogen atom, an alkyl group or an alkoxy group,
B is an alkylene group having 2 or more carbon atoms or -CH! −
It represents CH(OR)-CHz-, and n represents 0 or 1. Y represents a hydrogen atom, a halogen atom, or an alkyl group, and 8% represents a hydrogen atom or an alkyl group.

R3 represents a hydrogen atom or a methyl group. R2 represents a hydrogen atom or -X. A is -CO-1-cHz-, a direct word.The present invention having the above-mentioned summary will be explained in further detail below.

In the compound represented by the above general formula (I), the alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nibutyl, tert-butyl, hexyl, octyl, 2-ethylhexyl, tert-octyl,
Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and examples of the alkoxy group include alkoxy groups derived from the above-mentioned alkyl groups.

Therefore, representative examples of the compound represented by the above general formula (I) include the following compounds.

Na12-hydroxy-4-(2-methacryloyloxyethoxy)benzophenoneNα22-hydroxy-4-(2-acryloyloxyethoxy)benzophenoneNα32-hydroxy-4-(2-hydroxyNo,
4 No, 5 Nα6 Nα7 Nα8 No, 9 No, 1O No, 11 3-methacryloyloxypropoxy)benzophenone 2-hydroxy-4-(2-methacryloyloxybutoxy)benzophenone 2.2°-dihydroxy-4-methoxy-4° -(2-
2-hydroxy-4-methacryloyloxybenzophenone 2-hydroxy-4-(4-vinylbenzyloxybenzophenone bis(2-(3-hydroxy-4-benzoylphenoxy)ethyl comarate 2-(2-hydroxy) methacryloyloxyethoxy)benzophenone -3-allyl-5-methylphenyl)benzotriazole 2-(2-hydroxy-3-allyl-5-tertiary octylphenyl)benzotriazole 2-(2-hydroxy-3-allyl-5-methylphenyl)-5 -chlorobenzotriazole Nα122-(2-hydroxy-5-allylphenyl)
Hensitriazole Nα132-(2-hydroxy-5-vinylphenyl)
Benzotriazole The vinyl chloride resin used in the present invention is produced by copolymerizing a monomer mixture containing vinyl chloride as the main monomer and a compound represented by the above-mentioned formula (I), and in addition, , vinyl acetate, (meth)acrylic acid alkyl ester, etc. may be included as a copolymerization component.

The amount of the compound of form (I) above is from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on vinyl chloride.

Polymerization can be carried out by known methods. For example, conventional methods for producing vinyl chloride resins such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization can be applied.

The degree of polymerization of the vinyl chloride resin is not particularly limited, but preferably has an average degree of polymerization of 500 to 4,000, particularly 700 to 3,000.

Furthermore, the vinyl chloride resin used in the present invention may be one copolymerized so that the amount of the compound represented by the above-mentioned form (1) becomes a desired ratio, or one obtained by copolymerizing the compound represented by the above-mentioned form (I).
It may also be a blend of a copolymer containing the compound represented by at a relatively high concentration and a resin not containing it.

Examples of the plasticizer used in the present invention include phthalates such as dibutyl phthalate, butylbenzyl phthalate, dioctyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, dioctyl adipate, diisononyl Adipates such as adipate, diisodecyl adipate, di(butyl diglycol) adipate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri- Examples include phosphates such as (butoxyethyl) phosphate and octyl diphenyl phosphate, as well as polyesters, tetrahydrophthalates, azelates, sebacates, stearic acids, citric acids, and trimellitates. In particular, phthalates and phosphates are effective in the present invention.

The amount of these plasticizers added is 20 parts by weight per 100 parts by weight of the resin.
-90 parts by weight, preferably 30-80 parts by weight.

The stabilizers used in the present invention include carboxylic acids, organic phosphoric acids, or phenolic metals (lithium,
Potassium, sodium, calcium, barium, magnesium, strontium, zinc, cadmium, tin, cesium, aluminum, organic tin, etc.) salts, organic tin mercaptide compounds, inorganic metal compounds, organic phosphite compounds, epoxy compounds, pure organic stabilization Examples include auxiliary agents.

The carboxylic acids constituting the metal salts of the carboxylic acids, organic phosphoric acids, or phenols include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid, linoleic acid, Aliphatic acids such as liluic acid, neodecanoic acid, oleic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, and brassic acid. Carboxylic acids and mixed fatty acids obtained from natural oils and fats such as tallow fatty acids, coconut oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids; benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, tert-butylbenzoic acid, tert-octylsalicylic acid, etc. Aromatic carboxylic acids: dihydric carboxylic acids such as maleic acid and adipic acid, or half esters thereof, etc., and organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, Examples include mono- or di(nonylphenyl)phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, etc. As for phenols, phenol, cresol,
Examples include cyclohexylphenol, nonylphenol, and dodecylphenol.

The amount of these metal salts added is 0.000 parts per 100 parts by weight of the resin.
01 to 10 parts by weight, preferably 1 to 5 parts by weight.

Examples of the organic tin mercaptide compound include isooctylthioglycolate or isooctylmercaptopropionate of mono- or dimethyltin, mono- or dibutyltin, or mono- or dioctyltin.

The amount of these organic tin mercaptide compounds added is 10% of the resin.
0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight.
05 to 3 parts by weight.

Examples of the inorganic metal compounds include oxides, hydroxides, carbonates, phosphates, pyrophosphates of the above metals, double salt compounds of the above metals such as synthetic hydrotalcite, and zeolites).
1st prize will be given.

The amount of these inorganic metal compounds added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin.

Examples of the organic phosphite compounds include triphenylphosphite, tris(2,4-di-tert-butylphenyl)
Phosphite, tris (nonylphenyl) phosphite, tris (mono and dinonylphenyl) phosphite,
Diphenyldecyl phosphite, trioctyl phosphite, phenyldioctyl phosphite, trioctyl phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol Diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, tetra(tridecyl)bisphenol A diphosphite, tetra(Clz-Cts mixed alkyl)bisphenol A diphosphite, hexa(tridecyl) )-1,1,3-)lis(3-tert-butyl-4
-Hydroxy-6-methylphenyl)butane triphosphite, diphenyl acid phosphite, bis(nonylphenyl) acid phosphite, and the like.

The amount of these organic phosphite compounds added is 0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight, per 100 parts by weight of the resin.
It is 1 to 5 parts by weight.

The above-mentioned epoxy compounds include bisphenol type and novolac type epoxy resins, epoxidized products of natural oils and fats such as epoxidized soybean oil and epoxidized linseed oil, alkyl esters of epoxidized unsaturated fatty acids such as epoxidized linseed oil fatty acid octyl, vinyl Examples include alicyclic epoxy compounds such as cyclohexene diepoxide.

The amount of these epoxy compounds added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin.

Examples of the pure organic stabilizing aids include polyhydric alcohols such as pentaerythritol, dipentaerythritol, dipentaerythritol adipate, mannitol, and sorbitol; -Diketone compounds; organic nitrogen-containing compounds such as 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid didodecyl ester, 2-phenylindole, and melamine;

The amount of these pure organic stabilizing aids to be added is o, oot to 5 parts by weight, preferably 0.005 parts by weight, per 100 parts by weight of the resin.
~3 parts by weight.

These stabilizers can be used alone or in combination of two or more depending on the purpose, and it is generally preferable to use a combination of metal salt of organic acid/organophosphite compound/epoxy compound.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 100 parts by weight of vinyl chloride and 0.3 parts of the compound listed in Table-1
A vinyl chloride copolymer having a degree of polymerization of 1000 was produced by normal suspension polymerization using parts by weight.

100 parts by weight of the above vinyl chloride copolymer, 47 parts by weight of dioctyl phthalate, 3 parts by weight of tricylenyl phosphate, 0.8 parts by weight of zinc stearate, 0.8 parts by weight of phosphonic acid nonyl phenyl ester barium salt, tetra(
C+z-+s mixed alkyl) 0.8 parts by weight of bisphenol A diphosphite, 3 parts by weight of bisphenol A diglycidyl ether, 0.8 parts by weight of methylene bisstearic acid amide.
5 parts by weight and 2 parts by weight of sorbitan monopalmitate were taken, and a film having a thickness of 0.1 was prepared using a kneading roll.

Using this film, a weather resistance test was conducted using a weatherometer.

Further, as a comparative example, a vinyl chloride resin having a degree of polymerization of 1000 and 0.3 parts by weight of the ultraviolet absorber listed in Table 1 was also tested in the same manner.

The results are shown in Table-1.

Table 1 Example 2 A vinyl chloride copolymer having a degree of polymerization of 1400 was produced by ordinary suspension polymerization using 100 parts by weight of vinyl chloride and 1 part by weight of the compound listed in Table 2.

30 parts by weight of the above vinyl chloride copolymer, degree of polymerization 1400
70 parts by weight of vinyl chloride polymer, 45 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, 0.0 parts by weight of calcium stearate. 4 parts by weight, 0.5 parts by weight of zinc stearate, 0.5 parts by weight of mono/distearyl zinc phosphate
Parts by weight, 1.5 parts by weight of octyl diphenyl phosphite, 3 parts by weight of bisphenol A diglycidyl ether, 0.02 parts by weight of dibenzoylmethane, and 0.5 parts by weight of methylene bisstearic acid amide were mixed with a kneading roll to a thickness of 0. A .1 mm film was created.

Using this film, a weather resistance test was conducted using a weatherometer.

Further, as a comparative example, a vinyl chloride resin having a degree of polymerization of 1400 and 1 part by weight of the ultraviolet absorber listed in Table 2 was added to the same test.

Display results Shown in 2.

Table-2 Example 3 100 parts by weight of vinyl chloride and 0.1 parts of the compound listed in Table-3
The degree of polymerization is 1400 by normal pA turbid polymerization using parts by weight.
A vinyl chloride copolymer was produced.

100 parts by weight of the above vinyl chloride copolymer, 45 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, 0.8 parts by weight of zinc stearate, 0.2 parts by weight of zinc mono/distearyl phosphate, phosphonic acid 0.5 parts by weight of nonylphenyl ester barium salt, tetra(C+.-
1, mixed alkyl) bisphenol A diphosphite 1
parts by weight, 3 parts by weight of bisphenol A diglycidyl ether, 0.04 parts by weight of dibenzoylmethane, 0.5 parts by weight of methylene bisstearic acid amide, and tetrakis (2,
0.2 parts by weight of 2,6,6-tetramethyl-4-piperidyl)butane tetracarboxylate was taken and a film having a thickness of 0.1 mm was prepared using a kneading roll.

Using this film, a weather resistance test was conducted using a weatherometer.

Further, as a comparative example, a vinyl chloride resin having a degree of polymerization of 1400 and 0.1 part by weight of the ultraviolet absorber listed in Table 3 was also tested in the same manner.

The results are shown in Table-3.

Table-3 Example 4 100 parts by weight of vinyl chloride and the compound listed in Table-4 +8o,
Using 1 part by weight, the polymerization degree was 1000 by ordinary suspension polymerization.
A vinyl chloride copolymer was produced.

100 parts by weight of the above vinyl chloride copolymer, 45 parts by weight of dioctyl phthalate, 5 parts by weight of tricylenyl phosphate, 0.1 part by weight of mono/distearyl zinc salt,
0.6 parts by weight of zinc stearate, 0.1 parts by weight of calcium stearate, 0.9 parts by weight of phosphonic acid nonylphenyl ester calcium salt, 0.5 parts by weight of tetra(C+□4. mixed alkyl) bisphenol A diphosphite,
0.3 parts by weight of octyl diphenyl phosphite, 1 part by weight of epoxidized soybean oil, 0.5 parts by weight of methylene bisstearic acid amide, 2 parts by weight of sorbitan monostearate, and tetrakis (2,2,6,6-tetramethyl- 0.3 parts by weight of 4-piperidyl)butanetetracarboxylate was taken and a film having a thickness of 0.1 mm was prepared using a kneading roll.

Using this film, a weather resistance test was conducted using a weatherometer.

Further, as a comparative example, a vinyl chloride resin having a degree of polymerization of 1000 and 0.1 part by weight of the ultraviolet absorber listed in Table 4 was also tested in the same manner.

The results are shown in Table 4.

Table 4 [Effects of the Invention] From the above results, the vinyl chloride resin composition of the present invention has significantly improved weather resistance by copolymerizing an ultraviolet absorber, and maintains its physical properties for a long period of time. Therefore, it is clear that it is extremely suitable as an agricultural vinyl chloride resin composition to be used outdoors under harsh conditions.

On the other hand, the composition to which an ultraviolet absorber was added showed only a relatively short-term stabilizing effect, and the effect was insufficient.

Claims (1)

[Scope of Claims] An agricultural vinyl chloride resin composition comprising a vinyl chloride resin containing a plasticizer, a stabilizer, and other additives as necessary, the vinyl chloride resin comprising: It is manufactured from vinyl chloride and a monomer mixture containing as an essential component an ultraviolet absorbing compound represented by the following general formula (I) in an amount of 0.01 to 10% by weight based on vinyl chloride. Agricultural vinyl chloride resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, X indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. represents a hydrogen atom, an alkyl group or an alkoxy group, B represents an alkylene group having 2 or more carbon atoms or -CH_2-CH(OH)-CH_2-, n
indicates 0 or 1. Y represents a hydrogen atom, a halogen atom, or an alkyl group, and R_5 represents a hydrogen atom or an alkyl group. R_1 represents a hydrogen atom or a methyl group. R
_2 represents a hydrogen atom or -AX. A is -CO-,
-CH_2-, indicates a direct bond or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. )