JPH11335486A - Antifog composition for synthetic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifog composition for a synthetic resin capable of imparting excellent antifog properties, and improving a blocking phenomenon. SOLUTION: This antifog composition for a synthetic resin comprises (A) one or more kinds selected from a fatty acid ester of sorbitol, glycerol or polyglycerol, a fatty acid mono- or sesqui-ester of sorbitan, an EO(ethylene oxide) adduct of a fatty acid ester of the sorbitol, the sorbitan, the glycerol or the polyglycerol, and a fatty acid ester of an EO adduct of a polyhydric alcohol, and (B) one or more kinds selected from a fatty acid ester of pentaerythritol, a PO(propylene oxide) adduct of a fatty acid ester of the sorbitan or the sorbitol, and a fatty acid ester of the sorbitan obtained by esterifying 1 mol sorbitan with >=2 mol fatty acid, in the ratio of the components A/B regulated so as to be (30/70)-(90/10). The synthetic resin film is obtained by compounding 0.1-5.0 pts.wt. antifog composition with 100 pts.wt. synthetic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antifogging composition for synthetic resins which can impart excellent antifogging performance and blocking resistance by being added to a synthetic resin such as polyvinyl chloride.
The present invention also relates to a synthetic resin film having improved stickiness and blocking properties using the same, and having excellent low-temperature antifogging properties, initial antifogging properties, and antifogging durability.

[0002]

2. Description of the Related Art Polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer resin and the like are used as synthetic resin coating materials used for facility horticulture such as agricultural houses and tunnel cultivation. I have. Since these synthetic resins are hydrophobic, the water evaporated from the ground and crops aggregates on the film surface, causing clouding due to the attachment of fine water droplets, causing a decrease in light transmittance and dropping of water droplets. Causes poor growth and disease. Therefore, a method is generally used in which a surfactant such as a sorbitan fatty acid ester called an anti-fogging agent is kneaded into a resin and bleed out to make the film surface easier to wet.

On the other hand, a polyvinyl chloride resin film most frequently used as an agricultural film is blended with a large amount of a plasticizer and a small amount of a stabilizer in order to obtain a desired film physical property and weather resistance. Due to the nature of soft vinyl chloride itself, such as causing bleed-out over time,
The films are tightly adhered to each other, and the blocking phenomenon is likely to occur. In addition, because the film contains an anti-fogging agent, if the film is wound up with moisture and the anti-fogging agent is dissolved, the anti-fogging agent adheres to each other after drying and blocks more firmly. Cause In fact, when such a film is used in an agricultural house or tunnel, the opening and closing parts such as the entrance and the vent are overlapped with each other, so there are many opportunities to attach and remove the film during work, especially the vent In order to wind up the film, if the film causes blocking, a large amount of labor is required at the time of opening and closing, and there are problems such as damage and breakage of the film.

The antifogging agent generally used for agricultural vinyl chloride resin films is a mixture of a sorbitan fatty acid ester and an ethylene oxide adduct thereof.
As the fatty acid of the ester, stearic acid and palmitic acid are generally used, and the number of moles of ethylene oxide added is often 2 to 3 mol. However, while these antifoggants exhibit excellent antifogging performance, they have the greatest blocking.

As a means for solving the blocking phenomenon while maintaining the anti-fogging property of such a film, a method using a compound having a high melting point has been proposed, for example, a polyhydric alcohol behenate ester (Japanese Patent Publication No. -3692, Japanese Patent Publication No. 54
No. 30698) is used as an anti-fogging agent, but is inferior in anti-fogging properties (especially initial anti-fogging property and low-temperature anti-fogging property). Although there is a method of adding alcohol (Japanese Patent Application Laid-Open No. 2-49050), there is a problem that sufficient anti-blocking performance cannot be obtained, and at the present time, both anti-fogging property and anti-blocking property have not been achieved. .

Accordingly, an object of the present invention is to provide an antifogging agent composition for synthetic resins which can impart excellent antifogging performance and improve the blocking phenomenon.

[0007]

According to the present invention, there are provided: A component: sorbitol, fatty acid ester of glycerin or polyglycerin (A-1), sorbitan fatty acid mono- or sesquiester (A-2), sorbitol, sorbitan,
At least one selected from the group consisting of ethylene oxide adducts of fatty acid esters of glycerin or polyglycerin, and fatty acid esters of ethylene oxide adducts of sorbitol, sorbitan, glycerin or polyglycerin (A-3) (however, fatty acid esters The fatty acid constituting is a saturated or unsaturated fatty acid having 12 to 18 carbon atoms, the average addition mole number of ethylene oxide is 0.1 to 10 mol), B component: pentaerythritol fatty acid ester (B-1),
At least one selected from the group consisting of propylene oxide adduct of a fatty acid ester of sorbitan or sorbitol (B-2), and sorbitan fatty acid ester (B-3) obtained by esterifying a fatty acid to 2.0 moles or more per mole of sorbitan (B-3) However, the fatty acid constituting the fatty acid ester has 12 or more carbon atoms.
18 saturated or unsaturated fatty acids, and the average number of moles of propylene oxide added is 1 to 4 moles).
An antifogging agent composition for a synthetic resin in which the weight ratio of the components is A / B = 30/70 to 90/10, and this antifogging agent composition,
It is a synthetic resin film prepared by mixing 0.1 to 5.0 parts by weight with respect to 00 parts by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The component A of the present invention is a base for exhibiting antifogging performance and is selected from the group consisting of the above (A-1) to (A-3). The fatty acid constituting the fatty acid ester of the component A is a saturated or unsaturated fatty acid having 12 to 18 carbon atoms, preferably myristic acid, palmitic acid, stearic acid, oleic acid and mixtures thereof. As for the degree of esterification of the component A of the present invention, the degree of esterification represented by the following formula is preferably less than 0.5 from the viewpoint of anti-fogging property such that the wettability does not deteriorate and the bleed rate does not decrease.

[0009]

(Equation 1)

The average number of moles of ethylene oxide added in the above (A-3) is 0.1 to 10 mol, preferably 1 to 6 mol. These ethylene oxide adducts can be used as a mixture of two or more.

[0011] Of the component A of the present invention, (A-1)
Glycerin monostearate, diglycerin sesquistearate, diglycerin monopalmitate, tetraglycerin tristearate, etc. Palmitate etc., as (A-3), POE (2) sorbitol sesquistearate, POE (1) sorbitan monopalmitate, POE (3) sorbitan sesquistearate, POE (6) sorbitan monostearate And one or more of these can be used. In (A-3), fatty acid esters of ethylene oxide adduct of sorbitol,
Alternatively, an ethylene oxide adduct of a fatty acid ester of sorbitan, glycerin or polyglycerin is preferred. Here, POE (n) indicates that it is a polyoxyethylene n-mol adduct.

The component (B) of the present invention further imparts the desired anti-fogging property and improvement of the blocking phenomenon to the component (A), and is selected from the group consisting of the above (B-1) to (B-3). . The fatty acid constituting the fatty acid ester of component B has 12 carbon atoms.
-18 saturated or unsaturated fatty acids, preferably lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and mixtures thereof. Fatty acids have 12 carbon atoms
If it is smaller, the antifogging durability is reduced, and if it is more than 18, the low temperature antifogging property is reduced and a whitening phenomenon on the film surface is not preferred.

[0013] Of the component B, (B-1) is preferably one obtained by esterifying a fatty acid with 1 to 2.5 mol per mol of pentaerythritol. Specific examples include pentaerythritol monostearate, pentaerythritol sesquistearate, pentaerythritol sesquipalmitate, pentaerythritol sesquimyristate, pentaerythritol sesquilaurate, and pentaerythritol dilaurate.

(B-2) is preferably one obtained by esterifying a fatty acid with 1 to 2.5 mol per 1 mol of sorbitan or sorbitol. The number of moles of propylene oxide added is 1 to 4 moles relative to 1 mole of the fatty acid ester, and if it is less than 1 mole, sufficient improvement of the blocking phenomenon cannot be obtained, and if it exceeds 4 moles, the anti-fogging durability decreases. It is not preferable. Specifically, POP (1) sorbitan monostearate, POP (1) sorbitan monopalmitate, POP
(1) sorbitan sesquimyristate, POP (2) sorbitan monostearate, POP (4) sorbitan distearate and the like. Here, POP (n) indicates that it is a polyoxypropylene n-mol adduct.

(B-3) is a method of adding a fatty acid to 1 mole of sorbitan.
It is esterified to 2.0 mol or more, and in order to achieve both sufficient improvement of the blocking phenomenon and anti-fogging property, esterified fatty acid of 2.0 to 2.5 mol is preferable. Specifically, sorbitan distearate, sorbitan dipalmitate, sorbitan 2.5 stearate, sorbitan
2.5 millistate and the like.

When selecting the component B of the present invention, it is preferable to use the component (B-2) if the initial antifogging property and the low-temperature antifogging property are excellent and the blocking phenomenon is improved. When the antifogging durability is excellent and the blocking phenomenon is improved, it is preferable to use (B-3). In particular, when it is desired to mainly improve the blocking phenomenon, it is preferable to use (B-1). Further, one or more B components can be used.

The mixing ratio of the component A and the component B in the antifogging agent composition of the present invention is A / B = 30/70 to 90/10, preferably 50/50 to 80/20 by weight ratio. If A / B is less than 30/70, the low-temperature antifogging property or the antifogging durability is lowered, or the film surface is whitened, which is not preferable. On the other hand, if the ratio A / B is larger than 90/10, a sufficient improvement in the blocking phenomenon cannot be obtained.

The method of using the anti-fogging agent composition of the present invention is, for example, a method of kneading at the time of molding a synthetic resin, or dissolving the anti-fogging agent composition of the present invention in a suitable solvent, and using this solution as a synthetic resin molded article. A method of kneading at the time of molding is preferable.

Synthetic resins which can be used for the antifogging agent composition of the present invention include polyvinyl chloride resins such as polyvinyl chloride, vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl chloride copolymer resin, and polyethylene. And a polyolefin resin such as an ethylene-vinyl acetate copolymer resin (EVA), etc., and is particularly suitable for a vinyl chloride resin in which a blocking phenomenon is a problem. Especially number of polymerization degree 8
Polyvinyl chloride of from 00 to 2000, and copolymers mainly composed of vinyl chloride are preferred.

The amount of the antifogging agent composition of the present invention added to the synthetic resin is 0.1 to 100 parts by weight of the resin from the viewpoint of antifogging performance.
It is preferably at least 5.0 parts by weight, more preferably at most 5.0 parts by weight, particularly preferably from 0.5 to 4.0 parts by weight, from the viewpoint of preventing excessive bleed-out of the antifogging agent, stickiness of the surface and blooming phenomenon.

The synthetic resin film of the present invention may further comprise a plasticizer, a stabilizer, if necessary, in addition to the antifogging composition of the present invention.
Stabilizing aids (antioxidants, epoxy compounds, etc.), lubricants,
UV absorbers, fillers, coloring agents, light stabilizers, antifog agents, antistatic agents, processing aids, and the like can be added.

Examples of the plasticizer include di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-isodecyl phthalate, di-n-butyl phthalate, and di-2-butyl phthalate.
Examples include phthalic esters such as ethylhexyl isophthalate, adipic esters such as diisononyl adipate, phosphoric esters such as tricresyl phosphate, and epoxidized soybean oil.

Examples of the stabilizer include metal soap stabilizers such as zinc stearate, barium stearate, calcium stearate, calcium laurate, barium ricinoleate, dibutyltin dilaurate, dibutyltin dimethylmalate, dibutyldilauryl mercaptide and the like. And the like.

Examples of the stabilizing aid used in combination with the stabilizer include phosphites such as triphenyl phosphate and trinonylphenyl phosphate, and 3,5-di-t-butyl-4-hydroxy. Antioxidants such as phenolic compounds such as toluene, sulfur-containing compounds such as dialkylthiobispropionate, epichlorohydrin-bisphenol A polymer (epoxy resin), epoxy compounds such as epoxidized fatty acid esters, dibenzoyl Β-diketone compounds such as methane are exemplified.

Examples of the lubricant include stearic acid, fatty acid amide, polyethylene wax and the like. As the ultraviolet absorber, 2- (2'-hydroxy-3 ', 5'-di-t
-Butylphenyl) -5-chlorobenzotriazole,
Benzotriazole-based compounds such as 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole, benzophenone-based compounds such as 2,2'-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone;
Examples include salicylic acid ester compounds such as phenyl salicylate and pt-butylphenyl salicylate.

Examples of the filler include metal hydroxides such as magnesium hydroxide and aluminum hydroxide, inorganic oxides such as silica and alumina, and inorganic compounds such as metal silicates such as talc, magnesium silicate and calcium silicate. . Examples of the coloring agent include phthalocyanine blue, titanium oxide, carbon black and the like. Examples of the light stabilizer include hindered amine compounds.

Examples of the antifog include fluorine-based surfactants and fluorine-based oligomers. Examples of the antistatic agent include fatty acid monoglyceride and sorbitan fatty acid ester.

The synthetic resin film of the present invention is preferably a vinyl chloride resin film, particularly preferably an agricultural vinyl chloride resin film used for agricultural purposes.

[0029]

By adding the antifogging agent composition of the present invention to a synthetic resin film, especially a vinyl chloride resin film, excellent initial antifogging properties, low-temperature antifogging properties and antifogging durability are imparted, Further, the blocking phenomenon can be improved.

[0030]

Examples 1 to 16 The components A and B shown in Table 1 were blended in the proportions shown in Table 1 to prepare antifogging compositions of the present invention. Among the components A and B, those that are commercially available use them, and those that are not commercially available are prepared by charging a polyhydric alcohol and a fatty acid at a desired mixing ratio, at a temperature of 190 to 245 ° C., under normal pressure or reduced pressure. And an ethylene oxide or propylene oxide addition was performed as necessary. The fatty acid ester of EO adduct of sorbitol in the component A was synthesized by the method described in JP-B-55-9431, pp. 2-3, Reference Examples 1 and 2. Using this anti-fogging agent composition, a film was produced by the following method, and this film was evaluated for anti-fogging property, blocking resistance and transparency by the following method. Table 2 shows the results.

<Production Method of Film> A compound having the following composition was put into a Henschel mixer and stirred and mixed for 10 minutes to prepare a compound. This was melted and kneaded with a test roll having a surface temperature of 170 ° C. for 7 minutes, and then pressed at a temperature of 170 ° C. for 5 minutes to obtain a film having a thickness of 100 μm.

Composition: Polyvinyl chloride resin (average degree of polymerization: 1300) 100 parts by weight Di-2-ethylhexyl phthalate 45 parts by weight (Kao Co., Ltd., Vinicizer 80) Tricresyl phosphate 5 parts by weight (Daiwa Chemical Industry Co., Ltd. ) Stabilizer (Ba-Zn) 1.5 parts by weight (Katsuta Kako Co., Ltd., BZ-330M) Stabilizer 1.0 parts by weight (Katsuta Kako Co., Ltd., PSE-1020B) Epoxy resin 1.5 parts by weight (Shell, Epicoat) 828) Methylene bisstearyl amide 0.3 parts by weight (Nippon Kasei Co., Ltd., Bisamide LA) 1.0 parts by weight (Hayashi Kasei Co., Ltd., Micron White # 5000S) Antifog 0.1 parts by weight (Daikin Industries, Ltd., Unidyne DS) −403) 2.0 parts by weight of antifogging agent composition of the present invention <Test for antifogging performance> Small house made of stainless steel pipe (length 3)
30 x 290 x 250 mm height, roof surface angle 12 with respect to horizontal plane
Degree), cover the side with a commercially available agricultural polyvinyl chloride resin film, cover the roof with a film sample for anti-fog testing, immerse this house in a constant temperature water tank maintained at a constant temperature,
Leave in a constant-temperature room (the house is a closed system with the floor covered with water and filled with water vapor). Initial anti-fogging property after leaving at room temperature 5 ° C / water temperature 15 ° C for 2 hours, room temperature 5 ° C
/ Low temperature antifogging after leaving for 6 hours at a water temperature of 15 ° C, and room temperature of 5
The antifogging durability after standing for 25 days, 50 days, 75 days, and 100 days at 40 ° C / water temperature of 40 ° C was evaluated according to the following criteria.

Evaluation rank 5: Completely transparent and no fogging 4: Almost transparent, but slightly water droplets 3: Large water droplets adhere, but quite transparent 2: Large water droplets overall Adhered and opaque 1: Fine water droplets adhered entirely and were opaque. For example, an evaluation score of 3-4 is close to 3 at a level between 3 and 4, and 4-3 is 3 A level between 4 means close to 4, and a value of 3 or more is suitable for practical use.

For the initial anti-fogging property, the above-mentioned evaluation rank was evaluated according to the following criteria. ◎: Level exceeding 4 after 2 hours ○: Level 4 after 2 hours Δ: Level 3 after 2 hours ×: Level 2 after 2 hours XX: Level 1 after 2 hours For example, ○ to △ mean that the level is between △ and △ and close to ○, and △ to ○ mean that the level is between ○ and △ and close to △.

<Blocking Test> A sample (10 × 15 cm) was sampled from a molded polyvinyl chloride film, immersed in ion-exchanged water for 2 hours, and then two identical films were stuck together and drained with a pressure crawl. Was done. Furthermore, a 3 × 7 cm test piece was cut out from the sample piece, and 16 g /
While applying a pressure of cm ² , it was left in a constant temperature bath at 70 ° C. for 2 hours. Next, the test piece was taken out from the thermostat, allowed to cool in a thermostat at 23 ° C., and subjected to a peeling test with Tensilon. The smaller the load [peeling strength (g)] required for the peeling, the better the blocking resistance.

<Transparency test> In order to test the blooming phenomenon caused by the antifogging agent on the film surface, the film was subjected to 40
C. for 2 weeks and the haze meter measured the turbidity of the film. The transparency rank obtained from this was expressed in the following five stages.

Transparency rank ：: No whitening is observed at all ○: Very slight whitening is observed Δ: Slight whitening is observed ×: Whitening is clearly observed XX: Opaque △ to △ mean the level between △ and 、 and close to ○, and △ to ○ mean the level between ○ and △ and close to △.

Comparative Examples 1 to 5 For comparison, sorbitan monopalmitate (Kao Corp., Rheodol SP-P10) was used instead of the antifoggant composition of the present invention having the composition shown in the examples (Comparative Example 1). ), POE (2) sorbitan monostearate (Comparative Example 2), sorbitan monobehenate (Comparative Example 3), POE (2) sorbitan monostearate / glycerin monostearate = 70/30 (Comparative Example 4), POE (2) A film was prepared by adding 2.0 parts by weight of sorbitan monostearate / stearyl alcohol = 70/30 (Comparative Example 5), and the antifogging property, blocking resistance and transparency were evaluated in the same manner as in the examples. Table 2 shows the results.

[0039]

[Table 1]

[0040]

[Table 2]

Claims (2)

[Claims] A component: sorbitol, fatty acid ester of glycerin or polyglycerin (A-1), sorbitan fatty acid mono- or sesquiester (A-2), and sorbitol;
At least one selected from the group consisting of fatty acid esters of sorbitan, fatty acid esters of glycerin or polyglycerin, and fatty acid esters of sorbitol, sorbitan, ethylene oxide adducts of glycerin or polyglycerin (A-3); The fatty acid constituting the fatty acid ester is a saturated or unsaturated fatty acid having 12 to 18 carbon atoms, the average number of moles of ethylene oxide added is 0.1 to 10 mol), component B: pentaerythritol fatty acid ester (B-1),
At least one selected from the group consisting of propylene oxide adduct of a fatty acid ester of sorbitan or sorbitol (B-2), and sorbitan fatty acid ester (B-3) obtained by esterifying a fatty acid to 2.0 moles or more per mole of sorbitan (B-3) However, the fatty acid constituting the fatty acid ester has 12 or more carbon atoms.
18 saturated or unsaturated fatty acids, and the average number of moles of propylene oxide added is 1 to 4 moles).
An antifogging agent composition for synthetic resins wherein the weight ratio of the components is A / B = 30/70 to 90/10. 2. A synthetic resin film comprising the antifogging composition according to claim 1 in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the synthetic resin.