JP2009051881A - Non-dropping property-imparting composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-dropping property-imparting composition and a resin composition containing the same and excellent in non-dropping property, transparency, dust-proof property and sticking resistance, particularly an agricultural resin film. <P>SOLUTION: The non-dropping property-imparting composition comprises (A) 30-60 mass% of a nonionic surfactant having a melting point of ≥40°C obtained by reacting 1 mol of a fatty acid ester with 0.1-1.0 mol of propylene oxide, wherein the fatty acid ester is obtained by reacting 1 mol of sorbitol with 1-3 mol of a saturated fatty acid and has a proportion of a peak area derived from a 1,4-sorbitan fatty acid ester of 30-50% as measured by gas chromatography, (B1) 10-40 mass% of a fatty acid diethanolamide having a melting point of ≤30°C or the like, and (C1) 30-60 mass% of a fatty acid diethanolamide having a melting point of ≥40°C or the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a droplet-free imparting composition, a resin composition containing the composition, and an agricultural resin film. More specifically, the droplet-free property at a low temperature, the droplet-free durability at a high temperature, and the film-forming property. The present invention relates to a drip-proofing composition excellent in transparency, transparency during storage, dustproofness and stickiness resistance, and a resin composition containing the composition and an agricultural resin film.

  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 drip-free imparting agent in advance is employed in order to prevent the resin film surface from being fogged by moisture. 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 proposes a compound obtained by adding ethylene oxide and propylene oxide to a sorbitan fatty acid ester as a droplet-free imparting agent. In Patent Document 2, an alkyldi (polyoxyalkylene) amine ester compound A and a compound B having a melting point of 35 ° C. or lower are used as an antifogging agent. Further, Patent Document 3 uses an anti-fogging agent mixed component comprising an ethylene oxide adduct of a fatty acid ester of alkyldiethanolamide and sorbitan (or sorbitol). Patent Document 4 includes alkyldiethanolamine, fatty acid diethanolamide, polyoxyethylene alkylamine fatty acid ester as an antifogging imparting agent and antistatic agent composition in which diglycerin fatty acid ester, glycerin fatty acid ester, and polyoxyethylene sorbitan fatty acid ester are mixed. Etc. are used as antifogging agents.

However, these conventional technologies have problems such as stickiness caused by excessive bleed-out of the antifogging agent and drip resistance not sufficiently maintained in summer. Therefore, an agricultural resin film balanced in all of these performances has not yet been obtained.
JP 57-3847 (page 1-5) Japanese Patent Laid-Open No. 11-263887 (page 1-15) Japanese Patent No. 3868893 (page 1-20) JP 2006-161012 A (page 1-8)

  The object of the present invention is required for agricultural drip-free resin films, in winter (low temperature) drip-free (low temperature wettability), summer (high temperature) drip-free persistence (high temperature sustainability), A dripping-imparting agent that satisfies all of the droplet-free properties (initial wettability) immediately after stretching, transparency during film formation (transparency), transparency after storage (transparency over time), dust resistance and stickiness resistance And to provide a drip-free resin film for agriculture.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyoxy having a melting point of 40 ° C. or higher, in which the proportion of 1,4-sorbitan fatty acid ester produced by intramolecular dehydration of sorbitol or its fatty acid ester is a specific amount. A droplet-free imparting composition comprising a propylene sorbitol fatty acid ester, a fatty acid diethanolamide having a melting point of 30 ° C. or lower or a specific polyoxyethylene alkyl (or alkenyl) amine, a fatty acid diethanolamide having a melting point of 40 ° C. or higher, or a specific amine ester compound When used for an agricultural resin film, the obtained resin film was found to be excellent in the above-described droplet-free property, transparency, dustproof property, and stickiness resistance, and completed the present invention.

  That is, the present invention is a fatty acid ester obtained by reacting 1 to 3 mol of saturated fatty acid with respect to 1 mol of (A) sorbitol, and the ratio of the peak area derived from 1,4-sorbitan fatty acid ester by gas chromatography measurement is 30. 30 to 60% by mass of a nonionic surfactant having a melting point of 40 ° C. or higher, obtained by reacting 0.1 to 1.0 mol of propylene oxide with respect to 1 mol of fatty acid ester which is ˜50%, (B1) Fatty acid diethanolamide having a melting point of 30 ° C. or lower, or polyoxyethylene alkylamine having a melting point of 30 ° C. or lower, or polyoxyethylene obtained by adding 2 to 3 moles of ethylene oxide to 1 mol of (B2) alkylamine or alkenylamine Fatty acid having 10 to 40% by mass of alkenylamine and (C1) melting point of 40 ° C. or higher Ethanolamide, or (C2) 1 mol of alkylamine, 1 to 2 mol of polyoxyethylene alkylamine obtained by adding 2 to 3 mol of ethylene oxide and 1 to 2 mol of saturated fatty acid, and melting point of 40 ° C or higher In particular, the present invention relates to a droplet-free imparting composition comprising 30 to 60% by mass of the amine ester compound.

  The present invention also relates to a resin composition containing 0.1 to 5.0% by mass of the droplet-free imparting composition.

  The present invention also relates to an agricultural resin film comprising the resin composition.

  It was found that when the composition according to the present invention was used, the obtained agricultural resin film was excellent in low temperature wettability, high temperature sustainability, initial wettability, transparency, dust resistance and stickiness resistance.

  The present invention will be described in detail below.

  The (A) nonionic surfactant used in the present invention is a fatty acid ester obtained by reacting 1 to 3 mol, preferably 1 to 2 mol of a saturated fatty acid with respect to 1 mol of sorbitol. , 4-Sorbitan fatty acid ester-derived peak area ratio is obtained by reacting 0.1 to 1.0 mol of propylene oxide with respect to 1 mol of fatty acid ester of 30 to 50%, preferably 40 to 45%. Is. Here, the use of the amount of 1,4-sorbitan fatty acid ester in the fatty acid ester within the above range is to maintain the drip resistance and the like originally required as an antifogging agent while preventing dust, etc. It is for securing. (A) The production method of the nonionic surfactant may be a known method. For example, a saturated fatty acid is added to sorbitol in the presence of an alkali catalyst in the presence of an alkali catalyst to a sorbitol fatty acid ester obtained by dehydration reaction. It is obtained by adding propylene oxide under pressure conditions.

  The nonionic surfactant (A) has a melting point of 40 ° C. or higher. If the melting point is less than 40 ° C., the high temperature sustainability and stickiness resistance of the agricultural resin film using the melting point will be impaired. Specifically, polyoxypropylene (0.1-1.0 mol) sorbitol (or sorbitan) stearic acid (1-3 mol) ester, polyoxypropylene (0.1-1.0 mol) sorbitol (or sorbitan) ) Palmitic acid (1-3 mol) ester, polyoxypropylene (0.1-1.0 mol) sorbitol (or sorbitan) behenic acid (1-3 mol) ester, etc. are mentioned, and two or more of these are mixed May be used.

  The ratio of the component (A) in the drip-free imparting composition of the present invention is 30 to 60% by mass, preferably 35 to 50% by mass. This is because if the amount is less than 30% by mass, the high temperature sustainability and stickiness resistance are impaired, while if it exceeds 60% by mass, the low temperature wettability, initial wettability, transparency and dust resistance are impaired.

  Examples of the fatty acid diethanolamide having a melting point of 30 ° C. or lower of the component (B1) used in the present invention include hexanoic acid diethanolamide, heptanoic acid diethanolamide, octanoic acid diethanolamide, oleic acid diethanolamide, and the like, and beef tallow fatty acid diethanolamide. And mixed fatty acids such as palm oil fatty acid diethanolamide, palm oil fatty acid diethanolamide, and soybean oil fatty acid diethanolamide. Among these, oleic acid diethanolamide and coconut oil fatty acid diethanolamide are preferable. Moreover, you may use these 2 or more types in mixture.

  Polyoxyethylene alkylamine or polyoxyethylene alkenylamine having a melting point of 30 ° C. or less obtained by adding 2 to 3 moles of ethylene oxide to 1 mole of alkylamine or alkenylamine of component (B2) used in the present invention As polyoxyethylene (2-3 mol) octylamine, polyoxyethylene (2-3 mol) laurylamine, polyoxyethylene (2-3 mol) oleylamine and the like, and further polyoxyethylene (2-3) Mol) Mixed aliphatic amines such as coconut oil alkylamine, polyoxyethylene (2-3 mol) beef tallow alkylamine, and the like. Among these, polyoxyethylene (2 mol) laurylamine, polyoxyethylene (2 mol) coconut oil alkylamine, and polyoxyethylene (2.5 mol) tallow alkylamine are preferable. Moreover, you may use these 2 or more types in mixture.

  The melting point of the components (B1) to (B2) used in the present invention is 30 ° C. or lower. When the melting point exceeds 30 ° C., the low temperature wettability, initial wettability of the agricultural resin film using this component, This is because transparency and dust resistance are impaired.

  The ratio of the components (B1) to (B2) in the droplet-less imparting composition of the present invention is 10 to 40% by mass, preferably 15 to 30% by mass. This is because if it is less than 10% by mass, the low temperature wettability, initial wettability, transparency and dust resistance are impaired, and conversely if it exceeds 40% by mass, the high temperature sustainability and stickiness resistance are impaired.

  Examples of the fatty acid diethanolamide having a melting point of 40 ° C. or higher as the component (C1) used in the present invention include lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, and behenic acid diethanolamide. Of these, palmitic acid diethanolamide and stearic acid diethanolamide are preferred. Moreover, you may use these 2 or more types in mixture.

  Obtained by reacting 1 to 2 mol of polyoxyethylene alkylamine obtained by adding 2 to 3 mol of ethylene oxide to 1 mol of alkylamine of component (C2) used in the present invention, and 1 to 2 mol of saturated fatty acid. Examples of the amine ester compound having a melting point of 40 ° C. or higher include polyoxyethylene (2 to 3 mol) palmitylamine stearic acid (1 to 2 mol) ester, polyoxyethylene (2 to 3 mol) stearylamine stearic acid (1 to 2 mol). 2 mol) ester, polyoxyethylene (2-3 mol) stearylamine palmitic acid (1-2 mol) ester, polyoxyethylene (2-3 mol) palmitylamine behenic acid (1-2 mol) ester, And polyoxyethylene (2-3 mol) stearylamine behenic acid (1-2 mol) ester. Among these, polyoxyethylene (2 to 3 mol) stearylamine stearic acid (1 to 2 mol) ester and polyoxyethylene (2 to 3 mol) stearylamine palmitic acid (1 to 2 mol) ester are preferable. Moreover, you may use these 2 or more types in mixture.

  The reason why the melting point of the component (C) used in the present invention is 40 ° C. or more is that if the melting point is less than 40 ° C., the high temperature sustainability and stickiness resistance of the agricultural resin film using the same is impaired. is there.

  The ratio of the component (C) in the droplet-free composition of the present invention is 30 to 60% by mass, preferably 35 to 50% by mass. This is because when the ratio is less than 30% by mass, the high temperature sustainability, dust resistance and stickiness resistance are impaired, and when it exceeds 60% by mass, the low temperature wettability, initial wettability and transparency are impaired.

  The content of the droplet-free imparting composition thus obtained is preferably from 0.1 to 5.0% by mass, more preferably from 1.0 to 3.0% by mass. This is because if the content is too small, the desired effect cannot be obtained, and if it is too large, the transparency and stickiness are impaired.

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 is particularly useful in polyolefin resin.

  The droplet-free imparting composition of the present invention can be used in combination with a conventionally used droplet-free agent, a known stabilizer or a plasticizer when producing a resin film, and a known fluorine-based resin for obtaining a droplet-free fog-proofing property. It is also possible to use in combination with a silicone-based antifogging agent. As the known fluorine-based antifogging agent, conventionally used fluorine-based surfactants or copolymer oligomers can be used, and these may be used alone or in combination of two or more.

  The composition for imparting drip resistance of the present invention has a drip resistance (low temperature wettability) in winter (low temperature) and a drip persistence (high temperature sustainability) in summer (at high temperature) due to the synergistic effect of the three components. ), Droplet-free (initial wettability) immediately after spreading, transparency during film formation (transparency), transparency after storage (transparency over time), dust resistance and stickiness resistance became.

  The agricultural resin film of the present invention may be used as a single layer or two or more kinds of resins may be used as a laminate.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the meaning is exceeded.

<Synthesis example of polyoxypropylene sorbitol fatty acid ester>
A stainless steel autoclave was charged with 1.0 mol of industrial sorbitol and 1.0 mol of stearic acid, and the temperature was raised to 220-250 ° C. under a basic catalyst while introducing N ₂ gas, and the esterification reaction was carried out for 5 hours to perform sorbitol-based stearin. Acid esters were synthesized. A small amount of the obtained sorbitol-based stearate was sampled, and after hydrolysis, the hydrophilic group composition was confirmed by gas chromatographic analysis after hydrolysis to confirm that the 1,4-sorbitan content was 45%. Thereafter, N ₂ substitution was performed and 0.5 mol of propylene oxide was added at 140 ° C. over 3 hours, and this was neutralized with phosphoric acid to give polyoxypropylene (0.5 mol) sorbitol as a tan solid. A stearic acid (1.0 mol) ester (A-1) was obtained. This composite (A-1) is subjected to the test described below. Similarly, synthesis of the present compound polyoxypropylene sorbitol fatty acid esters (A-2) and (A-3) and comparative compounds (A′-1) to (A′-3) was performed as shown in Table 1. It was. The obtained present compounds (A-2) and (A-3) and comparative compounds (A′-1) to (A′-3) are also subjected to the test described below.

<Calculation method of 1,4-sorbitan ratio>
A small amount of sorbitol fatty acid ester was sampled and hydrolyzed into a hydrophilic group site and a hydrophobic group site with concentrated sulfuric acid, and then the hydrophilic group composition was quantitatively measured under the following gas chromatographic conditions.
Equipment used: GC-14B manufactured by Shimadzu Corporation
Column used: Silicone SE-30 10% Chromosorb WAW (SUS 3Φ × 2m)
Detector temperature: 325 ° C
Column temperature: 150-280 ° C. (temperature increase rate: 10 ° C./min)
The ratio of the 1,4-sorbitan component was calculated from the measured peak area of the gas chromatograph.

<Measuring method of melting point>
Melting | fusing point of this invention compound (A-1)-(A-3) and comparative compound (A'-1)-(A'-3) was measured by DSC method (DSC6220: Seiko Instruments Co., Ltd. product). Further, the melting point of the compounds described later was also measured by this measurement method.

<Synthesis example of polyoxyethylene alkyl (or alkenyl) amine>
1 mol of laurylamine was charged into a stainless steel autoclave, N ₂ substitution was performed, and 2.0 mol of ethylene oxide was added at 155 ° C. over 2 hours to obtain lauryldiethanolamine (B2-1). The compound of the present invention (B2-1) is subjected to the test described below. Similarly, the synthesis of polyoxyethylene alkyl (or alkenyl) amines (B2-2) and (B2-3) and comparative compounds (B2′-1) and (B2′-2) having a melting point of 30 ° C. or lower is shown. I went like 2. The obtained compounds of the present invention (B2-2), (B2-3) and comparative compounds (B2′-1) and (B2′-2) are also subjected to the test described below.

<Synthesis example of polyoxyethylene alkylamine fatty acid ester>
1 mol of stearylamine was charged into a stainless steel autoclave, N ₂ substitution was carried out, and 2.0 mol of ethylene oxide was added at 155 ° C. over 2 hours to synthesize stearyldiethanolamine. Thereafter, 1.0 mol of stearic acid was charged, and the temperature was raised to 160 ° C. while introducing N ₂ gas, and the esterification reaction was carried out for 5 hours to synthesize polyoxyethylene (2) stearylamine stearate (C2-1). did. The compound of the present invention (C2-1) is subjected to the test described below. Similarly, synthesis of amine ester compounds (C2-1) and (C2-3) and comparative compounds (C2′-1) and (C2′-2) having a melting point of 40 ° C. or higher was performed as shown in Table 3. The obtained (C2-2), (C2-3), (C2′-1), and (C2′-2) are also subjected to the test described later.

<Production of evaluation film>
Examples 1-9, Comparative Examples 1-5
Table 5 shows the drip-free imparting compositions 1 to 7 and the comparative compositions 1 to 7 shown in Table 4 for 100 parts by mass of an ethylene-vinyl acetate copolymer (MFR = 1.5 g / 10 min, VA = 10). Were added and dissolved and mixed. This resin was extruded from an inflation film forming machine to obtain an inflation film having a thickness of 50 μm. Table 5 shows the evaluation results of the obtained film.

<Drip-free evaluation>
The droplet-free evaluation of the film was performed by the following method, and the results shown in Table 5 were obtained.
1. Low temperature wettability: A film is placed on the upper inclined box, outside temperature: 5 ° C, water temperature: 15 ° C, inclination angle
Evaluate the film wet state up to 12 hours at 10 degrees.
2. Sustainability at high temperature: A film is stretched over the upper inclined box, and the film is wet for one month at an outside temperature of 20 ° C, a water temperature of 50 ° C, and an inclination angle of 10 ° C.
·Evaluation criteria
A: Uniformly wet and transparent on one side
○: Wet and transparent evenly on almost one surface
△: Some transparent parts but opaque overall
X: Completely opaque Initial wettability: Comprehensive evaluation of the wet state up to 6 hours after 1 and 2 above.
・ Evaluation criteria 1 poor <5 excellent

<Evaluation of transparency>
The transparency of each film during film formation and after storage for 6 months was determined visually, and the results shown in Table 5 were obtained.
·Evaluation criteria
A: Same as the additive-free film, with a transparent surface and no white powder.
○: Surface is almost transparent and no white powder is observed
Δ: White powder is deposited
×: State in which a white thin film covers the surface

<Dustproof evaluation>
Each film was stored outdoors, and dust and dust adhesion after 6 months were visually judged to obtain the results shown in Table 5.
·Evaluation criteria
A: The state is almost the same as an unused product, and no dust or dirt is observed on the surface.
○: Some dust or dust is observed on the surface, but transparency is not hindered.
(Triangle | delta): The state in which clear dust and dust are recognized and transparency is inhibited a little.
X: A state in which dust and dust are very large and transparency is hindered.

<Evaluation of stickiness resistance>
The stickiness resistance on each film surface was evaluated by a tentacle.
·Evaluation criteria
○: Similar to the additive-free film, the film is not sticky at all.
Δ: The film is slightly sticky, but there is no problem in use.
X: The film is so sticky that it cannot be used.

As shown in Table 5, the droplet-free imparting compositions 1 to 7 according to the present invention are very excellent in the low temperature wettability, high temperature sustainability, initial wettability, transparency, dust resistance and stickiness resistance of the added film. Performance can be demonstrated.

Claims (3)

(A) A fatty acid ester obtained by reacting 1 to 3 mol of saturated fatty acid with respect to 1 mol of sorbitol, and the ratio of the peak area derived from 1,4-sorbitan fatty acid ester is 30 to 50% by gas chromatography measurement. 30 to 60% by mass of a nonionic surfactant having a melting point of 40 ° C. or higher and (B1) a melting point of 30 ° C. or lower, obtained by reacting 0.1 to 1.0 mol of propylene oxide with respect to 1 mol of the fatty acid ester. Fatty acid diethanolamide, or (B2) polyoxyethylene alkylamine having a melting point of 30 ° C. or lower, or polyoxyethylene alkenylamine 10 to 40 obtained by adding 2 to 3 moles of ethylene oxide to 1 mole of alkylamine or alkenylamine % By mass and (C1) a fatty acid diethanolate having a melting point of 40 ° C. or higher. Or (C2) 1 mol of alkylamine and 1 to 2 mol of polyoxyethylene alkylamine obtained by adding 2 to 3 mol of ethylene oxide and 1 to 2 mol of saturated fatty acid to obtain a melting point of 40 ° C or higher A droplet-free imparting composition comprising 30 to 60% by mass of an amine ester compound. A resin composition comprising 0.1 to 5.0% by mass of the droplet-free imparting composition according to claim 1. An agricultural resin film comprising the resin composition according to claim 2.