JPH0912814A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE: To obtain a vinyl chloride resin composition having excellent durability by mixing a vinyl chloride resin with an organophosphorus compound represented by a specified formula and at least one metal-containing phsphorus compound in a specified ratio. CONSTITUTION: 100 pts.wt. vinyl chloride resin (e.g. PVC of a number-average molecular weight of 800-2,500) is mixed with 0.1-5 pts.wt. organophosphorus compound represented by formula I (R1 to R4 are each a 6-18C alkyl, cycloalkyl or aryl, alkenyl or the like) and 0.1-1.0 pt.wt. at least one metal-containing phosphorus compound represented by formula II or III [R1 to R5 are each an alkyl, an aryl, an aralkyl, an alkyl-substituted aryl, R6 O-(CH2 CH2 O)n or the like (n is 1-4; R6 is an alkyl or aryl; and M is Ba, Ca, Mg or Zn]. The resultant mixture is mixed with about 30-70 pts.wt. plasticizer, about 0.5-7 pts.wt. lubricant and/or heat stabilizer, about 0-5 pts.wt. antifogging agent or surfactant, 0-3 pts.wt. ultraviolet absorber, 0-2 pts.wt. hindered amine light stabilizer, etc., and the obtained mixture is kneaded to obtain a vinyl chloride resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is a novel chloride suitable for use in greenhouses and tunnel cultivation, which is excellent in cold resistance and weather resistance and has an excellent durability that can be used for a long period of time. The present invention relates to a vinyl resin composition.

[0002]

2. Description of the Related Art It is generally known that vinyl chloride resin is colored and deteriorated by heat during processing, and is deteriorated by ultraviolet rays in sunlight when used outdoors for a long time. In order to prevent these deteriorations, stabilizers such as barium / zinc / phosphite compounds, calcium / zinc / phosphite compounds, epoxy compounds, polyhydric alcohols, β-
Stabilization aids such as diketones, and light stabilizers such as ultraviolet absorbers and hindered amines are used. However, after two years have passed since the start of use, the deterioration becomes remarkable, and it becomes impossible to endure extended use in a house or tunnel. For example, 3 to 10 parts by weight of tricresyl phosphate (hereinafter referred to as TCP), tricylenyl phosphate (hereinafter referred to as TXP) and the like are used for the purpose of imparting long-term weather resistance to an agricultural vinyl chloride resin film. Techniques described in patent publications such as Japanese Examined Patent Publication No. 62-12930 and Japanese Examined Patent Publication No. 4-61771 are mentioned as these. However, these phosphoric acid esters are not sufficiently improved, and even if the amount added is further increased, the weather resistance is not improved and the cold resistance is deteriorated. Recently, a metal-containing phosphorus compound is used for the purpose of improving weather resistance.
There are techniques described in patent publications such as No. 8462 and Japanese Patent Publication No. 5-74616. However, even with these techniques, it was not possible to satisfy the weather resistance and the cold resistance of the vinyl chloride resin film for agriculture. Techniques for solving these drawbacks include JP-B-62-52772, JP-A-1-156356, and JP-A-2-49051. However, it cannot be said that weather resistance and cold resistance are sufficient.

[0003]

The present invention is superior to the composition containing TCP or TXP in terms of weather resistance and cold resistance, which are the drawbacks of the conventional resin films for agricultural use, and can be used for a long period of time. The present invention has been made for the purpose of providing a novel vinyl chloride resin composition most suitable for an agricultural film having excellent durability.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to develop a vinyl chloride resin composition having the above-mentioned preferred characteristics, the vinyl chloride resin contains a specific organic phosphorus compound and a metal. By sharing phosphorus compounds,
The inventors have found that the object can be achieved and completed the present invention.

Typical examples of the organic phosphorus compound of the general formula [1] used for the vinyl chloride resin in the present invention are as follows.

[0006]

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[0007]

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[0008]

[Chemical 6]

[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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Each of these organophosphorus compounds is independent,
Alternatively, depending on circumstances, two or more kinds may be used in combination. It may be produced by any method, and a reaction product containing the compound represented by the formula [1] may be used, but a pure product is preferable.

[2] and [3] used in the present invention.
Typical examples of the metal-containing phosphorus compound of the formula are as follows.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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These metal-containing phosphorus compounds may be used alone or in combination of two or more. Further, it may be manufactured by any method.

The vinyl chloride resin as the base of the film of the present invention has, for example, a number average degree of polymerization of about 800 to 2
500, preferably about 1000 to 1800 polyvinyl chloride, a copolymer mainly composed of vinyl chloride (for example, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, vinyl chloride-halogenated olefin copolymer) Etc.) or other compatible resins based on these polyvinyl chloride or vinyl chloride copolymers (eg polyester resin, epoxy resin, acrylic resin, vinyl acetate resin, urethane resin, acrylonitrile styrene-butadiene copolymer) , Partially saponified polyvinyl alcohol, etc.) and the like. These vinyl chloride resins may be obtained by any conventional production method such as cyclic polymerization method, emulsion polymerization method and suspension polymerization method. These vinyl chloride resins may be used alone or in combination of two or more.

For the vinyl chloride resin,
30 to 70 parts by weight, preferably 40 to 60 parts by weight, and 0.5 to 7 parts by weight, and preferably 1.0 to 5.0 parts by weight of lubricant and / or heat stabilizer per 100 parts by weight thereof. 0 to 5.0 parts by weight, preferably 1.0 to 4.0 parts by weight of antifogging agent or surfactant; 0 to 1% by weight, preferably 0.02 to 0.5% by weight of antifog agent 0 to 3.0 parts by weight,
Preferably 0.1 to 0.5 parts by weight of UV absorber; 0 to
2 parts by weight, preferably 0.03 to 1 part by weight of a hindered amine light stabilizer; 0 to 5.0 parts by weight, preferably 0.1.
1 to 1.0 parts by weight of an anti-sticking agent can be added.

Examples of the plasticizer include di-n-octyl phthalate, di-2-ethylhexyl phthalate,
Phthalic acid derivatives such as diisononyl phthalate and diisodecyl phthalate; Isophthalic acid derivatives such as diisooctyl isophthalate; Adipic acid derivatives such as dioctyl adipate; Others tricresyl phosphate, trixylenyl phosphate, epoxidized soybean oil and the like, among which dioctyl Phthalate, dioctyl adipate and epoxidized soybean oil are suitable.

Examples of the lubricants or heat stabilizers include polyethylene wax, fatty acid amide, stearic acid, zinc stearate, barium stearate, calcium stearate, barium ricinoleate, chelators such as organic phosphite, epoxy resins and the like. Is mentioned.

The above-mentioned antifogging agent or surfactant may be any of those usually used, and for example, a partial ester of a polyhydric alcohol consisting of a polyhydric alcohol and higher fatty acids is preferable. Specific examples of such substances include, for example, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate,
Sorbitan surfactants such as esters of sorbitan-glycerin condensates with higher fatty acids, sorbitan alkylene glycol condensates with higher fatty acids:
Glycerin-based surfactants such as glycerin monolaurate, glycerin monostearate, diglycerin monostearate, diglycerin monolaurate, diglycerin monopalmitate, triglycerin monostearate, triglycerin distearate: polyethylene glycol Polyethylene glycol surfactants such as monostearate, polyethylene glycol monopalmitate, polyethylene glycol alkyl phenyl ether:
Other trimethylolpropane monostearate and other trimethylolpropane thread surfactants: Pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol surfactants such as dipentaerythritol monostearate: or their isomers It can include those that include.

Examples of the antifogging agent include polymers containing a perfluoroalkyl group or a perfluoroalkenyl group, or low molecular weight fluorine-containing surfactants. Generally, at least 0.001% by weight, preferably Has a solubility in water of at least 0.01 wt.
In the above, those having an ability to reduce the surface tension of water to 35 dyn / cm or less, preferably 30 dyn / cm or less are preferable. Further, an oxygen atom may be present in the carbon chain of the perfluoroalkyl group.

Examples of commercially available products used as the above-mentioned anti-fog agent include Unidyne DS-401, Unidyne D
S-403, Unidyne DS-451 (all manufactured by Daikin Industries, Ltd.), Megafac F-142D, Megafac F-177 (all manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-170, Florard FC-176, Fluorard FC-430 (above, Sumitomo 3M), Surflon S-141, Surflon S-145, Surflon S-381, Surflon S-382, Surflon S-3.
93 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

As the ultraviolet absorber, for example, a benzotriazole type, a benzophenone type, a salicylic acid type or the like is used. The benzotriazole-based compounds include 2- (2'-hydroxy-3 ', 5'-di-te.
rt-Butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '. -Tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3'-isobutyl-
5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-te
rt-Butylphenyl) benzotriazole, 2- (2
′ -Hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-5 ′-(1,1,
3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

Further, as the benzophenone type,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-
Examples include hydroxy-4-octoxybenzophenone.

Examples of salicylic acid-based compounds include phenyl salicylate and paraoctyl phenyl salicylate. These ultraviolet absorbers can be used alone or in combination of two or more, and benzophenone type and benzotriazole type are particularly preferable.

The above-mentioned hindered amine light stabilizers are well known, for example, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (1,
2,2,6,6-Pentamethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine] succinate] condensate, poly { [6- (1,1,3,3-
Tetramethylbutyl) imino] -1,3,5-triazine-2,4-diyl [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2
2,6,6-tetramethyl-4-piperidyl) imino]}, tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-
Piperidyl-tridecyl-1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2, 4, 8, 10
-Ester of tetraspiro [5,5] undecane and butanetetracarboxylic acid.

Further, other usual resin additives such as a filler, an antioxidant, an antistatic agent, a colorant and the like can be contained as required. The filler is usually used for suppressing stickiness of the film or maintaining heat retention property, and as such, it is preferable to use silica, talc, aluminum hydroxide, hydrotalcite, calcium sulfate, silicic acid. Calcium, calcium hydroxide, magnesium hydroxide, kaolin clay, mica, alumina,
Inorganic materials such as magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate and zirconium hydroxide can be used. The type and amount of the filler are determined depending on the thickness of the film, but usually 0.05 to 7% by weight, preferably 0.1 to 5% by weight, based on the vinyl chloride resin as the base material. Used in a range.

In order to mix each resin additive with the above vinyl chloride resin, the required amount is weighed, charged into a ribbon blender, a Banbury mixer, a super mixer or other conventionally known compounding machine or mixer and kneaded. Good.

The resin composition thus obtained can be formed into a film by a method known per se, such as a calendering method or an extrusion molding method.

If the thickness of the film of the present invention is too thin, the strength is insufficient, and on the contrary, if it is too thick, it causes inconvenience to the film forming work and the like. Preferably 0.05-0.2 m
It is appropriate to set the range of m.

[0048]

EXAMPLES Specific examples and comparative examples of the present invention will be described below. In Examples 1 to 6 and Comparative Examples 7 to 10, DO was added to 100 parts by weight of polyvinyl chloride resin (polymerization degree: 1300).
P is 49 parts by weight in Examples 1 to 6 and Comparative Example 9, 45 parts by weight in Comparative Examples 7, 8 and 10, 2.0 parts by weight of epoxy resin, and 2.0 parts of antifogging agent (sorbitan monopalmitate). The base compound formed by adding parts by weight contains the additives shown in Table 1 in a predetermined amount or a comparative predetermined amount, and after mixing by a usual means, a predetermined thickness (for example, 0.1 m) is obtained by calendering.
The film is produced in the form of m).

[0049]

[Table 1]

With respect to each of the films thus obtained (Examples 1 to 6 and Comparative Examples 7 to 10), a sample of each film was mounted on an exposure table and exposed outdoors for 18 months to deteriorate the appearance of the film. A weather resistance test in which changes were visually evaluated. Internal dimensions of each film are 100 mm x 10
A cold resistance test in which a film was fixed on a 0 mm fixing plate and left at room temperature of -10 ° C for 90 minutes, and then a 100 g copper ball was dropped from a position of 1.8 m in height to measure the film rupture rate. A sample of each film was allowed to stand at room temperature for one month and then subjected to a bloom bleed test in which the degree of discharge of the additive was visually evaluated. Table 1 shows the results.

In the table, (a) is chemical formula 7 and (b) is chemical formula 11
The organophosphorus compound (c) represented by Chemical formula 15 is a metal-containing phosphorus compound represented by Chemical formula 15, and (d) is a metal-containing phosphorus compound represented by Chemical formula 25.

[0052]

As can be seen from the test results in Table 1, the agricultural vinyl chloride film produced from the vinyl chloride resin composition of the present invention shows a browning on the film surface in the conventional TCP and TXP blending. To be In addition, there are drawbacks such as poor cold resistance. Further, although the weather resistance and the cold resistance are improved by using the organophosphorus compound of Comparative Example 9, the weather resistance and the cold resistance are improved by sharing the organophosphorus compound of the present invention and the metal-containing phosphorus compound as in Examples 1 to 6. The sex is further improved, and it has a great effect that it can be used for a long period of time by being used for greenhouses, tunnel cultivation and the like.

Claims (1)

[Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, of the organophosphorus compound represented by the general formula 1 and 0.1 to 0.5 parts by weight of the metal-containing phosphorus compound represented by the formula 2 or 3 are used alone or in a mixture.
A vinyl chloride resin composition, characterized in that the vinyl chloride resin composition is compounded in an amount of 1.0 part by weight. Embedded image Embedded image Embedded image