JPH10338789A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition excellent in weatherability and durability, etc., and capable of using for agricultural films, etc., by combinedly using a specific organophosphorus compound, a nitrogen-containing polyhydric alcohol and magnesium oxide. SOLUTION: This resin composition is obtained by compounding (A) 100 pts.wt. chlorine-containing resin with (B) 0.1-5.0 pts.wt., preferably 0.3-3.5 pts.wt. organophosphorus compound of formula I (R1 to R4 are each a 6-18C alkyl, cycloalkyl, aralkyl, allyl, etc.), (C) 0.01-3.0 pts.wt., preferably 0.03-2.0 pts.wt. nitrogen-containing polyhydric alcohol of formula II R5 to R7 are each (CH2 )n OH [(n) is 1-4]} and (D) 0.01-3.0 pts.wt., preferably 0.03-2.0 pts.wt. magnesium oxide compound. Thereby, it can be expected to provide agricultural film excellent in weatherability and capable of carrying out extension over a long term, hardly causing blooming and having good bonding property due to a high-frequency machine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for use in cultivation of a house or a tunnel, has excellent weather resistance, has excellent durability which can be used for a long time, and has a high frequency sewing machine adhesiveness between films. The present invention relates to a novel, stabilized chlorine-containing resin composition which is most suitable for agricultural films having excellent ballooning properties.

[0002]

2. Description of the Related Art It is generally known that a vinyl chloride resin is deteriorated in color by heat and deteriorates by ultraviolet rays in sunlight when used outdoors for a long time. In order to prevent such deterioration, stabilizers such as barium / zinc / phosphite compounds, calcium / zinc / phosphite compounds, stabilizing aids such as epoxy compounds, polyhydric alcohols, β-diketones, and ultraviolet rays Light stabilizers such as absorbers and hindered amines have been used. However, even if these are applied to agricultural films, the deterioration becomes remarkable after two years from the start of use, and the film cannot be used in a stretched use in a house or a tunnel.

[0003] Further, when the film is stretched, in order to finish the film to a predetermined size, an adhesive process using a high-frequency sewing machine is generally performed to join the films together. Adhesion processing using a high-frequency sewing machine utilizes the fact that a soft chlorine-containing resin film has a large dielectric loss and heat-bonds the film by internal heat generation of the film in a high-frequency electric field. If the film surface becomes dirty during the bonding process or if the electrode surface is not properly adjusted, a spark may be generated and the bonding may not be performed properly. Further, depending on the type of the additive contained in the film, the adhesive property is often impaired by bleeding out, for example, a metal salt compound which is incompatible with the vinyl chloride resin on the film surface. Such a phenomenon that the adhesive property is impaired appears immediately after the film is made and the seam is peeled off at the time of the adhesive processing by the high frequency sewing machine,
There are cases such as peeling during expansion in the house and peeling after expansion in the house. Repair of the peeling of the adhesive seam after expansion in particular requires a great deal of manpower and time.

On the other hand, not only for agricultural use, but also for soft chlorine-containing resin films, a ballooning phenomenon is often observed on the surface due to various additives incorporated therein. This is also similar to the problem of adhesive workability by the high frequency sewing machine.
This is an undesired phenomenon seen shortly after film formation or several years after stretching. That is, when the balloon phenomenon occurs, for example, in the case of an agricultural vinyl chloride film,
When coated on a house or a tunnel, dust tends to adhere to the surface, resulting in a decrease in light transmittance and adversely affecting the growth of crops.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to improve the disadvantages of such conventional agricultural resin films such as weather resistance, ballooning property, and high-frequency sewing machine adhesiveness, and to provide an excellent durability that can be used for a long period of time. The object of the present invention is to provide a novel chlorine-containing resin composition that is most suitable for agricultural films having properties.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a chlorine-containing resin composition having the above-mentioned preferable characteristics, and as a result, a specific organic phosphorus compound, a nitrogen-containing polyhydric alcohol and It has been found that the object can be achieved by using magnesium oxide in combination, and the present invention has been completed.

The organophosphorus compound used in the chlorine-containing resin in the present invention has a general formula [Chemical Formula 1]
2, R3, and R4 are the same or different and are represented by an alkyl group having 6 to 18 carbon atoms, a cycloalkyl group, an aralkyl group, an allyl group, an alkyl-substituted allyl group, or an alkenyl group). The chemical formulas are [Formula 3], [Formula 4], [Formula 5], [Formula 6], and [Formula 7].

[0008]

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[0009]

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[0010]

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[0011]

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[0012]

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Each of these organic phosphorus compounds is
Alternatively, depending on circumstances, two or more kinds may be used in combination. Further, any method may be used, and a reaction product containing the compound represented by the formula [1] can be used, but a higher purity is preferable. The compounding amount is 0.1 to 5.0 parts by weight, preferably 0.3 to 3.5 parts by weight, per 100 parts by weight of the chlorine-containing resin. If the amount is less than 0.1 part by weight, sufficient weather resistance cannot be obtained even when the component [Chem. 2] and magnesium oxide are used in combination. If the amount is more than 5.0 parts by weight, the film is undesirably colored during processing.

The nitrogen-containing polyhydric alcohol used in the present invention has the general formula [Chemical Formula 2] wherein R5, R6, and R7 are the same or different, and are (CH ₂ ) _n OH (n = 1 to 4).
Represents a group. It is represented by｝. The amount of these components is 0.01 to 3.0 parts by weight, preferably 0.03 to 2.0 parts by weight, per 100 parts by weight of the chlorine-containing resin. If the amount is less than 0.01 part by weight, the adhesiveness of the high frequency sewing machine becomes inferior even when the component [Chem. 1] and magnesium oxide are used in combination, which is not preferable. On the other hand, if it is more than 3.0 parts by weight, the ballooning property is inferior and is not preferred. Typical examples are [Chemical Formula 8], [Chemical Formula 9], [Chemical Formula 10], and [Chemical Formula 11].

[0015]

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[0016]

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[0017]

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[0018]

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Commercially available examples of the above-mentioned nitrogen-containing polyhydric alcohol include Tanac of Nissan Chemical Industries, Ltd.

The amount of the magnesium oxide used in the present invention is 0.01 to 100 parts by weight of the chlorine-containing resin.
3.0 parts by weight, preferably 0.03 to 2.0 parts by weight. When the amount is less than 0.01 part by weight, sufficient weather resistance and ballooning property cannot be obtained, and when the amount is more than 3.0 parts by weight, the transparency of the film at the time of processing is unfavorably deteriorated.

Examples of commercially available magnesium oxide include:
Kyowa Mag 30 manufactured by Kyowa Chemical Industry Co., Ltd., and the like.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The chlorine-containing resin serving as the base of the film of the present invention has, for example, an average degree of polymerization of about 800.
To 2500, preferably about 1000 to 1800 polyvinyl chloride, a copolymer based on vinyl chloride (eg, vinyl chloride / ethylene vinyl chloride copolymer, vinyl chloride /
Vinyl acetate copolymer, vinyl chloride / halogenated olefin copolymer, etc.), or a polyester resin, epoxy resin, acrylic resin, urethane resin having good compatibility with these polyvinyl chloride or vinyl chloride copolymer.
It is possible to use a blend of MBS and ABS resin. These chlorine-containing resins are suspension polymerization, emulsion polymerization,
Although a product obtained by any conventional production method such as a bulk polymerization method may be used, a suspension polymerization method is generally preferred. One of these chlorine-containing resins may be used, or two or more of them having different degrees of polymerization may be used in combination.

Also, the plasticizer is used in an amount of 30 to 70 parts by weight, preferably 40 to 60 parts by weight, and 0.5 to 7.0 parts by weight, preferably 1.0 to 100 parts by weight, per 100 parts by weight of the chlorine-containing resin.
5.0 parts by weight of a lubricant and / or heat stabilizer, 0 to 5.0 parts by weight, preferably 0.5 to 4.0 parts by weight of an antifogging agent or surfactant, 0 to 1.0% by weight, Preferably 0.02-
0.5% by weight of antifog, 0 to 3.0 parts by weight, preferably 0.1 to 0.5 part by weight of ultraviolet absorber, 0.01 to 2.
0 parts by weight, preferably 0.03 to 1.0 parts by weight of a hindered amine light stabilizer, and 0 to 5.0 parts by weight, preferably 1 to 1.0 parts by weight of an antiblocking agent can be blended.

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; Phthalates and dioctyl adipates are suitable.

Examples of the above lubricant and / or heat stabilizer include polyethylene wax, fatty acid amide stearic acid,
Chelators such as zinc stearate, barium stearate, calcium stearate, barium ricinoleate, and organic phosphites, and epoxy resins.

The antifogging agent or the surfactant can be any one which can be used usually, and for example, a polyhydric alcohol partial ester type comprising a polyhydric alcohol and a higher fatty acid is preferable. Specific examples of such a product include, for example, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate sorbitan and glycerin condensate and higher fatty acid ester, sorbitan and alkylene glycol condensate and higher fatty acid ester Sorbitan surfactants such as: glycerin monolaurate, glycerin monostearate, diglycerin monostearate, diglycerin monolaurate, diglycerin monobalmitate, triglycerin monostearate, tridiglycerin monostearate and the like Glycerin-based surfactants: polyethylene glycol-based surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalmitate polyethylene glycol alkyl phenyl ether : Other trimethylolpropane surfactants such as trimethylolpropane monostearate: Pentaerythritol surfactants such as pentaerythritol monopalmitate, pentaerythritol monostearate, dipentaerythritol monostearate: or isomers thereof And the like.

The antifogging agent includes, for example, a polymer containing a perfluoroalkyl group or a perfluoroalkenyl group, or a low molecular fluorine surfactant, and is generally at least 0.001% by weight, preferably at least 0.001% by weight. Preferred are those that have a solubility in water of at least 0.01% by weight and have the ability to reduce the surface tension of water at 25 ° C. to 35 dyn / cm or less, preferably 30 dyn / cm or less. The perfluoroalkyl group may have an oxygen atom interposed in the carbon chain.

Commercial products used as the antifogging agent include, for example, Unidyne DS-401 and Unidyne DS-401.
403, Unidyne DS-451 (manufactured by Daikin Industries, Ltd.), Megafac F-142D, Megafac F-
177 (from Dainippon Ink and Chemicals, Inc.), Florad FC-170, Florard FC-176, Florado FC-430 (from Sumitomo 3M), Surflon S-141, Surflon S-145, Surflon S-
381, Surflon S-382, Surflon S-393
(Above, manufactured by Asahi Glass Co., Ltd.).

As the above-mentioned ultraviolet absorber, a generally known ultraviolet absorber such as, for example, a benzotriazole type, a benzophenone type or a salicylic acid type is used. Benzotriazole-based compounds include 2- (2′-hydroxy-3 ′,
5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t
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-tert-butylphenyl) benzotriazole, 2- (2'hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5
'-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

As benzophenones, 2,2
'-Dihydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-oct Xybenzophenone and the like.

Examples of salicylic acid include phenyl salicylate and paraoctyl phenyl salicylate. These UV absorbers can be used alone or
Although a combination of two or more species can be used, benzophenones and benzotriazoles are particularly preferred.

The above hindered amine light stabilizers are well-known, for example, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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 root decyl-1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidinol, and 3,9-bis (2-hydroxy-1,1-dimethyl Ethyl) -2,4,8,1
0 Tetraspiro [5,5] undecane and an ester of butanetetracarboxylic acid.

Further, other usual resin additives such as a filler, an antioxidant, an antistatic agent, and a coloring agent can be contained as required. Fillers are usually used to suppress stickiness of the film or to maintain heat retention, such as silica, talc, aluminum hydroxide, hydrotalcite, calcium sulfate, calcium silicate, Inorganic materials such as calcium hydroxide, kaolin clay, mica, alumina, sodium aluminate, lithium phosphate, and zirconium hydroxide are exemplified. The type and amount of the filler are determined according to the thickness of the film.
Usually 0.05-7.0% by weight, preferably 0.1-5.
It is used in the range of 0% by weight.

In order to mix each of the resin additives with the above-mentioned chlorine-containing resin, a necessary amount thereof is weighed, and the mixture is kneaded into a ribbon blender, a Banbury mixer, a super mixer or other conventionally known compounding machines and mixers. .

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

When the thickness of the film of the present invention is too small, the strength becomes insufficient, which is not preferable. On the other hand, when the thickness is too large, it is inconvenient for filming work and the like. Preferably 0.05 to 0.2 m
It is appropriate to set the range of m.

Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples of the present invention, but the present invention is not limited thereto.

[0038]

【Example】

(Examples 1 to 4, Comparative Examples 1 to 6) After a vinyl chloride resin composition having the composition shown in Table 1 was mixed by ordinary means,
A 0.1 mm agricultural vinyl chloride resin film was formed by calendering, and the weather resistance, the high-frequency sewing machine adhesion, and the ballooning property were evaluated by the following methods. Table 1 shows the results
Shown in

[0039]

[Table 1]

[Test Method] (1) Weather Resistance A film composed of each composition was prepared by using an accelerated weather resistance tester (Metal Weather KU-R3C manufactured by Dainippon Plastics Co., Ltd.).
In IA), the change in the deterioration of the appearance of the film after 100 hours was visually evaluated. (2) Weldability of high frequency sewing machine A film of each composition was adhered to each film of the same composition by a high frequency sewing machine for 1 m, and the peel strength and the degree of welding were evaluated by a tensile tester. (3) Blow-out property After immersing the film composed of each composition in water at 40 ° C. for 24 hours, the film was taken out and evaluated visually.

[Evaluation Criteria] (1) Weather resistance: no browning observed ○: slight browning observed △: browning observed ×: many browning observed XX: browning observed over the entire surface ( 2) Adhesion of high frequency sewing machine ◎… The whole surface is adhered and the material is broken. Peeling off (3) Speech bubbles ◎… No ballooning ○… Slight ballooning occurs △… Ballooning occurs ×… Some ballooning occurs ××… Many ballooning occurs

[0042]

The agricultural vinyl chloride resin film formed from the chlorine-containing resin composition of the present invention has a specific organophosphate compound and a nitrogen-containing resin content in addition to the conventional formulation, as is clear from the results shown in Table 1. By using polyhydric alcohol and magnesium oxide together, compared to conventional vinyl chloride resin film for agricultural use, it has excellent weather resistance, so it can be spread over a long period of time, and has less ballooning and good adhesion to high frequency sewing machines There is a big effect that.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/521 C08K 5/521

Claims (1)

[Claims] 1. A compound represented by the general formula [1] (wherein R1, R2, R3 and R4 are the same or different and have an alkyl group having 6 to 18 carbon atoms, based on 100 parts by weight of the chlorine-containing resin).
A cycloalkyl group, an aralkyl group, an allyl group, an alkyl-substituted allyl group, or an alkenyl group) in an amount of 0.1 to 5.0 parts by weight, preferably 0.3 to 3.5 parts by weight, R}, R6 and R7 in the formula are the same or different and represent a (CH ₂ ) _n OH (n = 1 to 4) group. The nitrogen-containing polyhydric alcohol represented by
1 to 3.0 parts by weight, preferably 0.03 to 2.0 parts by weight, and 0.01 to 3.0 parts by weight of a magnesium oxide compound;
A stabilized chlorine-containing resin composition characterized by preferably containing 0.03 to 2.0 parts by weight. Embedded image Embedded image