JPH0657828B2 - Antistatic agent with antifogging property - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antistatic agent having antifogging property.

[Prior art]

Organic materials, such as synthetic resins, are widely used as general-purpose materials because they have various excellent materials, but they are generally large in electrical insulation and generate static electricity due to friction. However, it has the undesirable property of being easily charged. That is, when such electrification occurs, for example, it becomes difficult to peel a thin synthetic resin film, which reduces the efficiency of the manufacturing process or the packaging work process, and in an extreme case causes an accident due to spark discharge, In addition, this electrification causes dirt such as dust to be adsorbed on the product, impairing the appearance, and adversely affecting printing and painting.

As a method of preventing such a charging phenomenon,
A method of applying various surfactants such as alkylamines, quaternary ammonium salts, fatty acid polyhydric alcohol esters, polyoxyethylene alkyl ethers, and alkylaryl sulfonates as antistatic agents, and applying these to the surface of products , A method of immersing in a product, a method of spraying and adsorbing on a product surface, or a method of kneading and blending in the case of a plastic product have been proposed, and in particular, a method of kneading a surfactant into the inside is proposed. It is said to be an excellent method in terms of durability of antistatic effect.

However, the conventionally known antistatic agent has a slower antistatic effect and, when applied to a synthetic resin such as high-density polyethylene, which is difficult to impart the antistatic effect, does not last long. However, there was a drawback that the effect was not fully exhibited.

In addition, most of many synthetic resins exhibit hydrophobicity due to their structure, and when water vapor hits, small water droplets are formed and the surface becomes cloudy. For example, synthetic resin film packaging materials for fresh foods. Alternatively, in the case of a transparent film-shaped synthetic resin product such as an agricultural vinyl house film, there is a problem that the contents cannot be seen through, and the light transmittance is lowered, so that the action effect as a greenhouse is lowered. It was

As a method of solving this problem, there is a method of using an additive called an antifogging agent, a drip agent, an antifog agent or an antifogging agent for changing the surface property of the synthetic resin from hydrophobic to hydrophilic. Are known. Since the function of the additive for making the surface of the plastic hydrophilic is a property of the surfactant having antistatic property, the additive having the antifogging property and the antistatic property is used as the additive. Many methods using an activator have also been studied.

However, in reality, there are many restrictions, and an antistatic agent that is effective as an antistatic agent and that also functions as an antifogging agent and that has a high degree of antifogging property that satisfies the needs of consumers has not yet been obtained. The current situation is not.

〔Purpose〕

It is an object of the present invention to provide an antistatic agent having an antifogging property, which can prevent the synthetic resin product from being charged and can prevent the film-shaped synthetic resin product from being clouded by water droplets.

〔Constitution〕

According to the present invention, there is provided an antistatic agent having an antifogging property, which comprises an alcoholoxylate quaternary ammonium borate ester salt represented by the following general formula (I).

[Wherein R ¹ , R ² , R ³ , R ⁴ and x represent the following, respectively.

R ¹ : a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms R ² , R ³ : (However, y is 1 to 15), a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, provided that at least one of R ^{2 and} R ³ is (However, y is 1 to 15).

R ⁴ : hydrogen or methyl group x: 1 to 15] The antistatic agent having antifogging property of the present invention is represented by the general formula (I) above.
Since it contains a compound represented by, those effects exhibit excellent antistatic properties and antifogging properties and those effects last for a long period of time, especially when applied to a film-like synthetic resin, The anti-fogging property of preventing the fogging due to water droplets can be imparted extremely effectively.

Hereinafter, the present invention will be described in more detail.

In the alcoholic quaternary ammonium borate ester salt of the general formula (I) of the present invention, R ² and R ³ are It may be in the form of monool, diol or triol having 1 to 3 hydroxyl groups. As the antifogging agent having antifogging property of the present invention, a polyol type of diol or triol is particularly preferable.

R ¹ bonded to the quaternary nitrogen is a long-chain alkyl or alkenyl group having 8 to 22 carbon atoms as represented by hardened tallow alkyl.

R ² and R ³ are (However, y is 1 to 15) and is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, at least one of which is (However, y is 1 to 15).

R ⁴ is hydrogen or a methyl group.

The average number of moles of alkylene oxide added (x + y or x + 2y) in the molecule is preferably 2 to 45, and in the case of triol, x + 2y = 3 to 45 is particularly preferable.

The alcohol quaternary ammonium borate ester salt of the present invention is a beef tallow alkyl primary amine produced by producing a borate ester of alkylene glycol from a diol such as ethylene glycol, propylene glycol and 2,3-butanediol and boric acid. Alkyl oxides such as ethylene oxide and propylene oxide, alone or in combination with amines such as beef tallow alkyl secondary amine, tallow alkyl tertiary amine, coconut alkyl primary amine, coconut alkyl secondary amine, dimethylethanolamine, triethylamine, etc. It can be obtained by addition reaction by polymerization or block polymerization. The N-bonding group of the starting amine is appropriately selected depending on the intended product, and for example, ether amine having an ether bond in the alkyl group can be used.

The content of the antifogging agent having antifogging property of the present invention is 0.05 to 5 parts by weight with respect to 100 parts by weight of the synthetic resin in the case of an internal compounding type into the synthetic resin by kneading or the like. Is appropriate. When the amount added is less than 0.05 parts by weight, a satisfactory antistatic effect is not exhibited, while when it exceeds 5 parts by weight, bleed-out increases more than necessary and stickiness occurs on the product surface, which is not preferable. In the method of internal blending, the more preferred blending amount of the antifogging agent of the present invention is 0.1 to 3 parts by weight.

When the product is applied, dipped or sprayed on the surface of the product to be adsorbed, it is used by dissolving and blending it in a solvent that does not affect the product in an amount of 0.05 to 3% by weight. Solvents that do not affect the products include, for example, water, ethanol, isopropyl alcohol and the like, and these are used alone or as a mixture. When the antistatic agent having antifogging property of the present invention is applied, dipped or sprayed on the surface of a product to be adsorbed, a satisfactory antistatic effect can be obtained. The solution concentration is preferably 0.1 to 1% by weight in order to suppress stickiness on the surface of the product, but it is also possible to set it to about 1 to 3% by weight and there is no particular limitation.

The antistatic agent of the present invention exhibits excellent antistatic property and antifogging property both when kneaded and when used as a coating type, and the antistatic agent bleeding or adsorbed on the surface of the synthetic resin product is washed off. It also exhibits excellent antistatic properties in a water resistance test for evaluating the durability of antistatic properties and antifogging properties.

Examples of the synthetic resin that can be used as the antistatic agent having the antifogging property of the present invention include the following. polyethylene,
Obtained by polymerizing polypropylene, poly-1-butene, poly-1-octene, or the like, or a polyolefin resin composed of a copolymer of these constituent monomers, vinyl chloride, vinylidene chloride, or the like as a homopolymer or a copolymer. Vinyl chloride resin, vinylidene chloride resin, polystyrene resin of styrene polymer, impact-resistant polystyrene resin obtained by mixing synthetic resin with this resin,
ABS resin, which is an impact-resistant resin composed of acrylonitrile, butadiene and styrene, acrylic resin, acrylic acid, acrylic acid ester, acrylamide, acrylonitrile, methacrylic acid, methacrylic acid ester, etc., obtained by homopolymerization or copolymerization, ethylenediamine Polyamide resin having repeating unit of acid amide obtained from diamine such as and dicarboxylic acid such as adipic acid, polyester resin obtained from diol such as ethylene glycol and saturated carboxylic acid such as terephthalic acid, component of this polyester resin An unsaturated polyester resin obtained by further introducing an unsaturated dibasic acid such as maleic acid into the above. These resins may be molded alone or may be obtained by mixing.

In the present invention, these synthetic resins have the general formula
By kneading or coating the antistatic agent having the antifogging property represented by (I), it is possible to impart the antistatic property and the antifogging property to the synthetic resin, but in this case, it is conventionally used. There is no problem even if an antistatic agent or antifogging agent is used in combination. Rather, by using it together with a conventionally used antistatic agent or antifogging agent, a synergistic effect with the antistatic agent having the antifogging property of the present invention can be expected, and its addition amount can be reduced accordingly. it can.

In the present invention, as an antistatic agent or antifogging agent that can be used in combination, lauric acid, palmitic acid, stearic acid, fatty acids such as coconut fatty acid and beef fatty acid, and polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerin and sorbit are dehydrated. Polyhydric alcohol fatty acid ester obtained by condensation; Polyethylene glycol fatty acid ester obtained from polyethylene glycol and fatty acid, or ethylene oxide adduct thereof; Higher alcohol obtained from higher alcohol and organic acid such as acid anhydride Fatty acid ester; higher alcohol sulfate ester salt obtained by sulfating higher alcohols such as lauryl alcohol and sperm alcohol with chlorosulfonic acid, sulfuric acid anhydride, etc .; unsaturated fatty acids such as oleic acid and unsaturated fatty acid esters Le; SO ₂ and C ₂ straight chain hydrocarbons under UV irradiation; Rusuruhon salt obtained by sulfonating due dodecylbenzene oleum or chlorosulfonic acid; an animal or vegetable oil sulfate obtained by sulfating Paraffin sulfonic acid obtained by reacting with and further saponifying; polyamidoamine type cation obtained by condensing fatty acid with ethylenediamine or aminoethylethanolamine, and then condensing with urea or guanidine; tertiary amine and methyl chloride A quaternary ammonium obtained by reacting with an alkylating agent such as;
Examples thereof include ethylene oxide adducts obtained by adding ethylene oxide to higher alcohols, alkylphenols, fatty acids, fatty acid amides, and aliphatic amines.

〔effect〕

The antifogging agent having the antifogging property of the present invention prevents the static charge of a synthetic resin product by internally blending or adsorbing the product by a method suitable for the product such as kneading or coating, and particularly, a film. The synthetic resin product can be provided with anti-fogging property that prevents fogging due to water droplets.

〔Example〕

Next, the present invention will be described in more detail by way of examples. The antifogging property of the present invention was evaluated by the "antifogging test" shown below.

[Anti-fogging test]

Put 100 ° C water at 40 ° C in a 200m beaker, and quickly fix the test film with rubber on the beaker mouth. Immerse only the lower half of this beaker in a constant temperature water bath at 40 ° C for 15, 3
The degree of cloudiness due to water vapor after 0, 45, 60, 90 and 120 minutes is visually judged according to the following judgment criteria.

Judgment Criteria ⊚: No cloudiness is generated, the film is completely transparent ◯: Slightly cloudy, the film is almost transparent Δ: Cloudy, the film is semitransparent ×: Cloudy, the film is opaque In addition, the surface is antistatic. The resistivity and half-life of the charged voltage were measured. The surface resistivity evaluates the resistance of the sample to charging, and the electrification half-life evaluates the ease of discharging the sample once charged.

[Surface resistivity]

Hold the product in a constant temperature and humidity room at a temperature of 23 ° C and a humidity of 65% for a specified time 30
mm × 60 mm × 2 mm sample is pressure-bonded between electrodes, charged for 40 seconds, read the measured value for 1 minute after stopping application with an ultra-insulator, and calculate surface specific resistance σ (Ω) by the following formula Ask by.

Rs: Resistance value (Ω) D: Effective circumference of main electrode (cm) g: Electrode gap (cm) [Electrical voltage half-life] Temperature was kept in a constant temperature and humidity chamber at 23 ° C and humidity of 65 ° C for a predetermined time 30
A sample of mm × 60 mm × 2 mm is fixed on a rotating disk of a static Honest meter, and an electric charge of 10 KV is applied for 15 seconds. After the application is stopped, measure the time (seconds) until the charged voltage decays to 1/2 with a synchroscope. Immediately after the application of the 10 KV charge was stopped, it was confirmed that the sample was charged.
If it discharges immediately and the half-life of the charged voltage cannot be measured,
It is displayed as "0.2 seconds or less", and when the electrification voltage cannot be measured even if it is applied and it is not charged at all, it is displayed as "not charged". Both of them show that the charge is discharged quickly when they are charged, and the antistatic property is excellent. However, "no charge" indicates that the antistatic property is more excellent.

[Water resistance test]

The test resin plate is immersed in a sample solution of a predetermined concentration for 3 seconds, and then dried in a constant temperature bath at 50 ° C. for 30 minutes. Next, this sample is left in running water (10 m / sec) for 3 minutes, and then dried again in a constant temperature bath at 50 ° C. for 30 minutes. An antifogging test or a charging test is performed before and after the running water treatment.

Further, as the antistatic agent having antifogging property used in the examples of the present invention, those shown in the following table were used.

Examples 1, 2 and 3 The antistatic properties of the compound 1 of the present invention for high density polyethylene were evaluated, and the results are shown in Table 1.

That is, 100 parts by weight of powdered high-density polyethylene (Idemitsu Polyethylene 640UF) manufactured by Idemitsu Petrochemical was added to the compound 1 of the present invention.
1, 2, and 3 parts by weight of the antistatic agent were added and kneaded at a temperature of 135 ° C. using a Labo Plastomill manufactured by Toyo Seiki. Next, this product was immediately molded into a plate of 200 mm × 200 mm × 1.5 mm at a temperature of 180 ° C. using a press molding machine manufactured by Shoji Tekko Co., Ltd. The antistatic properties of the samples thus obtained were evaluated and shown as Examples 1, 2 and 3.

Further, as a conventional antistatic agent, N, N-bis (2-hydroxyethyl) tallow amine was added instead of the compound 1 of the present invention, and evaluated.

From Table 1, the antistatic agent of the compound 1 of the present invention shows an excellent antistatic effect on high density polyethylene, which is less likely to have an antistatic property among synthetic resins, and is applied with a charge of 10 KV. In the test for examining the voltage half-life, it showed a very excellent antistatic property of "no charge".

Example 4 The antistatic property of the compound 1 of the present invention for low density polyethylene was evaluated, and the results are shown in Table 1.

That is, Mitsubishi Yuka's low density polyethylene (Yukaron MS-3
0) To 100 parts by weight of the present invention, 2 parts by weight of the antistatic agent of the compound 1 of the present invention was added, and a temperature of 135 was applied using a Labo Plastomill manufactured by Toyo Seiki.
Kneaded at ℃. Next, using a 50t press molding machine manufactured by Shoji Tekko Co., Ltd., this product was immediately heated to 200 mm x 200 mm x 1.5 mm at 180 ° C.
Was formed into a plate shape. The obtained product was evaluated for antistatic property and shown as Example 4.

This compound 1 antistatic agent of the present invention "does not charge" even when low-density polyethylene is applied with a charge of 10 KV.
That is, it showed a very excellent antistatic effect.

Example 5 The antifog property of the compound 1 of the present invention against high-density polyethylene was evaluated by film forming, and the results are shown in Table 2.

That is, 1 part by weight of the antistatic agent of the present invention was added to 100 parts by weight of powder grade high density polyethylene manufactured by Idemitsu Petrochemical and kneaded at a temperature of 200 ° C. with a 40 mm extruder manufactured by Chuo Machine Co., Ltd. to form strand pellets. Obtained. Next, this strand pellet was formed into a film having a thickness of 40 μm at a temperature of 200 ° C. using a Labo Plastomill inflation device manufactured by Toyo Seiki. The film thus obtained was evaluated for anti-fogging property.

Further, as a conventional anti-fogging agent, stearic acid monoglyceride was added in place of the compound 1 of the present invention and evaluated in the same manner as Comparative Example 2.

The antifogging agent having the antifogging property of the compound 1 of the present invention exhibits an excellent antifogging effect on a high density polyethylene resin which is particularly difficult to produce the antifogging effect among synthetic resins, and the compound 1 Also showed very good anti-fogging property in a water resistance test in which the surface of the high-density polyethylene resin was treated with running water to check the anti-fogging property.

Examples 6, 7 and 8 The antistatic properties of the compounds 2, 3 and 4 of the present invention for high density polyethylene were evaluated, and the results are shown in Table 3.

That is, 100 parts by weight of powdered high-density polyethylene (Idemitsu Polyethylene 640UF) manufactured by Idemitsu Petrochemical Co.
Example 1 was prepared by adding 3 and 4 separately to 1 part by weight.
A plate-like molded product of 200 mm × 200 mm × 1.5 mm was obtained by the same method as described above. The samples thus obtained were evaluated for antistatic properties and were set as Examples 6, 7 and 8.

As a result, the antistatic agents of the compounds 2, 3 and 4 of the present invention showed an excellent antistatic effect on the high-density polyethylene resin, which has a particularly low antistatic effect among the synthetic resins.

Examples 6, 10 and 11 Using the compound 1 of the present invention as a coating type antistatic agent, the antistatic properties for polymethylmethacrylic resin, hard vinylidene chloride resin and polyester resin were evaluated, and the results are shown in Table 4.

That is, a sheet of polymethylmethacrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd.), hard vinyl chloride resin and polyester resin is cut into a size of 30 mm x 60 mm, respectively,
2% by weight of the antistatic agent of Compound 1 of the present invention dissolved in water
The sample was immersed in an aqueous solution of the antistatic agent as a solution for 3 seconds, and then dried in a constant temperature bath at 50 ° C. for 30 minutes to obtain a surface resistivity measurement sample. Also, the samples prepared in the same manner were each left in water flowing at a speed of 10 m / sec for 3 minutes,
Then, it was dried in a constant temperature bath at 50 ° C. for 30 minutes to obtain a sample subjected to a water resistance test. The antistatic properties of the thus obtained products were evaluated, and they were set as Examples 9, 10 and 11, respectively.

Further, instead of the antistatic agent of Compound 1 of the present invention, N, N-
Bis (2-hydroxyethyl) tallow amine was used as a conventional antistatic agent, and this was dissolved in 2% by weight of water,
What was evaluated in the same manner as above was shown as a comparative example.

The compound 1 antistatic agent of the present invention exhibits a good antistatic effect even when used as a coating type antistatic agent, and
It was more water resistant than conventional antistatic agents, and even when treated with water, it showed a very good antistatic effect.

Examples 12 and 13 The compound 1 of the present invention was added to a polystyrene resin to evaluate the antistatic property with respect to the polystyrene resin. The results are shown in Table 5.

Idemitsu Petrochemical's fine-grained polystyrene (Idemitsu styrene
To 100 parts by weight of HH31), a predetermined amount of an antistatic agent of the compound 1 of the present invention and a straight chain sodium alkyl sulfonate having an average carbon number of 15 used as an antistatic agent for polystyrene were added respectively. Using a 20 mm twin-screw extruder manufactured by Kneading, kneading was performed at a temperature of 200 ° C. to prepare strand pellets. The strand pellets were injection-molded into a plate shape of 80 mm × 80 mm × 1 mm using a 40 mm injection molding machine TS-150 manufactured by Nissei Plastic Industry Co., Ltd. The surface resistivity of the samples obtained by injection molding was measured.

The compound 1 of the present invention was a compound having excellent performance of further improving the antistatic effect of the conventional antistatic agent when used in combination with the conventional antistatic agent.

Example 15 High-density polyethylene was blended with an antistatic agent of the compound 1 of the present invention, and plate-formed and film-formed, and its antistatic property and antifogging property were compared with those of conventional antistatic agents and antifogging agents. .

That is, in the same manner as in Example 1, 1 part by weight of the antistatic agent of the present invention was added to 100 parts by weight of high density polyethylene (Idemitsu Polyethylene 640UF) manufactured by Idemitsu Chemical Co., Ltd. to form a plate of 200 mm × 200 mm × 1.5 mm. Further, a film was obtained by inflation molding by the same method as in Example 5 with the same composition.

Next, instead of the compound 1 of the present invention, N, N-bis (2-hydroxyethyl) tallow amine was used as a conventional antistatic agent and molded into a plate, and stearic acid was used as a conventional antifogging agent. A film was obtained by inflation molding using monoglyceride.

The antistatic property and the antifogging property of the thus obtained product were evaluated, and the results are shown in Table 6.

The compound 1 of the present invention was a compound having extremely excellent antistatic property and antifogging property with respect to high-density polyethylene even when compared with conventional antistatic agents and antifogging agents.

Claims (1)

[Claims] 1. An antistatic agent having an antifogging property, which comprises an alcoholate quaternary ammonium borate salt represented by the following general formula (I). [Wherein R ¹ , R ² , R ³ , R ⁴ and x represent the following, respectively. R ¹ : a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms R ² , R ³ : (However, y is 1 to 15), a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, provided that at least one of R ^{2 and} R ³ is (However, y is 1 to 15). R ^4: hydrogen or a methyl group x: 1 to 15]