JP2005130845A - Drip-proofness giving composition for resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a drip-proofness giving composition for a resin film, capable of forming the film which is excellent in transparency and the drip-proofness at a low temperature and retains the drip-proofness even at a high temperature. <P>SOLUTION: This composition is obtained by conducting addition reaction of 0.1-3.0 mol of ethylene oxide and 0.1-1.0 mol of propylene oxide with 1 mol of a sorbitan fatty acid ester, wherein the ester is obtained by reacting 1 mol of solbitan in which 1,4-sorbitan is contained in an amount of ≥60 wt% with 1-3 mol of a 16-18C saturated fatty acid. The composition is mixed into a resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a novel drip-free imparting composition and a drip-free resin film, and more particularly excellent in drip resistance at low temperatures, excellent drip-free durability at high temperatures, and prevention of ejection during film storage. The present invention relates to an excellent drip-free imparting composition and an agricultural resin film containing the composition.

  2. Description of the Related Art Conventionally, in growing vegetables, a method has been adopted that enables cultivation even at low temperatures by using a resin film such as polyethylene or vinyl chloride as a covering material. In this case, since the resin film to be used is required to always transmit sunlight, a method of kneading a non-drip imparting agent in advance is employed in order to prevent fogging due to moisture on the surface of the resin film. As this non-droplet imparting agent, higher fatty acid esters such as polyethylene glycol, glycerin, sorbitan and sorbitol, and nonionic surfactants obtained by adding ethylene oxide or propylene oxide to these higher fatty acid esters have been used.

For example, Patent Document 1 discloses a compound in which 0.1 to 5.0 mol of ethylene oxide and 0.1 to 5.0 mol of propylene oxide are added to a normal sorbitan fatty acid ester as a drip-free imparting agent. Proposed. Patent Document 2 discloses that a compound obtained by esterifying an adduct of 1 to 20 mol of ethylene oxide of sorbitol with a fatty acid having 10 to 22 carbon atoms is added to a vinyl chloride resin as a drip-free imparting agent. Yes. Patent Document 3 proposes an adduct of sorbitan fatty acid ester of propylene oxide, butylene oxide, or phenylene oxide in an amount of 0.1 to 3.0 mol as a drop-less modifier for a vinyl chloride synthetic resin film.
However, none of the compounds can solve all the problems to be solved by the present invention.
JP-A-57-3847 (pages 1 to 5) Japanese Patent Publication No. 55-9431 (pages 1 to 4) Japanese Patent Publication No. 48-31748 (Pages 1-3)

As performance required for the above-mentioned agricultural drip-free resin film, (1) good drip-free property (low-temperature drip-free property) at low temperatures in winter.
(2) Exhibit excellent drip-free properties immediately after film stretching.
(3) In particular, from the viewpoint of economic efficiency, the agricultural vinyl film has been exposed to high temperatures especially in the summer, as the number of cases in which it is used for a long period of less than one year to one year or more has increased. Drip-proof nature should last for a long time. (High temperature durability)
(4) The film is excellent in transparency. (Spout prevention)
However, the present situation is that an agricultural resin film that satisfies all has not been developed yet. The problem to be solved by the present invention is to obtain an agricultural drip-free resin film having all the performances of (1), (2), (3) and (4).

As a result of research to solve the problems of such agricultural resin films, the present inventors have obtained a specific amount of ethylene oxide and a specific amount of a compound obtained by esterifying a specific sorbitan with a specific higher fatty acid. It has been found that a compound to which propylene oxide has been added exhibits the above-described excellent drip-free property, and has led to the completion of the present invention.
That is, the present invention relates to a 1,4 sorbitan fatty acid ester obtained by reacting 1 to 3 mol of a saturated fatty acid having 16 to 18 carbon atoms with respect to 1 mol of sorbitan having an amount of 1,4 sorbitan in the sorbitan of 60% by weight or more. A droplet-free imparting composition for a resin film obtained by adding 0.1 to 3.0 mol of ethylene oxide and 0.1 to 1.0 mol of propylene oxide, and 0 to 100 parts by weight of the resin. It is related with the resin film for agriculture characterized by containing 0.2-5.0 weight part.

  By using the droplet-free imparting composition of the present invention, it is possible to obtain an agricultural resin film that is very excellent in low-temperature droplet-free properties, high-temperature durability and droplet-free properties immediately after film stretching, and further in preventing ejection. .

The present invention will be described in detail below.
The drip property-imparting composition of the present invention (hereinafter referred to as a drip agent) comprises 1 mol of sorbitan in which the amount of 1,4 sorbitan in sorbitan is 60% by weight or more, and saturated fatty acids 1 to 3 having 16 to 18 carbon atoms. 0.1 mol of ethylene oxide and 0.1-1 mol of propylene oxide are present in the presence of an alkali catalyst with respect to 1 mol of 1,4 sorbitan fatty acid ester obtained by dehydrating the mol in the presence of an alkali catalyst. It can be obtained by adding 0.0 mol.
At that time, propylene oxide may be added after addition of ethylene oxide, ethylene oxide may be added after addition of propylene oxide, or ethylene oxide and propylene oxide may be added simultaneously.

  The content of 1,4 sorbitan in sorbitan used as a raw material for the sorbitan fatty acid ester according to the present invention, the number of moles of ethylene oxide added and the number of moles of propylene oxide added to 1 mole of sorbitan fatty acid ester form the basis of the present invention. The content of 1,4 sorbitan in the sorbitan is 60% by weight or more, preferably 70% by weight or more, and the addition mole number range of ethylene oxide is 0.1 to 3.0 moles, and propylene oxide The added mole number range of is 0.1 to 1.0 mol. When the 1,4 sorbitan content is less than 60% by weight, the low-temperature droplet-less property is slightly inferior, and the film ejection prevention property is also inferior. When the added mole number of ethylene oxide exceeds 3.0 moles, the high temperature sustainability is inferior, and when the added mole number of propylene oxide exceeds 1.0 mole, the high temperature sustainability is particularly inferior. Further, when the number of added moles of either ethylene oxide or propylene oxide is less than 0.1 mole, it is also not preferable because the film ejection preventing property is poor.

  Examples of the saturated fatty acid having 16 to 18 carbon atoms include palmitic acid and stearic acid. When a saturated fatty acid having less than 16 carbon atoms is used, the low-temperature drip resistance is excellent, but the high-temperature sustainability is slightly inferior. When a saturated fatty acid having 18 or more carbon atoms is used, the high-temperature sustainability is excellent but the ejection prevention property is remarkably inferior. The reaction mole number of the saturated fatty acid having 16 to 18 carbon atoms with respect to 1 mole of sorbitan according to the present invention is in the range of 1 to 3 moles, particularly preferably 1.5 to 2.5 moles. If it exceeds 3 mol, the low-temperature drip resistance will be unfavorable, and if it is less than 1 mol, the high-temperature sustainability will be remarkably inferior.

  The sorbitan having a 1,4-sorbitan content of 60% by weight according to the present invention can be obtained by a known method. For example, it can be obtained by subjecting D-sorbitol to a dehydration reaction at 100 to 200 ° C. under an acidic catalyst, but is not particularly limited. Moreover, what is marketed can also be used.

  The droplet-free preparation of the present invention thus obtained is usually added in an amount of 0.2 to 5.0 parts by weight, preferably 1 to 2.5 parts by weight, based on 100 parts by weight of the resin. The droplet-free agent of the present invention can be used in combination with conventional droplet-free agents, known stabilizers, and plasticizers as long as it does not impair the object of the present invention when producing a resin film. In order to obtain it, it is also possible to use together with a well-known fluorine type and silicone type antifog agent. As the known fluorine-based antifogging agent, conventionally used fluorine-based surfactants or copolymer oligomers can be used, and they may be used alone or in combination of two or more.

  Examples of the resin used in the present invention include olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene, ethylene-propylene block copolymers, ethylene-propylene random copolymers, Ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, etc. Olefin copolymer, ethylene-vinyl acetate copolymer, copolymer of olefin and polar vinyl compound such as ethylene-methyl methacrylate copolymer, acrylic resin such as polymethyl methacrylate, ionomer resin, polyester resin, polyamide Resin, polycarbonate resin, phenol resin, polyvinyl chloride resin, It can be exemplified polyurethane resin, etc., but particularly useful for the polyvinyl chloride resin. Polyvinyl chloride resins include vinyl chloride homopolymer, vinyl chloride and vinyl acetate and esters thereof, acrylic acid and esters thereof, methacrylic acid and esters thereof, ethylene, propylene, vinylidene chloride, maleic acid, fumaric acid And other copolymers.

The droplet-free film of the present invention is produced by a known method. For example, in a vinyl chloride resin film, a resin additive is compounded into a vinyl chloride resin with a ribbon blender, a Banbury mixer, a super mixer or other conventionally known blending machines and mixers, and a melt extrusion molding method (T-die method, Inflation method, etc.), calendering method, solution casting method and the like.
For polyolefin resin films, master batches or resin powders with high concentrations of resin additives are used, and additive-free resins (pellets or powders, etc.) are blended to achieve appropriate additive concentrations. Manufactured by a melt extrusion molding method (T-die method, inflation method, etc.).

  EXAMPLES Next, the present invention will be described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. It is a measurement of the content of 1,4-sorbitan in sorbitan, but the column is Silicone SE-30 10% (manufactured by GL Sciences) with gas chromatography (GC, GC-14B, manufactured by Shimadzu Corporation). The temperature was raised as 150 to 280 ° C. Here, the area percentage of 1,4-sorbitan was regarded as the content (% by weight).

A. Synthesis of Dropless Agent (1) of the Present Invention A glass autoclave was charged with 1000 g of industrial sorbitol and 1 g of methanesulfonic acid, dehydrated under reduced pressure at 140 ° C. for 4 hours, and neutralized and desalted with 89% phosphoric acid. Thereafter, 890 g of sorbitan having a 1,4 sorbitan content of 75% by weight was obtained. To 1.0 mol of the obtained sorbitan, 1.5 mol of industrial stearic acid (palmitic acid 35%, stearic acid 65%) and 3 g of caustic soda were charged, and the temperature was raised to 190 to 200 ° C. while introducing N ₂ gas. Sorbitan stearate was synthesized by esterification for 5 hours.
After this, N ₂ substitution was performed and 3.0 mol of ethylene oxide was added at 150 ° C. for 2 hours, and then 0.5 mol of propylene oxide was added at 145 ° C. for 1 hour, and phosphoric acid was added. The catalyst was neutralized and then desalted to obtain a tan wax [polyoxyethylene (3.0 mol) polyoxypropylene (0.5 mol) sorbitan stearate]. The dripping agent (1) of the present invention is subjected to the test described below.

B. Synthesis of Dropless Agents (2) to (7) of the Present Invention As in A, the dropless agents (2) to (7) of the present invention were synthesized as shown in Table 1.
The drop-free agents (2) to (7) of the present invention are also used for the tests described below.

C. Synthesis of Comparative Dropless Agents (1) to (7) A comparative dropletless agent was synthesized as described below and subjected to the test described below.
The formulation is shown in Table 2.

i) Synthesis of comparative drop-free agent (1) 1.0 mol of industrial sorbitol is charged in a glass autoclave, 1.5 mol of industrial palmitic acid (65% palmitic acid, 35% stearic acid) and 3 g of caustic soda are charged. While introducing N ₂ gas, the temperature was raised to 220 to 250 ° C. and esterification was performed for 5 hours to synthesize sorbitan palmitate.
A small amount of the obtained sorbitan palmitate was sampled, and after hydrolysis, the hydrophilic group composition was analyzed by gas chromatography, and it was confirmed that the 1,4 sorbitan content was 42% by weight. Thereafter, N ₂ substitution was carried out, and 0.3 mol of propylene oxide was added at 145 ° C. over 1 hour, and the catalyst was neutralized with phosphoric acid, followed by desalting treatment to form a tan wax [polyoxypropylene (0 .3 mol) sorbitan palmitate ester].

ii) Synthesis of comparative drop-free agent (2) 1.0 mol of industrial sorbitol was charged into a glass autoclave, 1.5 mol of industrial stearic acid (35% palmitic acid, 65% stearic acid) and 3 g of caustic soda were charged. While introducing N ₂ gas, the temperature was raised to 220 to 250 ° C. and esterification was performed for 5 hours to synthesize sorbitan stearate.
A small amount of the obtained sorbitan stearate was sampled, and after hydrolysis, the hydrophilic group composition was analyzed by gas chromatography, and it was confirmed that the 1,4 sorbitan content was 45% by weight. Thereafter, N ₂ substitution was carried out and 0.5 mol of propylene oxide was added at 145 ° C. over 1 hour. The catalyst was neutralized with phosphoric acid and then desalted to give a tan wax [polyoxypropylene (0 .5 mol) sorbitan stearic acid ester].

ii) Synthesis of comparative drop-free agent (3) 1.0 mol of industrial sorbitol was charged into a glass autoclave, 1.5 mol of industrial stearic acid (35% palmitic acid, 65% stearic acid) and 3 g of caustic soda were charged. While introducing N ₂ gas, the temperature was raised to 220 to 250 ° C. and esterification was performed for 5 hours to synthesize sorbitan stearate.
A small amount of the obtained sorbitan stearate was sampled, and after hydrolysis, the hydrophilic group composition was analyzed by gas chromatography, and it was confirmed that the 1,4 sorbitan content was 55% by weight. After this, N ₂ substitution was carried out and 0.5 mol of ethylene oxide and 0.5 mol of propylene oxide were added at 145 ° C. over 1 hour. The catalyst was neutralized with phosphoric acid and then desalted, and a tan wax [Polyoxyethylene-propylene (0.5 mol) sorbitan stearate ester] was obtained.

iii) Synthesis of comparative dripping agent (4) A glass autoclave was charged with 1000 g of industrial sorbitol and 1 g of methanesulfonic acid, dehydrated under reduced pressure at 140 ° C. for 4 hours, and neutralized and desalted with 89% phosphoric acid. 890 g of sorbitan having a 1,4 sorbitan content of 70% by weight was obtained. To 1.0 mol of the obtained sorbitan, 1.3 mol of industrial palmitic acid (65% palmitic acid, 35% stearic acid) and 3 g of caustic soda were charged, and the temperature was raised to 190 to 200 ° C. while introducing N ₂ gas. Sorbitan palmitate was synthesized by esterification for 5 hours.
Thereafter, the catalyst was neutralized with phosphoric acid and then desalted to obtain a tan wax [sorbitan palmitate ester].

iv) Synthesis of comparative drop-free agent (5) A glass autoclave was charged with 1000 g of industrial sorbitol and 1 g of methanesulfonic acid, dehydrated under reduced pressure at 140 ° C. for 4 hours, and neutralized and desalted with 89% phosphoric acid. 890 g of sorbitan having a 1,4 sorbitan content of 75% by weight was obtained. 1.0 mol of sorbitan obtained was charged with 1.5 mol of industrial myristic acid (95% myristic acid, 5% palmitic acid) and 3 g of caustic soda under a basic catalyst at 190 to 200 ° C. while introducing N ₂ gas. The temperature was raised to 5 and esterification was carried out for 5 hours to synthesize sorbitan myristic acid ester.
Thereafter, N ₂ substitution was carried out, and 0.3 mol of propylene oxide was added at 145 ° C. over 1 hour, and the catalyst was neutralized with phosphoric acid, followed by desalting treatment to form a tan wax [polyoxypropylene (0 .3 mol) sorbitan myristic acid ester].

v) Synthesis of comparative drop-free agent (6) A glass autoclave was charged with 1000 g of industrial sorbitol and 1 g of methanesulfonic acid, dehydrated under reduced pressure at 140 ° C. for 4 hours, and neutralized and desalted with 89% phosphoric acid. 890 g of sorbitan having a 1,4 sorbitan content of 73% by weight was obtained. To 1.0 mol of the obtained sorbitan, 1.5 mol of industrial stearic acid (palmitic acid 35%, stearic acid 65%) and 3 g of caustic soda were charged, and the temperature was raised to 190 to 200 ° C. while introducing N ₂ gas. Sorbitan stearate was synthesized by esterification for 5 hours.
Thereafter, N ₂ substitution was carried out and 2.0 mol of ethylene oxide was added at 160 ° C. over 2 hours. The catalyst was neutralized with phosphoric acid and then desalted to give a tan wax [polyoxyethylene (2 0.0 mol) sorbitan stearate].

vi) Synthesis of comparative drop-free agent (7) 1.0 mol of industrial sorbitol is charged into a glass autoclave, 1.5 mol of industrial stearic acid (35% palmitic acid, 65% stearic acid) and 3 g of caustic soda are charged. While introducing N ₂ gas, the temperature was raised to 220 to 250 ° C. and esterification was performed for 5 hours to synthesize sorbitan stearate.
A small amount of the obtained sorbitan stearate was sampled, and after hydrolysis, the hydrophilic group composition was analyzed by gas chromatography, and it was confirmed that the 1,4 sorbitan content was 55% by weight. Thereafter, N ₂ substitution was carried out and 2.0 mol of ethylene oxide was added at 145 ° C. over 2 hours. The catalyst was neutralized with phosphoric acid and then desalted to give a tan wax [polyoxyethylene (2 0.0 mol) sorbitan stearate].

D. Production of film 100 parts by weight of polyvinyl chloride resin, 30 parts by weight of dioctyl phthalate, 10 parts by weight of dioctyl adipate, 5 parts by weight of tricresyl phosphate, 4 parts by weight of epoxy resin, 3 parts by weight of calcium-zinc liquid stabilizer, calcium -2 parts by weight of a zinc-based powder stabilizer and 2.5 parts by weight of a droplet-free agent were mixed and kneaded at 180 ° C with a hot roll to prepare a film having a thickness of 0.1 mm, and the droplet-free property was evaluated.

E. Evaluation of droplet-free properties The droplet-free properties of each film were evaluated, and the results shown in Table 3 were obtained.
Evaluation basis ◎: Uniformly wet and transparent on one side ○: Uniformly wet and transparent on almost one side ×: Partially transparent part, but totally opaque XX: Completely opaque Low temperature initial: A film is placed on the upper inclined box, outside Air temperature: 5 ° C, water temperature: 15 ° C,
Evaluate the wet state of the film after 12 hours at an inclination angle of 10 degrees.
Sustained at high temperature: A film is placed on the upper inclined box, outside temperature: 20 ° C, water temperature: 50 ° C,
Evaluate the wet state of the film after 5 days at an inclination angle of 10 degrees.
Outdoor initial: Evaluate the wet state 5 hours after the house extension.
Outdoor persistence: Evaluation of the wet state on October 28, 2002, and February 3, 2003.

F. Evaluation of spout prevention properties The spout properties of each film were determined with the naked eye, and the results shown in Table 3 were obtained.
Evaluation criteria 5: The same as the additive-free film, the surface is transparent and no white powder is observed 4: The white powder is deposited in stripes 3: The white thin film covers almost the entire surface State 2: State covered with a white thin film 1: State where viscous oil is sprayed over the entire surface

  As is apparent from the results shown in Table 3, by using the drip-free imparting composition of the present invention, low-temperature drip-free properties, high-temperature durability, drip-free properties immediately after film stretching, and ejection prevention properties A very excellent agricultural resin film can be obtained.

Claims (2)

  Ethylene oxide is added to 1 mol of sorbitan fatty acid ester obtained by reacting 1 to 3 mol of saturated fatty acid having 16 to 18 carbon atoms with respect to 1 mol of sorbitan in which the amount of 1,4 sorbitan in sorbitan is 60% by weight or more. A drip-free imparting composition for a resin film obtained by adding ~ 3.0 mol and 0.1 to 1.0 mol of propylene oxide. An agricultural resin film excellent in droplet resistance and jetting prevention properties, comprising the droplet-free imparting composition according to claim 1 in an amount of 0.2 to 5.0 parts by weight per 100 parts by weight of the resin.