JPS6211024B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vinyl chloride resin composition with excellent weather resistance. With the development of greenhouse horticulture, the demand for covering materials for greenhouses has increased, and agricultural vinyl chloride resin film, which is inexpensive and has a well-balanced performance, remains the most widely used to this day. However, due to the recent severe petroleum situation, there is a demand for long-term use of coating materials, and there is a demand for coating materials that are durable and have a long service life. Permanent covering materials include glass, glass fiber-reinforced acrylic sheets, corrugated polycarbonate sheets, and other hard films such as biaxially oriented polyethylene terephthalate films and hard vinyl chloride resin films, but these are expensive and require complicated construction. Due to such problems, it has not become widely popular. In addition, for agricultural vinyl chloride resin films, vinyl chloride resin can be made from homopolymers to copolymers, modified by blending with other resins, and plasticizers can be made from dioctyl phthalate (hereinafter abbreviated as DOP), which is commonly used. Although other plasticizers have been substituted, or stabilizers and other additives have been added, changed, or increased in amount, only a few additives have been found to be effective in improving weather resistance. There were only phosphate esters such as tricresyl phosphate and tricylyl phosphate (Special Publication No. 50-35542, Special Publication No. 51-3740).
issue). Even agricultural vinyl chloride films improved in this way and having good weather resistance had a useful life of about one year, or two years at most. In view of this situation, the present inventors have conducted extensive studies on improving the weather resistance of vinyl chloride resin films, and have found that weather resistance is significantly improved by blending both an alkyl sulfonic acid ester and an epoxy compound with vinyl chloride resin. After discovering this, they conducted further research and finally completed the present invention. That is, the present invention provides vinyl chloride resin with the general formula [In the formula, X and Y are an alkyl group or an aryl group, R
is an alkylene group. ] This is a weather-resistant vinyl chloride resin composition characterized by blending an alkanedisulfonic acid ester compound represented by the following and an epoxy compound. The vinyl chloride resin used in the present invention includes polyvinyl chloride, other monomers mainly composed of vinyl chloride, such as vinyl acetate, ethylene, propylene,
Alkyl vinyl ether, acrylic ester,
Examples include copolymers with methacrylic acid esters, acrylonitrile, vinylidene chloride, etc., or blends of these with chlorine-containing polymers or copolymers such as chlorinated polyethylene, chlorinated polypropylene, and chlorinated polyisoprene.
In addition, in the present invention, as long as the above-mentioned resin is used, its type, degree of polymerization, and polymerization method are not affected in any way. The alkanedisulfonic acid ester compound (hereinafter referred to as the present sulfonic acid ester) used in the present invention has the general formula [In the formula, X and Y are an alkyl group or an aryl group, R
is an alkylene group. ] Any compound is acceptable as long as it is represented by
Among these, preferred is a phenyl group in which X and Y are a phenyl group or a phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms, R has 6 to 22 carbon atoms,
More preferably, it has 10 to 18 alkylene groups. In addition, the above-mentioned alkylene group is not limited to a linear one, and may be a branched one. Moreover, it may not be saturated but may have 1 to 3 unsaturated bonds. Specific examples include diphenyl hexanedisulfonate, diphenyl docosandisulfonate, diphenyl hexadecanedisulfonate, ditolyl octanedisulfonate, ditolyl undecanedisulfonate, dixylyl hexadecanedisulfonate, diethyl phenyl eicosandylsulfonate, docosan. Diethyl phenyl disulfonate, phenyl tolyl hexadecane disulfonate,
Examples include phenylxylyl pentadecanedisulfonate, which may be used alone or in combination of two or more. Of course, alkanedisulfonic acid ester compounds other than these can also be used, and other sulfonic acid ester compounds, especially alkyl alkyl sulfonates and aryl alkyl sulfonates having about 6 to 22 carbon atoms, can also be used in combination. It is also effective to use The amount of the sulfonic acid ester added may vary depending on the amount of plasticizer, stabilizer, epoxy compound, etc., but is preferably 1 part by weight per 100 parts by weight of vinyl chloride resin.
~50 parts by weight. If the amount of this sulfonic acid ester added is less than 1 part by weight, no improvement in weather resistance will be obtained even if the epoxy compound is added, and if it is used in excess of 50 parts by weight, it may bleed or deteriorate physical properties, resulting in unfavorable results. Become. In the present invention, the epoxy compounds used in combination with the present sulfonic acid ester include epoxidized soybean oil,
Examples include plasticizer-type epoxy compounds such as epoxidized linseed oil and epoxidized fatty acid esters, and epoxy resins such as condensates and partial polymers of epichlorohydrin and bisphenol A or low molecular weight phenolic resins. The appropriate amount of the epoxy compound to be added is 0.2 to 10 parts by weight per 100 parts by weight of vinyl chloride resin.
Preferably it is 1 to 5 parts by weight. If the epoxy compound is less than 0.2 parts by weight, the weather resistance will hardly improve even if the present sulfonic acid ester compound is blended. Moreover, if more than 10 parts by weight of the epoxy compound is added, it will bleed, and when made into a film, it will stick to each other, and when the film is spread out in a house, dust will adhere to it, making it unusable for practical use. The composition of the present invention can be obtained by mixing the vinyl chloride resin with the sulfonic acid ester and the epoxy compound in a blender or kneader. Furthermore, when making a film, a plasticizer such as DOP, a stabilizer such as calcium stearate, barium stearate, etc. are blended into the above composition, and the mixture is molded by a known method such as a calendar method, solution casting method, or melt extrusion method. can. Additionally, other additives such as plasticizers, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, droplet agents, lubricants, fillers, pigments, etc. may be added to the above formulations for practical use. Ru. In addition, when using the composition of the present invention as an agricultural film, if an epoxy resin is used as the epoxy compound, "bumps" may occur.
Since translucency may be gradually impaired, it is desirable to use an organic tin stabilizer, phosphite ester, or phosphate ester to suppress the generation of "bubbles". However, it goes without saying that they are sufficiently weather resistant even when not used together. In addition, it is preferable to apply an acrylic resin to the agricultural film to make it dustproof, since this reduces dust adhesion even after long-term use and provides good light transmission. Furthermore, dustproofing improves weather resistance. Since the composition of the present invention has improved weather resistance,
When used as an agricultural film, conventional film that required re-stretching every year now only needs to be stretched once every 2 to 3 years, making it very suitable for industry. The present invention will be explained below with reference to Examples. Note that parts in the examples represent parts by weight. Example 1 Vinyl chloride homopolymer (degree of polymerization 1200) 100
50 parts of DOP, 1 part each of zinc stearate, barium stearate, 2 parts of sorbitan monostearate, and 0.1 part of ultraviolet absorber, 5 parts of diphenyl hexadecanedisulfonate, and 5 parts of epoxidized soybean oil.
After kneading with a calender roll at 180°C for 5 minutes, a film with a thickness of 0.1 mm was obtained. Table 1 shows the results of an exposure test (hereinafter referred to as outdoor spreading test) conducted by spreading this film in a simple greenhouse. Note that the results of the outdoor expansion test were determined visually. ○ indicates good condition with no change; △ indicates deterioration; × indicates progressed deterioration and is unsuitable as a covering material. Comparative Example 1 A film with a thickness of 0.1 mm was obtained in the same manner as in Example 1, except that the present sulfonic acid ester was not used and 5 parts of DOP was added instead. Table 1 shows the results of the outdoor stretching test for this film. Comparative Example 2 A film with a thickness of 0.1 mm was obtained in the same manner as in Example 1, except that epoxidized soybean oil was not used. Table 1 shows the results of the outdoor stretching test for this film.

[Table] Example 2 Vinyl chloride homopolymer (degree of polymerization 1400) 100
part, DOP 35 parts, tricresyl phosphate 5 parts
1 part each of calcium stearate, zinc stearate, 2.5 parts of sorbitan monopalmitate, and 0.3 parts of an ultraviolet absorber, a mixture of a phenyl ester of an alkyl sulfonic acid having 12 to 18 carbon atoms and a diphenyl ester of an alkyl disulfonic acid (by weight) ratio 6:4) and 12 parts of epoxy resin (trademark “Epicoat”)
828” (manufactured by Ciel Kagaku Co., Ltd.) was added and kneaded for 10 minutes with a calendar roll at 170℃, and the thickness was 0.13 mm.
A film of mm was obtained. Table 2 shows the results of the outdoor stretching test for this film. Comparative Example 3 A film with a thickness of 0.13 mm was obtained in the same manner as in Example 2, except that 12 parts of DOP was added instead of using the sulfonic acid ester mixture.
Table 2 shows the results of the outdoor stretching test for this film. Comparative Example 4 A film with a thickness of 0.13 mm was obtained in the same manner as in Example 2, except that the epoxy resin was not used. Table 2 shows the results of the outdoor stretching test for this film.

[Table] Example 3 Vinyl chloride-vinyl acetate (5% by weight) copolymer
100 parts, DOP55 parts, tricresyl phosphate 8
1 part calcium stearate, 1.5 parts zinc stearate, 0.2 parts UV absorber, 2 parts dixylyl dodecanedisulfonate, and 3 parts epoxidized linseed oil.
After kneading with a calender roll at 170°C for 10 minutes, a film with a thickness of 0.13 mm was obtained. Table 3 shows the results of the outdoor stretching test for this film. Example 4 A film with a thickness of 0.13 mm was obtained in the same manner as in Example 3, except that phenyl xylyl pentadecanedisulfonate was used instead of dixylyl dodecanedisulfonate. Table 3 shows the results of the outdoor stretching test for this film. Example 5 A film with a thickness of 0.13 mm was obtained in the same manner as in Example 3, except that 1 part of diphenyl docosandisulfonate and 2 parts of dixylyl dodecanedisulfonate were used instead of dixylyl dodecanedisulfonate. Ta. Table 3 shows the results of the outdoor stretching test for this film. Comparative Examples 5 and 6 A film with a thickness of 0.13 mm was obtained in the same manner as in Example 3, except that the present sulfonic acid ester or epoxidized linseed oil was not used. The film of Comparative Example 5 does not contain the present sulfonic acid ester, and the film of Comparative Example 6 does not contain epoxidized linseed oil. The results of the outdoor expansion test for these films are shown in the third
Shown in the table.

The coating materials in [Table] have excellent weather resistance.
Example 6 and Comparative Examples 7 and 8 On one side of the films obtained in Example 1 and Comparative Examples 1 and 2, an acrylic resin solution prepared under the following conditions was coated with a roll coater so that the amount was 3 g/m ² It was coated and dried in an oven at 120°C for 30 seconds to obtain a dustproof film. Preparation of acrylic resin solution 70 parts of methyl methacrylate, 25 parts of n-butyl methacrylate, 5 parts of methacrylic acid, 0.5 parts of lauryl peroxide and 100 parts of toluene were placed in a reaction vessel and reacted at 70°C for 5 hours. After cooling to room temperature, the solution was diluted with isopropyl alcohol to obtain a coating solution with a resin concentration of 30%. An outdoor expansion test was conducted on these films with the acrylic resin coated side facing outward. 4th result
Shown in the table.

[Table] The film of Example 6 not only has excellent weather resistance, but also
Because there is little dust adhesion, a sufficient amount of light can be transmitted over a long period of time, making it an excellent covering material with a particularly long lifespan.

Claims (1)

[Claims] 1 General formula for vinyl chloride resin [In the formula, X and Y are an alkyl group or an aryl group, R
is an alkylene group. ] A weather-resistant vinyl chloride resin composition comprising an alkanedisulfonic acid ester compound represented by the following formula and an epoxy compound. 2 X and Y of the alkanedisulfonic acid ester compound represented by the general formula are phenyl groups or phenyl groups having 1 to 3 alkyl groups having 1 to 4 carbon atoms, and R is alkylene having 6 to 22 carbon atoms. A composition according to claim 1, wherein the composition is a group consisting of: