JPS59105044A - Weather-resistant vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. which gives an agricultural vinyl chloride resin film having excellent weather resistance, by blending a sulfonate ester compd. and an epoxy compd. CONSTITUTION:1-50pts.wt. sulfonate ester compd. of the formula [wherein R is an alkyl group (pref. 6-22C alkyl); R' is an alkyl or aryl group (pref. phenyl group which may be substituted with a 1-4C alkyl)] and 0.2-10pts.wt. epoxy compd. such as epoxidized soybean oil are blended with 100pts.wt. vinyl chloride resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a vinyl chloride resin composition. More specifically, the present invention relates to a vinyl chloride resin composition for producing agricultural vinyl chloride resin films having excellent weather resistance.

With the development of greenhouse horticulture, the demand for covering materials for greenhouses has increased, and agricultural vinyl chloride resin films, which are inexpensive, durable, and have a good balance of performance, have been 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 hard films such as 2M stretched polyethylene terephthalate film and hard vinyl chloride resin film, but these are expensive and require complicated construction. Problems such as this have not yet become widespread.

In addition, for agricultural vinyl chloride resin films, vinyl chloride resin is made from homopolymer to copolymer 9, modified by blending with other resins 91, and plasticizer is made from the commonly used dioctyl phthalate (hereinafter abbreviated as DOP). Although other plasticizers were used, or stabilizers and other additives were added, changed, or increased in amount, only a few additives were found to be effective in improving weather resistance. There were only phosphoric acid esters such as tricresyl phosphate and tricylyl phosphate (%, Publication No. 50-35542, Japanese Patent Publication No. 51-3740).

Even agricultural vinyl chloride films improved in this way and having good weather resistance have a useful life of about one year, or two years at most.

In view of this situation, the present inventors have conducted intensive studies on improving the weather resistance of vinyl chloride resin films, and have found that the weather resistance is significantly improved by blending both an alkyl sulfonic acid ester and an epoxy compound with vinyl chloride resin. They discovered this, conducted further research, and finally completed the present invention.

That is, the present invention provides a vinyl chloride resin having the general formula ■η R-5-0-R' (1)1 [wherein R is an alkyl group and R/ is an alkyl group or an aryl group. ] A weather-resistant vinyl chloride resin composition characterized by blending a sulfonic 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 evaporated vinyl acetate, ethylene, fluoropyrene, alkyl vinyl ether, acrylic ester, methacrylic ester, acrylic ester, acrylonitriated Examples include copolymers with vinylidene chloride and the like, and 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.

An important point in the present invention is that a sulfonic acid ester compound represented by general formula I and an epoxy compound are blended with the vinyl chloride resin.

In the sulfonic acid ester compound used in the present invention, 10 is an alkyl group or an aryl group. ) Any compound may be used as long as it is a compound represented by R, but preferred among them are those in which R has 6 to 22 carbon atoms, more preferably 10 to 18 carbon atoms.
and R' is a phenyl group or a phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms, and particularly preferred ones are those in which R and R' satisfy the above conditions. It is something. The alkyl group may be linear or branched, or may be unsaturated and have 1 to 3 unsaturated bonds.

Some specific examples include phenyl hexane sulfonate, enyl tocosane sulfonate, tolyl octanesulfonate, tolyl undecane sulfonate, xylyl hexadecane sulfonate, ethyl-phenyl eicosane sulfonate, tocosan. ethyl-phenyl sulfonate,
Examples include octadecyl 2-ethylhexane sulfonate, which may be used alone or in combination of two or more. It goes without saying that sulfonic acid ester compounds other than these may also be used.

The amount of sulfonic acid ester compound added is based on plasticizer, stabilizer,
Although p varies depending on the amount of the epoxy compound etc., it is preferably 1 to 50 parts by weight per 100 parts by weight of vinyl chloride resin. If the amount of the sulfonic acid ester compound added is less than 1 part by weight, no improvement in weather resistance will be obtained even if the epoxy compound is blended, and if it is used in excess of 50 parts by weight, bleeding may occur9 and physical properties will deteriorate, which is undesirable. result.

In the present invention, epoxy compounds used in combination with sulfonic acid ester compounds include epoxidized soybean oil, epoxidized linseed oil, plasticizer-type epoxy compounds such as epoxidized fatty acid esters, and epichlorohydrin and bisphenol A.
Alternatively, coniboxy resins such as condensates and partial polymers with low molecular weight phenolic resins are also included.

The amount of epoxy compound added is vinyl chloride resin 10.
0.2 to 10 parts by weight is suitable), preferably 1 to 5 parts by weight. If the epoxy compound is less than 0.62 parts by weight, the weather resistance will hardly improve even if a sulfonic acid ester compound is added. Moreover, if more than 10 parts by weight of the epoxy compound is added, it will bleed, and if it is made into a film, it will stick to each other, and if the film is spread out in a greenhouse, it will collect too much dust, making it unusable for practical use.

The composition of the present invention can be obtained by mixing a vinyl chloride resin with a sulfonic acid ester compound and an epoxy compound using a pre-mixer or mixer.

Furthermore, when forming a film, a plasticizer such as DOP, a stabilizer such as calcium stearate, barium stearate, etc. are blended with the above composition, and the calender method, solvent casting method,
It can be molded by a known method such as melt extrusion.

In addition, other additives such as plasticizers, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, droplet agents, lubricants, fillers, pigments, etc. may be added to the above formulations as necessary to put them into 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, spots may occur, which may gradually impair the translucency. It is desirable to use an organotin-based stable wound surface/acid ester or phosphate ester to suppress the generation of polyurethane. However, it goes without saying that they are sufficiently weather resistant even when not used together.

It is preferable to apply an acrylic resin to the agricultural film to make it dust-proof, since this reduces dust adhesion and provides good translucency even after long-term use. Dust-proofing also improves weather resistance.

Since the composition of the present invention has improved weather resistance, when used as an agricultural film, it is now necessary to re-cover once every 2 to 3 years, which is extremely important in industry. It is in good condition.

- The present invention will be explained below with reference to Examples. (1 part each of this product, sorbitan monopalmitate) 2. ．． 5 parts and 0.3 parts of an ultraviolet absorber, as a sulfonic acid ester compound, a phenyl ester mixture of an alkyl sulfonic acid having 12 to 18 carbon atoms (trademark: Mesamono σ', manufactured by Bayer AG) 1
After adding 2 parts of epoxy resin (trademark "Epicote 828" manufactured by Shell Chemical Co., Ltd.) and kneading the mixture for 10 minutes using a calendar roll at 170°C, a film having a thickness of 0.13 mm was obtained. Table 2 shows the results of the outdoor stretching test for this film.

Comparative Example 3 A film having 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 the sulfonic acid ester compound used in Example 2.

Table 2 shows the results of the outdoor stretching test for this film.

Comparative Example 4 Example 2 except that epoxy resin is not used in Example 2
Films with a thickness of 0.13 mm were obtained in the same manner as above.

Table 2 shows the results of the outdoor stretching test for this film.

Table 2 It can be seen from Table 2 how excellent the coating material according to the present invention is.

Example 3 100 parts of vinyl chloride-vinyl acetate (5% by weight) copolymer, 55 parts of DOP, 8 parts of tricresyl phosphate, 1 part of calcium stearate, 1.5 parts of zinc stearate and 0.2 parts of ultraviolet absorber Two parts of octadecyl dodecanesulfonate and three parts of epoxidized linseed oil were added as a sulfonic acid ester compound, and the mixture was kneaded for 10 minutes with a calendar roll at 170°C, to obtain a film with a thickness of 0.13 mm.

The results of the outdoor expansion test for this film are shown in Table 3.

Example 4 Except for using tolyl pentadecane sulfonate in place of octadecyl dodecane sulfonate in Example 8, the performance was m.
A film having a thickness of O-13 nm was obtained in the same manner as in Example 3. 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 phenyl tocosane sulfonate and 2 parts of tetradecyl dodecane sulfonate were used in place of octadecyl dodecane sulfonate. 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 sulfonic acid ester compound or epoxidized linseed oil was not used8. The film of Comparative Example 5 does not contain epoxidized linseed oil, and the film of Comparative Example 6 does not contain epoxidized linseed oil.

Table 3 shows the results of outdoor stretching tests for these films.

Table 3 It can be seen from Table 3 how excellent the coating material obtained by the present invention is.

Example 6 and Comparative Example 7.8 An acrylic resin solution prepared under the following conditions was coated on one side of the film obtained in Example 1 and Comparative Example 1.2 using a roll coater so that the coating amount was 3b2. It was coated and dried for 30 seconds in an open air at 120°C 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 part of lauryl peroxide and 100 parts of toluene were placed in a reaction vessel and heated to 70°C.
The reaction was carried out for 5 hours. After cooling to room temperature, the solution was diluted with Improbeer alcohol to obtain a coating solution with a resin concentration of 30%.

An exposure test was conducted by spreading these films in a simple greenhouse with the acrylic resin coated side facing outward. The results are shown in Table 4.

The film of Example 6 in Table 4 not only had excellent weather resistance, but also had little dust adhesion, so it could provide a sufficient amount of light transmission for a long time, and was excellent as a coating material, having a particularly long life.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) A vinyl chloride resin having the general formula (1) [wherein R is an alkyl group and χ is an alkyl group or a haaryl group]. ] A weather-resistant vinyl chloride resin composition comprising a sulfonic acid ester compound represented by the following formula and an epoxy compound. 2 R of the sulfonic acid esterified metal represented by general formula I
is an alkyl group having 6 to 22 carbon atoms, and R' is a phenyl group or a phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms. Composition according to item 1.