JPS6121493B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel antifogging resin composition, an antifogging composition useful for synthetic resins, and an antifogging agent for compounding synthetic resins. Currently, various synthetic resin films are manufactured and used in a wide range of fields, but resin films such as polyethylene, polyvinyl chloride, and polyvinylidene chloride are especially used as covering materials for agricultural or horticultural plants. Widely used for food packaging. These resins inherently have hydrophobic surfaces. For this reason, when used as a covering material for agricultural or horticultural plants, for example, changes in the temperature, humidity, etc. of the environment will cause the resin surface to become cloudy, which reduces the transparency of sunlight. At worst, it may cause poor germination of seeds and poor growth of seedlings. In addition, many water droplets are generated on the resin surface due to rain, fog, etc., which causes not only the above-mentioned damage but also the water droplets falling directly onto new shoots and accumulating. When used for food packaging, the water droplets that occur can make it difficult to see inside or make the product appear less fresh. Therefore, the resins normally used for these purposes include nonionic surfactants such as polyhydric alcohol partial fatty acid esters, polyalkylene glycol higher fatty acid esters, polyalkylene glycol higher alcohol ethers, polyalkylene glycol alkyl phenol ethers, and metal stones. Anionic surfactants such as ken alkylnaphthalene sulfonate and higher alcohol sulfate, and cationic surfactants such as alkylpyridinium halide and alkylpyridinium sulfate are blended as antifogging agents to prevent the surface of the resin from fogging. There are also many patents related to them. For example, in JP-A-52-69954, sorbitol ethylene oxide resin acid ester was blended with soft vinyl chloride to achieve certain effects, and in JP-A-52-69950, the same antifogging agent polyolefin resin was blended, and No. 31-6845 discloses a composition of a polyol alkylene oxide fatty acid ester, and JP-A No. 54-35187 discloses a composition of a polyol polycarboxylic acid monocarboxylic acid ester. However, the antifogging agents mentioned in these patents are
There are restrictions on the amount used due to thermal stability, compatibility with resins (which has a large effect on the transparency of the finished film), and sustainability and weather resistance (especially important for agricultural use). It has the disadvantage that it cannot withstand long-term use. The present invention has been made to solve these drawbacks. That is, the present invention uses an ester obtained by esterifying an alkylene oxide adduct of a polyhydric alcohol having 2 to 12 carbon atoms with a higher fatty acid having 8 to 22 carbon atoms and an organic dibasic acid or acidic amino acid having 4 to 36 carbon atoms to a synthetic resin. Provided is an antifogging synthetic resin composition in which 0.05 to 15 parts by weight are added to 100 parts by weight. The present invention also provides an antifogging composition comprising the ester of the present invention or the above-mentioned ester, and an anti-fogging agent for compounding synthetic resins containing the above-mentioned ester. The antifogging composition according to the present invention has significantly improved thermal stability, resin compatibility, and antifogging durability. The present invention will be explained in detail below. The polyhydric alcohols referred to in the present invention include ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, diglycerin, triglycerin, tetraglycerin, sorbitan,
Examples include sorbitol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, batyl alcohol, mannitol, and glycose. Fatty acid is n-octanoic acid, iso
-Octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, iso-palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, oleic acid, ricinoleic acid,
Examples include linolenic acid and linoleic acid. Further, the organic dibasic acid or acidic amino acid includes succinic acid, glutamic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, alkenylsuccinic acid, dimer acid, glutamic acid, aspartic acid, and the like.
Moreover, alkylene oxide includes ethylene oxide, propylene oxide, butylene oxide (1,2- or 2,3-), and the like. The antifogging composition comprising the ester of the present invention can be incorporated into various synthetic resins, but is particularly suitable for polyvinyl chloride, polyvinylidene chloride, and their copolymers polyethylene, polypropylene, and polybutylene. By containing this ester in an arbitrary amount, a good antifogging agent for synthetic resin formulation can be obtained, and the ester can be used alone or as a mixture with other substances. The antifogging agent composition according to the present invention can be easily obtained by etherifying or esterifying the above-mentioned components by conventional methods. That is, an alkylene oxide is added to a polyhydric alcohol at 120 to 180°C in the presence of an alkali metal hydroxide to obtain a polyalkylene glycol polyol ether. Next, it is obtained by esterifying it with a mixed fatty acid of higher fatty acid and organic dibasic acid or acidic amino acid at 160 to 210°C. When obtaining the antifogging agent composition according to the present invention, from the viewpoint of its performance, the preferred component ratio is 1 to 10 mol of alkylene oxide to 1 mol of polyhydric alcohol, and 1 to 10 mol of fatty acid to 1 mol of polyalkylene glycol polyhydric alcohol ether. The amount of organic dibasic acid or acidic amino acid is 0.1 to 1.5 mol.
The following representative synthesis examples of the antifogging composition of the present invention are shown below. Synthesis Example 1 Put 1.6Kg of sorbitol and NaOH8.0 into the autoclave of 4, and add N ₂ 2Kg/cm ² at 100-140℃.
1.95Kg of ethylene oxide after replacing the air three times with
was gradually added to react at 145℃ and 2-4Kg/ ^cm2 ,
Polyethylene glycol sorbitol ether
Obtained 3.54Kg. Next, 201 g of polyethylene glycol sorbitol ether obtained above, commercially available stearic acid
213.3gr and 30g of adipic acid were placed in a four-necked flask and heated at 200 to 210°C while passing _N2 gas.
After heating and stirring for ~5 hours, the mixture was neutralized at 100°C and filtered. Yield: 373.9g Acid value: 3.0 Saponification value: 154.0 Hydroxyl value: 227.0 Melting point: 43.9-44.1℃ Synthesis example 2. Charge 2.18Kg of sorbitol and 10.9g of NaOH into the autoclave of 4, and add N ₂ 2 at 100-140℃.
After replacing air three times at a rate of Kg/cm ² , 694 g of propylene oxide was gradually added and the reaction was carried out at 145° C. at 2 to 4 Kg/cm ² . 888 gr of ethylene oxide was added in the same manner to 970 g of the produced propylene oxide adduct of sorbitol to obtain polypropylene glycol polyethylene glycol sorbitol ether. Next, 460 g of the polypropylene glycol polyethylene glycol ether obtained above, 426.5 g of commercially available steering acid, and 59.9 g of adipic acid were charged into two four-necked flasks, and while passing _N2 gas,
After heating and stirring at 210℃ for 3 to 5 hours, neutralize at 100℃,
I got it through time. Yield: 835g Acid value: 1.69 Saponification value: 146 Hydroxyl value: 214 Melting point: 42.5°C Representative synthesis examples are shown above, and Table 1 shows the analytical values and melting points (increased melting points) of the esters synthesized in this way. Illustrate. In Table 1, POP (n) indicates the number of moles of propylene oxide added, and POE (n') indicates the number of moles of ethylene oxide added. Next, examples will be shown. This shows the superiority of the ester of the present invention. Example 1 Ester antifogging agent obtained in Synthesis Examples 1 to 9

[Table] Acid adipic acid ester

[Table] Films were processed by adding adipic acid ester to vinyl chloride resin in the following formulation, and the antifogging properties, blooming, and weather resistance of these films were observed.

[Table] Anti-fog test method Make a 100mm x 100mm film, immerse it in a beaker filled with water, and
It was placed in a constant temperature room at 40°C and taken out at regular intervals for one year to observe the adhesion of water droplets on the surface. Evaluation was made on a five-point scale from A to E, with A being transparent and E being opaque due to water droplets attached. Weather resistance test method A 100 mm x 100 mm film was left outdoors in vertical sunlight to observe changes in the surface. The surface condition was observed at regular intervals for one year. Weather resistance evaluation is as follows. ◎Soft and transparent ○Soft and slightly opaque △Hard and slightly opaque ×Hard and opaque Blooming test A 100 mm x 100 mm film was immersed in water at 50°C for 5 days, and its surface was observed every day. The evaluation was made on a scale of 1 to 5, with a score of 1 indicating whitening of the entire surface and a score of 5 indicating no change at all. The above observation results are summarized in Table 2. All synthetic resin compositions containing the antifogging composition of the present invention exhibit excellent antifogging effects, and have good film transparency and long-lasting effects. These effects are due to the addition of alkylene oxide, and effects are observed when 1 to 20 moles of oxide are added to 1 mole of polyhydric alcohol, but 1 to 10 moles is particularly preferred. The antifogging resin composition of the present invention is a base synthetic resin.
0.05 to 15 parts by weight of the above per 100 parts by weight

【table】

[Table] It is appropriate to add an ester antifogging composition. This ester antifogging agent composition hardly loses its transparency, so it can be added in large amounts of as much as 15 parts by weight, and is useful as an antifogging agent for synthetic resin formulations. The ester of the present invention is also useful for adjusting other characteristic values of the film, such as surface smoothness, chargeability, plasticity, and ultraviolet absorption. The resin composition of the present invention may contain other components such as plasticizers, stabilizing agents, lubricants, antioxidants, ultraviolet stabilizers, pigments, antistatic agents, bactericides, insecticides, fragrances, etc. as necessary. You can also do it.

Claims (1)

[Scope of Claims] 1. A product obtained by esterifying an alkylene oxide adduct of a polyhydric alcohol having 2 to 12 carbon atoms with a fatty acid having 8 to 22 carbon atoms and an organic dibasic acid and/or an acidic amino acid having 4 to 36 carbon atoms. 1. A synthetic resin composition characterized in that 0.05 to 15 parts by weight of ester is added to 100 parts by weight of a synthetic resin. 2. The synthetic resin composition according to claim 1, wherein the synthetic resin is polyvinyl chloride, polyvinylidene chloride and its copolymer, polyethylene, polypropylene, or polybutylene. 3 Contains an ester obtained by esterifying an alkylene oxide adduct of a polyhydric alcohol having 2 to 12 carbon atoms with a fatty acid having 8 to 22 carbon atoms and an organic dichloric acid and/or an acidic amino acid having 4 to 36 carbon atoms. An antifogging agent for synthetic resin formulations characterized by: