JP2006206855A - Aqueous titanium composition and antistatic treatment agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous titanium composition which can be mixed with water at any ratio, is stable over a long period without causing muddiness and precipitation, and furthermore has reactivity with functional groups other than a hydroxy group and a carboxy group, and an antistatic treatment agent composed of the aqueous titanium composition and an antistatic agent, particularly the antistatic treatment agent capable of forming a film having extremely superior water resistance and washing resistance. <P>SOLUTION: The aqueous titanium composition which can be mixed with water at any ratio and is stable to the water containing an electrolyte is obtained by bringing a reaction product of a titanium alkoxide with an aliphatic amine or an hydroxy acid into contact with an hydroxy acid to mix each other, and further bringing the resulting mixture into contact with a compound having two or more hydroxy groups to mix them at a molar number of the hydroxy group of the compound having two or more hydroxy groups to the titanium of 0.05-5.0. By utilizing this aqueous titanium composition, an antistatic film having resistance to water and a detergent liquid can be formed by bringing the aqueous titanium composition into contact with a specific antistatic agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous titanium composition and an antistatic treatment agent using the aqueous titanium composition, and more particularly to a stable aqueous titanium composition that can be mixed with water at an arbitrary ratio. Using this as a cross-linking agent for water-based resin, paint, ink, adhesive, barrier coating agent, etc., as surface treatment agent for titanium oxide-containing thin film such as high refractive index film, anchor coating agent, coupling agent, paper etc. It can be used as a catalyst for esterification and silicone curing as a coating agent for fibers and fibers, as a binder for rust preventive agent as an inorganic binder, as a ceramic sintering agent, and as a photocatalyst precursor and a ferroelectric material. Further, an antistatic film having excellent water resistance and washing resistance can be formed by using an antistatic treatment liquid in which the present water-based titanium composition and an antistatic agent are combined. This antistatic treatment liquid is used for plastic products such as fibers, films, sheets and containers using polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride resin, polystyrene, ABS resin, etc. that require antistatic properties, EPDM, NBR, It can be suitably applied to surface treatments of various rubber products using fluororubber, paper and wood products whose surfaces are resin-processed, and all materials that are easily charged, such as glass products.

  Titanium alkoxide reacts with a compound having a hydroxyl group, a carboxyl group or the like in the molecule as a crosslinking agent, and is therefore used as an adhesion improving agent, a coating crosslinking agent, a coating heat resistance improving agent, and the like. Further, it is widely used industrially as a catalyst for titanium oxide thin film production and esterification by the sol-gel method. However, since titanium alkoxide has very high hydrolyzability, insoluble matter is likely to be generated during operation and storage even by moisture in the air. Moreover, when using titanium alkoxide, it is necessary to use a large amount of an organic solvent, and the environmental load is extremely high. For this reason, an aqueous titanium composition has been studied as a titanium compound having a low environmental load and resistance to hydrolysis. The water-based titanium compound technology currently available on the market is a method in which a chelating agent is reacted with titanium alkoxide. Examples thereof include titanium triethanolamate obtained by reacting an amine and a titanium alkoxide, and titanium oxalate obtained by reacting an oxalic acid that is a dicarboxylic acid and a titanium alkoxide. This is described in, for example, (Patent Document 1) and (Non-Patent Document 1). However, titanium lactate obtained by reacting lactic acid, which is an oxyacid, and titanium alkoxide, tends to cause white precipitation during storage. In addition, titanium triethanolaminate obtained by reacting alkanolamine triethanolamine and titanium alkoxide is initially water-soluble, but when mixed with water and stored at 40 ° C, it becomes cloudy after one month. It loses fluidity and becomes a brown gel state. (Patent Document 2) describes a method for producing a titanium-containing aqueous solution using an aliphatic amine, but it takes a long time to make the aqueous solution, and when a small amount of water is added, the composition becomes a white solid. It is impossible to obtain a uniform and transparent liquid. Moreover, when using the conventional aqueous titanium compound as a surface treating agent, since the conventional aqueous titanium compound has low viscosity, the film forming property is remarkably poor, and it is difficult to obtain a uniform coated surface. Therefore, there is a method to increase the viscosity by mixing a water-based resin composition such as polyvinyl alcohol, but the conventional water-based titanium compound reacts with a hydroxyl group very quickly and gels at room temperature. The work was difficult. In addition, the conventional water-based titanium compound, although the reaction with the hydroxyl group and the carboxyl group proceeds rapidly, the reactivity with the epoxy group, the isocyanato group, etc. is poor, and it was necessary to select and use the functional group to react. . In addition, as an antistatic agent, an article subjected to an antistatic treatment using a low molecular weight antistatic agent has poor water resistance and washing resistance, and the film can be removed by washing with water or washing with a detergent. The antistatic property is lost after a short exposure. Regarding water resistance, there is an example that can be solved by a copolymer of an acrylic monomer or the like and an antistatic agent, but when exposed to water or a detergent solution for a long time, the antistatic property is lost.

JP 53-98393 A JP 2001-322815 A JP 2001-107030 A JP-A-1-230653 Sugiyama Iwayoshi, “Contained Metal Organic Compounds and Their Use”, M.M. R. Functional substance series No. 5, Japan, CMI Co., Ltd., March 18, 1983, p. 73-74

  The present invention is a water-based titanium composition that can be mixed with water at an arbitrary ratio, does not cause turbidity or precipitation over a long period of time, and is also reactive with functional groups other than hydroxyl groups and carboxyl groups. The primary object is to provide a compound. Conventional titanium alkoxides are hydrolyzed by moisture in the air and have a problem in handling. The present invention is not affected by moisture, is easy to handle, is stable not only with water but also with water containing an electrolyte, and is excellent when used as a crosslinking agent, adhesion improver, thin film raw material, etc. It is an object of the present invention to provide an aqueous titanium composition that can exhibit the original performance of the composition, has excellent work stability, and can reduce the discharge of organic solvents.

Moreover, by using polyhydric alcohol as a compound having two or more hydroxyl groups used when synthesizing an aqueous titanium compound, not only the reactivity of titanium alkoxide or titanium chelate but also the hydroxyl group contained in the polyhydric alcohol is utilized. And increasing the reactivity with functional groups other than hydroxyl groups and carboxyl groups.
The second object relates to an antistatic treatment agent, and in particular, aims to form a film having excellent water resistance and washing resistance. By mixing and using this water-based titanium compound and a specific antistatic agent having a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group, the antistatic agent reacts with the water-based titanium compound and adheres to the substrate. In order to improve and improve the resistance of the antistatic film, it is possible to improve the water resistance and washing resistance, which were difficult to obtain with conventional antistatic agents, and because it is water soluble, it improves work safety. Excellent and can reduce organic solvent emissions.

The present inventors have intensively studied a water-based titanium composition that can be mixed with water at an arbitrary ratio and that does not cause turbidity or precipitation over a long period of time. As a result, oxyacid was further contacted and mixed with the reaction product of titanium alkoxide and aliphatic amine or oxyacid, and the number of moles of the hydroxyl group of the compound having two or more hydroxyl groups was 0.05 to 5.0 with respect to titanium. Thus, it was possible to mix with water at an arbitrary ratio by contacting and mixing, and to find a stable aqueous titanium composition against water containing an electrolyte.
In addition, the present inventors have found that an antistatic film having resistance to water and a detergent solution can be formed by using the aqueous titanium composition and contacting and mixing with a specific antistatic agent.

  That is, the present invention provides a reaction product of a titanium alkoxide and an aliphatic amine or oxyacid, further mixed with an oxyacid and a compound having two or more hydroxyl groups, and the number of moles of the hydroxyl group of the compound having two or more hydroxyl groups is titanium. The present invention relates to an antistatic treatment agent characterized in that it is an aqueous titanium composition characterized in that it is 0.05 to 5.0, and further this aqueous titanium compound and an antistatic agent are mixed.

  The present invention provides a stable aqueous titanium composition that can be mixed with water at an arbitrary ratio and does not cause turbidity or precipitation over a long period of time. Therefore, since a titanium-containing aqueous solution can be obtained even if a small amount of water is used, the content of titanium can be increased, and since white solids are not formed even when water is added, production and use are easy. Since this water-based titanium composition is not affected by moisture compared with conventional titanium alkoxides and is easy to handle, and is stable not only with water but also with water containing an electrolyte, a crosslinking agent, an adhesion improver, When used as a thin film raw material, the original performance of an excellent titanium composition can be exhibited, the work stability is excellent, and the discharge of organic solvents can be reduced. If the combination of titanium alkoxide (A), aliphatic amine (B), oxyacid (C), and compound (D) having two or more hydroxyl groups and their reaction conditions are selected, the expression conditions of the function can be arbitrarily set Can be set to For example, when used as a crosslinking agent, the reaction can be suppressed at a low temperature and can be adjusted to be cured at a higher temperature.

  Furthermore, by using a polyhydric alcohol as a compound having two or more hydroxyl groups in the aqueous titanium compound, it is possible to react with a compound having a functional group such as an epoxy group other than a hydroxyl group or a carboxyl group or an isocyanato group. is there. In addition, by using this titanium compound and combining with a specific antistatic agent (E) having an epoxy group or the like, it is possible to form a film that is particularly water-soluble and very excellent in water resistance and washing resistance. . By using this composition, it is possible to improve water resistance and washing resistance, which were difficult to obtain with conventional antistatic agents, and because it is water-soluble, it has excellent work safety and discharge of organic solvents. Can also be reduced.

  The present invention is described in further detail below. The aqueous titanium compound in the antistatic composition of the present invention is a reaction product of the following titanium alkoxide (A) with an aliphatic amine (B) or oxyacid (C), and further an oxyacid (C), 2 or more The antistatic treatment agent is a mixture of the aqueous titanium compound and an antistatic agent (E).

The titanium alkoxide (A) is represented by the following general formula (I).

R _{1 to} R ₄ are alkyl groups. Carbon number of a preferable alkyl group is an integer of 1-8, and n is an integer of 1-10. More specifically, tetraisopropyl titanate, tetranormal propyl titanate, tetranormal butyl titanate, tetra t-butyl titanate, tetraisobutyl titanate, tetranormal ethyl titanate, tetraisooctyl titanate, tetranormal butyl titanate dimer, tetranormal butyl There are titanate tetramer, tetranormal butyl titanate heptamer and the like. Although not limited to those exemplified here, these titanium alkoxides can be used alone or in admixture of two or more.

  Examples of the aliphatic amine (B) include the following. For example, in alkylamine, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, t-butylamine, n-amylamine, sec-amylamine, dimethylamine, diethylamine, di-n-propyl There are amine, diisopropylamine, di-n-butylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, 3- (diethylamino) propylamine, 3- (di-n-butylamino) propylamine, aliphatic Examples of cyclic amines include piperidine and pyrrolidine. Examples of alkoxyalkylamines include 3-methoxypropylamine and 3-ethoxypropylamine. Hydroxyalkylamines include N, N. Examples include dimethylethanolamine, N, N-diethylethanolamine, N, N-di-n-butylethanolamine, monoethanolamine, triethanolamine, and triisopropanolamine. Tetramethyl is used as the quaternary ammonium hydroxide. Examples include ammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide. Of course, it is not limited to those exemplified here, but can be used alone or in combination of two or more. Of these aliphatic amines, hydroxyalkylamine is particularly preferred.

  The amount of the aliphatic amine added is preferably an alkanolamine when directly reacting with the titanium alkoxide, and 1 mol or more of the aliphatic amine is required per 1 mol of the titanium alkoxide, and further, 1 mol of the titanium alkoxide. The aliphatic amine is preferably reacted at 2 moles or more. When the amount of aliphatic amine is 1 mol or less with respect to 1 mol of titanium alkoxide, a water-based titanium compound cannot be obtained, and when added to water, a white precipitate is deposited.

  As the oxyacid (C), an oxyacid having 2 to 20 carbon atoms can be used, and an oxyacid having 2 to 10 carbon atoms is preferably used. Examples of oxyacids include the following. Examples include lactic acid, citric acid, glycolic acid, malic acid, tartaric acid, glyceric acid, oxypropionic acid, oxybutyric acid, oxyisobutyric acid, mandelic acid, trovic acid, gluconic acid and the like. Of course, although not limited to those exemplified here, these oxycarboxylic acids can be used alone or in admixture of two or more. Of these, malic acid, lactic acid, glycolic acid, and citric acid are more preferable. When using oxyacid and reacting with titanium alkoxide, 1 mol or more of oxyacid is required per 1 mol of titanium alkoxide. Furthermore, 2 mol or more of oxyacid may react with 1 mol of titanium alkoxide. preferable. When the oxyacid is 1 mol or less, a water-soluble titanium compound cannot be obtained, and white precipitation may occur when water is added. When oxyacid is used as an additive, the amount of oxyacid added must be 0.1 mol or more per 1 mol of titanium alkoxide. Addition of oxycarboxylic acid stabilizes the aqueous titanium composition, suppresses a rapid reaction, gives stable workability, and does not easily cause turbidity and precipitate even when contacted with an aqueous solution containing an electrolyte.

  Examples of the compound having two or more hydroxyl groups include the following. Examples include 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, glycerin, and the like. Examples of the resin composition include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, hydroxyethyl cellulose, and hydroxypropyl cellulose. Of course, although not limited to those exemplified here, these compounds may be used alone or in combination of two or more.

  The amount of the compound having two or more hydroxyl groups is such that the number of moles of the hydroxyl group of the compound having two or more hydroxyl groups is 0.01 to 10.0, preferably 0.05 to 5.0, with respect to titanium. If the addition amount is 0.01 mol or less or 10.0 or more, a water-soluble titanium compound cannot be obtained, and white precipitation may occur when water is added.

  As the antistatic agent (E), an antistatic agent having at least one hydroxyl group or carboxyl group in the molecule or an antistatic agent having one or more epoxy groups in the molecule can be preferably used. Examples of the antistatic agent having one or more nitrogen atoms in the molecule include N-dodecyl-N-hydroxyethyldodecanamide, N-hydroxyethyl-N-octadecyltetradecanamide, N-hydroxyethyl-N-octadecyl. Docosanamide, N, N-bis (2-hydroxytetradecyl) ethanolamine, N-hydroxyethyldodecylamine, alkyldi (aminoethyl) glycine, cocoylbis (2-hydroxyethyl) methylammonium chloride, oleylbis (2-hydroxy) Ethyl) methylammonium, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, a copolymer of dimethyldiallylammonium chloride and acrylic acid, and a quaternary ammonium salt-containing acrylic resin. . Examples of the antistatic agent having one or more epoxy groups in the molecule include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butoxypolyethylene glycol monoglycidyl ether, and glycidyl trimethyl ammonium chloride. Of course, it is not limited to those exemplified here, but can be used alone or in combination of two or more. These antistatic agents are preferably added in an amount of 0.1 mol or more per 1 mol of titanium alkoxide in the present aqueous titanium composition. When the addition amount of the antistatic agent is 0.5 mole ratio or less with respect to 1 mole of titanium alkoxide, the antistatic property cannot be obtained, and the water resistance and washing resistance are deteriorated.

  With respect to the method for synthesizing the aqueous titanium compound, after the reaction between titanium alkoxide and an aliphatic amine or oxyacid, an oxyacid or a compound having two or more hydroxyl groups can be added in no particular order. The same applies to the mixing with the antistatic agent, and the antistatic agent may be added to the aqueous titanium compound, or conversely, the aqueous titanium compound may be added to the antistatic agent.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis of Aqueous Titanium Composition A 28.4 g (0.1 mol) of tetraisopropyl titanate was charged into a 100 ml four-necked flask, and 21.0 g (0.2 mol) of diethanolamine was added over 30 minutes while stirring. After completion of the addition, it was refluxed at 85 ° C. for 30 minutes and cooled.
After cooling, 19.2 g (0.1 mol) of citric acid was mixed and dissolved. After confirming dissolution, 15.0 g of a 5% completely saponified polyvinyl alcohol (average molecular weight: about 80000) aqueous solution was mixed and dissolved. The number of moles of hydroxyl groups in the fully saponified polyvinyl alcohol relative to titanium in the aqueous titanium compound was 0.20. This chemical was designated as an aqueous titanium composition A.

Synthesis of aqueous titanium composition B 28.4 g (0.1 mol) of tetranormal butyl titanate was charged into a 100 ml four-necked flask, and 29.8 g (0.2 mol) of triethanolamine was added over 30 minutes with stirring. added. After completion of the addition, it was refluxed at 85 ° C. for 30 minutes and cooled. After cooling, 13.4 g (0.1 mol) of malic acid was mixed and dissolved, and after confirmation of dissolution, 20 g of 5% hydroxyethyl cellulose (average molecular weight: about 60000) was mixed and dissolved. The number of moles of hydroxyl groups in hydroxyethyl cellulose relative to titanium in the aqueous titanium compound was 0.15. This chemical solution was designated as an aqueous titanium composition B.

Synthesis of aqueous titanium composition C 28.4 g (0.1 mol) of tetraisopropyl titanate was charged into a 100 ml four-necked flask, and 29.8 g (0.2 mol) of triethanolamine was added over 30 minutes while stirring. It was. After completion of the addition, it was refluxed at 85 ° C. for 30 minutes and cooled. After cooling, 15.0 g (0.1 mol) of tartaric acid was mixed and dissolved, and after confirmation of dissolution, 20 g of 5% carboxymethylcellulose (average molecular weight: about 60000) was mixed and dissolved. The number of moles of hydroxyl groups in hydroxyethyl cellulose relative to titanium in the aqueous titanium compound was 0.15. This chemical was designated as an aqueous titanium composition C.

Synthesis of aqueous titanium composition D 28.4 g (0.1 mol) of tetraisopropyl titanate was charged into a 100 ml four-necked flask, and 17.8 g (0.2 mol) of dimethylmonoethanolamine was added over 30 minutes with stirring. added. After completion of the addition, it was refluxed at 85 ° C. for 30 minutes and cooled.
After cooling, 19.2 g (0.1 mol) of citric acid was mixed and dissolved, and after confirming dissolution, 0.9 g (0.01 mol) of glycerin was mixed and dissolved.
The number of moles of hydroxyl groups in glycerin relative to titanium in the aqueous titanium compound was 0.10. The aqueous titanium composition was titanium compound D.

Synthesis of water-based titanium composition E The same operation as titanium compound B was performed except that diethanolamine was replaced with 18.0 g (0.2 mol) of lactic acid. This chemical was designated as an aqueous titanium composition E.

Synthesis of aqueous titanium composition F The same operation as titanium compound C was carried out except that diethanolamine was replaced with 38.4 g (0.2 mol) of citric acid. This chemical was designated as an aqueous titanium composition F.

実施例７〜１３および比較例２〜３
各水系チタン組成物と帯電防止剤、水を混合した帯電防止処理液を表２に示す。

Examples 1 to 6 and Comparative Example 1
Add 4.4 g of each of the above aqueous titanium compositions A to F to water and each aqueous solution of sodium acetate, ammonium acetate, and acetic acid having a concentration of 0.5 mol / L of aqueous electrolyte solution to make a mixed solution. Turbidity or precipitate formation was observed. The pH of 0.5 mol / L aqueous solution of sodium acetate, ammonium acetate and acetic acid was 8.8 alkaline, 6.9 neutral, and 2.5 acidic. As a comparative example, the same test was conducted using Olgatics TC-400 (manufactured by Matsumoto Pharmaceutical Co., Ltd.) which is titanium triethanolamate. The results are shown in Table 1.

Examples 7-13 and Comparative Examples 2-3
Table 2 shows antistatic treatment liquids in which each aqueous titanium composition, antistatic agent, and water are mixed.

Preparation of test piece After the antistatic composition was diluted 10 times with water, the diluted solution was applied by the dip method in the same amount as the weight of the polyester cloth. After coating, it was dried at 100 ° C. for 2 minutes. Thereafter, it was cured at 160 ° C. for 2 minutes.
This was used as a test piece.
Laundry test The test piece was placed in a detergent aqueous solution adjusted to a concentration of 1 g / L and washed for 5 minutes using a washing machine. After washing was completed, rinsing was performed twice for 2 minutes. This process was repeated 5 times. After completion of the fifth rinsing step, the sample was washed in running water for 20 minutes and dried in a dryer for 15 minutes to obtain a test piece after washing.
Friction voltage measurement test Friction voltage was measured based on JISL 1094 in a thermostatic chamber set at room temperature 20 ° C and humidity 40%.
These measurement results are shown in Table 2.

Claims (8)

  A titanium alkoxide, an aliphatic amine and / or an oxycarboxylic acid and a compound having two or more hydroxyl groups are essential components, and these are contacted and mixed, and the number of moles of hydroxyl groups of the compound having two or more hydroxyl groups is relative to titanium. An aqueous titanium composition that is 0.1 or more.   An antistatic treatment agent comprising an antistatic agent and the aqueous titanium compound of claim 1.   The aqueous titanium composition according to claim 1, wherein the compound having two or more hydroxyl groups is a polyhydric alcohol of a compound having 3 or more carbon atoms.   The aqueous titanium composition according to claim 1, wherein the compound having a hydroxyl group is a (co) polymer of vinyl alcohol.   The aqueous titanium composition according to claim 1, wherein the aliphatic amine is an alkanolamine or a quaternary ammonium hydroxide.   The water-based titanium composition according to claim 1, wherein the number of moles of oxycarboxylic acid in contact with and mixing with the titanium alkoxide is 0.1 or more with respect to the titanium alkoxide.   The antistatic treatment agent according to claim 2, wherein an antistatic agent having at least one hydroxyl group or carboxyl group in the molecule is used.   The antistatic treatment agent according to claim 2, wherein an antistatic agent having at least one epoxy group in the molecule is used.