KR20090046706A - Water-soluble titanium oligomer composition - Google Patents

Abstract

assignment

The present invention provides a titanium oligomer composition that is stable to water and soluble in water, has high crosslinking performance when used as a crosslinking agent of an aqueous resin, and generates no cracks when applied to a plastic film or the like as a surface treating agent. It is to provide a water-soluble titanium oligomer composition having good wettability and a uniform coated surface.

Resolution

A water-soluble titanium oligomer composition comprising a titanium composite composition having a chemical structure and composition formed by reacting and / or mixing at least a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c).

Description

Water-soluble titanium oligomer composition {WATER-SOLUBLE TITANIUM OLIGOMER COMPOSITION}

The present invention relates to a water-soluble titanium oligomer composition, and more particularly to a water-soluble titanium oligomer composition containing a titanium composite composition having a specific chemical structure and composition.

Titanium alkoxides and titanium alkoxide compounds reacted with β-diketones with starting materials such as titanium alkoxides include surface treatment agents for plastic films, crosslinking agents for organic resins, raw materials for the synthesis of titanium oxide by the sol-gel method, catalysts for esterification, and the like. It is widely used as. However, these compounds are highly hydrolyzable, and are hydrolyzed by water contained in the air in titanium alkoxide, and are also hydrolyzed by exposure to water vapor over a long period of time in the titanium chelate compound.

Therefore, in order to suppress the hydrolyzability of these titanium compounds and to improve applicability | paintability, the titanium compound oligomerized using water may be used. However, the oligomerization alone does not have sufficient inhibitory effect on hydrolyzability, and when exposed to water vapor or the like over a long period of time, there is a problem that white turbidity or white precipitate is generated.

On the other hand, in order to improve the stability to water, the titanium chelate compound using the triethanolamine and lactic acid which are water-soluble substituents, and the compound which reacted or mixed glycol and an amine with titanium alkoxide are also known. However, these compounds are water-soluble compounds of monomers, and when used as a surface treatment agent for plastic films, have problems of poor wettability, easy cracking, and cracking in one coating, so that thick films cannot be formed. there was. Moreover, in the titanium chelate compound which used triethanolamine, there existed a problem that the stickiness remained on the surface at low temperature drying, and the blocking phenomenon occurred in a plastic film by residual triethanolamine.

Patent Document 1: Japanese Unexamined Patent Publication No. 2004-256505

Non-Patent Document 1: Sugiyama Iwayoshi "Containing Metal Organic Compounds and Their Use", M.R.Functional Substance Series No. 5, p. 112 to p.116 (Nippon CMI Co., Ltd.)

This invention is made | formed in view of the said background art, The subject is providing the titanium oligomer composition soluble in water which is stable with respect to water or water vapor, and when used as a crosslinking agent of water-based resin, it has high crosslinking performance, and is a surface treating agent. The present invention provides a water-soluble titanium oligomer composition which is free from cracks or the like when applied to a plastic film or the like, has good wettability, and obtains a uniform coated surface.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the "chemical" obtained by reacting or mixing an amine compound and a glycol compound with respect to the titanium oligomer compound which oligomerized the titanium alkoxide and a titanium chelate compound with water was carried out. The present invention was completed by finding out that the titanium composite composition of "a structure and a mixed composition" is stable to water and can be dissolved in water, and solves the above problems.

That is, the present invention contains a titanium composite composition having a chemical structure and composition formed by reacting and / or mixing at least a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c). In the composition.

Moreover, this invention contains said water-soluble titanium oligomer composition, It is a crosslinking agent of water-based resin characterized by the above-mentioned. Moreover, this invention is a surface treating agent containing the said water-soluble titanium oligomer composition.

The water-soluble titanium oligomer composition of the present invention is very stable to water or water vapor, despite being water-soluble. In addition, when used as a crosslinking agent of the aqueous resin, it is possible to crosslink the aqueous resin to increase the heat resistance, water resistance, and the like of the aqueous resin, and to apply a plastic film or the like to a uniform coating surface where cracking does not occur due to curing or the like if necessary. Can be obtained.

Moreover, when using the water-soluble titanium oligomer composition of this invention as a surface treating agent, plastics, such as a polyethylene terephthalate (it abbreviates as "PET" hereafter) and a biaxially stretched polypropylene film (henceforth abbreviated as "OPP"), Adhesiveness, such as an organic resin, can be improved with respect to adherends, such as a film, and the film | membrane which a crack does not generate | occur | produce can be produced. Moreover, since wetting property, film production uniformity, adhesiveness, surface modification property, etc. with respect to various to-be-adhered materials are excellent, it can adhere to the adherend which is difficult to adhere | attach with very high adhesiveness.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated, this invention is not limited to the following embodiment, It can change arbitrarily and can implement.

[Titanium Composite Composition]

The water-soluble titanium oligomer composition of the present invention is a titanium composite having a "chemical structure and composition" formed by "reacting and / or mixing" at least a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c). It contains a composition.

[Titanium Compound Oligomer (a)]]

The titanium compound oligomer (a) is not particularly limited, but the "titanium chelate compound having a structure in which a chelating agent is coordinated with titanium alkoxide represented by the following formula (1) or titanium alkoxide represented by the following formula (1) is condensed: It is preferable to have a structure.

[Formula 1]

[In formula (1), R <^1> -R <^4> represents a C1-C18 alkyl group each independently.]

Although "titanium alkoxide represented by Formula (1)" which is a starting material before condensation, R <^1> -R <^4> in said Formula (1) is a C1-C18 alkyl group each independently, respectively, C1-C8 is independently It is preferable that it is an alkyl group, and it is especially preferable that they are a C1-C5 alkyl group each independently.

Specifically as "titanium alkoxide represented by Formula (1)", For example, tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy citanium, tetra isopropoxy citanium, tetra n-butoxy titanium, Tetraisobutoxytitanium, diisopropoxydin-butoxytitanium, ditert-butoxydiisopropoxytitanium, tetratert-butoxytitanium, tetraisooctoxytitanium, tetrastearoxytitanium and the like. These can be used individually or in mixture of 2 or more types.

As a starting material before condensation, a titanium chelate compound having a structure in which a chelating agent is coordinated to "titanium alkoxide represented by formula (1)" in addition to "titanium alkoxide represented by formula (1)" is mentioned as a preferable one. have. Although there is no limitation in particular as such a chelating agent, At least 1 sort (s) chosen from the group which consists of (beta) -diketone, (beta) -ketoester, a polyhydric alcohol, an alkanolamine, and an oxycarboxylic acid improves stability to the hydrolysis of a titanium compound, etc. It is preferable at the point to make it.

The β-diketone compound is not particularly limited as long as it is coordinated as a chelating agent. For example, specifically 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, dibenzoylmethane, Tenoyl trifluoroacetone, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, and the like. These can be used alone or in combination of two or more.

The β-ketoester is not particularly limited as long as it is coordinated as a chelating agent. For example, specifically, acetoacetic acid methyl, acetoacetate, acetoacetic acid propyl, acetoacetate acetate, methyl pivaloyl acetate, and methyl isobutyl Monoacetate, methyl caproyl acetate, methyl lauroyl acetate, and the like. These can be used alone or in combination of two or more.

The polyhydric alcohol is not particularly limited as long as it is coordinated as a chelating agent, but may be 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2, 3-pentanediol, glycerin, diethylene glycol, hexylene glycol, etc. are mentioned. These can be used alone or in combination of two or more.

The alkanolamine is not particularly limited as long as it is coordinated as a chelating agent. However, N, N-dimethylethanolamine, N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyl diethanolamine, triethanolamine, diethanolamine, Monoethanolamine etc. are mentioned. These can be used alone or in combination of two or more.

The oxycarboxylic acid is not particularly limited as long as it is coordinated as a chelating agent. Examples thereof include glycolic acid, lactic acid, tartaric acid, citric acid, malic acid and gluconic acid. These can be used alone or in combination of two or more.

A titanium compound oligomer (a) is obtained by condensation of said "titanium alkoxide represented by Formula (1)" or "titanium chelate compound which has a structure in which a chelating agent is coordinated with the titanium alkoxide". Although there is no limitation in particular as a method of condensing here, The method of performing this titanium alkoxide or this titanium chelate compound by making water react in an alcohol solution, or the state in which the amine compound (b) mentioned later and water coexist in an alcohol solution coexist. Reaction in is preferred.

Regarding the amount of water used for condensation and oligomerization, the molar number of water is 0.2 to 2 mol relative to 1 mol of the total amount of the titanium alkoxide and / or titanium chelate compound, that is, 1 mol of the titanium atom. It is preferable from a viewpoint of film manufacturability, applicability | paintability, etc., It is more preferable that it is 0.3-1.7 mol, It is especially preferable that it is 0.5-1.6 mol, It is still more preferable that it is 1.0-1.5 mol.

In addition, the above does not limit the manufacturing method of the titanium compound oligomer (a) in this invention, The chemical structure, such as the degree of condensation of the titanium compound oligomer (a), is specified by manufacturing methods, such as a condensation method, It is. Since the titanium compound oligomer (a) may have a two-dimensional or three-dimensional chemical structure, the chemical structure can only be specified by the production method, and thus has the same chemical structure produced by different production methods. Titanium compound oligomer (a) is also used in the present invention.

When this titanium compound oligomer (a) is represented by a composition formula, when the number of moles of water reacted with respect to 2 mol of titanium atoms is x mol, the titanium compound oligomer (a) represented by following formula (2) is normally obtained by condensation.

TiO _{x / 2} (OR) _4-x (2)

[In Formula (2), R represents either of R ¹ to R ⁴ in Formula (1).]

When 1 mol of water is reacted with 1 mol of titanium atoms, that is, when 2 mol of water is reacted with 2 mol of titanium atoms, x = 2, so that Equation (2) is

TiO ₁ (OR) ₂ (3)

When 1.5 mol of water is reacted with 1 mol of titanium atoms, that is, when 3 mol of water is reacted with 2 mol of titanium atoms, x = 3, so that Equation (2) is

TiO _3/2 (OR) ₁ (4).

It is preferable as a degree of condensation of a titanium compound oligomer (a) which has a composition formula obtained by substituting the value of x corresponding to "the amount of preferable water used for condensation and oligomerization" mentioned above to Formula (2).

The titanium compound oligomer (a) in the present invention is not particularly limited as long as it is an oligomer, but on average, 1.5 to 20 dimers are preferred, 2 to 15 dimers are more preferred, and 4 to 13 dimers are particularly preferred, and 5 to 12 More preferred is a dimer. It is preferable that condensation degree is large from a viewpoint of stability with respect to water, a film manufacturability, applicability | paintability, etc. Formula (3) shows that in principle, it has infinite degree of condensation in one dimension, and the actual titanium compound oligomer (a) produced has a finite degree of condensation. More preferably, the titanium compound oligomer (a) in the present invention has a chemical structure produced using an amount of water having an infinite degree of condensation in principle.

At the time of condensation, the titanium alkoxide or the titanium chelate compound may be used as an alcohol solution using a solvent such as alcohol, and in some cases, the titanium compound oligomer (a) may be obtained via heat treatment such as reflux. The alcohol used at this time is not particularly limited, but is preferably an alkyl group having 1, R ¹ ~ R ⁴ in the formula (1) in terms of alcohol does not alter the reactivity of the titanium compound is an oligomer (a). Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, etc. are mentioned. These can be used alone or in combination of two or more.

Although the amount of such alcohol is not particularly limited, it is preferable to dilute the amount of water used for condensation and oligomerization using the alcohol so that the concentration is 0.5 to 20% by mass relative to the total amount of water and the alcohol. It is preferable at the point which suppresses generation | occurrence | production of a white precipitate, It is more preferable to dilute so that it may become a concentration of 0.7-15 mass%, It is especially preferable to dilute so that it may become a concentration of 1.0-10 mass%.

It is preferable that a titanium compound oligomer (a) has a structure which further coordinates a chelating agent to the titanium compound oligomer mentioned above. That is, the titanium alkoxide represented by the formula (1) or a titanium chelate compound having a structure in which a chelating agent is coordinated therein is also condensed, and it is also preferable to have a structure in which the chelating agent is coordinated. That is, the structure in which the chelating agent is reacted before condensation and / or after condensation is preferable in terms of enhancing stability against hydrolysis of the titanium compound oligomer (a).

Although there is no limitation in particular as a chelating agent used after condensation, The chelating agent mentioned above can be used preferably. Especially preferred are β-diketones, β-ketoesters or alkanolamines.

[Amine Compound (b)]

The amine compound (b) to be reacted and / or mixed with the titanium compound oligomer (a) for obtaining a titanium composite composition is not particularly limited, but a substituted or unsubstituted aliphatic amine or quaternary ammonium hydroxide is used as a titanium oligomer compound ( It is preferable at the point which improves stability to hydrolysis etc. of a), and makes it soluble.

As a substituent in "substituted or unsubstituted aliphatic amine", an alcoholic hydroxyl group is preferable. As a substituted aliphatic amine, an alkanolamine is especially preferable.

Specific examples of the unsubstituted aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine and tert-butyl which are aliphatic alkylamines. Amine, amylamine, sec-amylamine, dimethylamine, diethylamine, din-propylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine; aliphatic cyclic Amines such as piperidine and pyrrolidine. These can be used alone or in combination of two or more.

Specific examples of the alkanolamine include N, N-dimethylethanolamine, N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, and N-methyl. Diethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, triethanolamine, diethanolamine, monoethanolamine Etc. can be mentioned. These can be used alone or in combination of two or more.

As quaternary ammonium hydroxide, For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzyl ammonium hydroxide, 2-hydroxyethyl trimethyl ammonium hydroxide, etc. are mentioned. These can be used alone or in combination of two or more.

[Glycol Compound (c)]]

Although it does not specifically limit as a glycol compound (c) which reacts and / or mixes with the said titanium compound oligomer (a) for obtaining a titanium composite composition, The glycol compound which has a hydroxyl group in each adjacent carbon atom is preferable, Specifically, For example, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, glycerin and the like can be mentioned. . Among them, 1,2-ethanediol, 1,2-propanediol or 2,3-butanediol are particularly preferable in terms of improving stability and acceptability of the titanium oligomer compound.

By using the glycol compound (c), stability to hydrolysis and the like of the titanium oligomer compound (a) can be improved and solubilized.

[[Ratio of Each Component in Titanium Composite Composition]]

Although the usage ratio of "titanium compound oligomer (a)", "amine compound (b)" and "glycol compound (c)" is not particularly limited, the molar ratio of (b) and (a) is (b) / (a) = 0.1 / 10-10 / 0.1 are preferable, (b) / (a) = 0.3 / 10-10 / 0.3 are more preferable, 0.5 / 10-10 / 0.5 are especially preferable. When (a) is too small with respect to the total amount of (a) and (b), it will cause crosslinkability, film | membrane manufactureability, adhesiveness, etc., and when too much (a), the solubility to water and hydrolysis will be There may be a lack of stability, for example.

(c) / (a) = 0.1 / 10-10 / 0.1 are preferable, as for the molar ratio of (c) and (a), (c) / (a) = 0.5 / 10-10 / 0.5 is more preferable, 1 / 10-10 / 1 are especially preferable. When (a) is too small with respect to the total amount of (a) and (c), it will cause crosslinking property, film | membrane productivity, adhesiveness, etc. to fall, while too much (a) will have solubility to water and hydrolysis. There may be a lack of stability, for example.

About the chemical structure of the compound (henceforth abbreviated as "compound A") which has a structure obtained by reaction of a titanium compound oligomer (a), an amine compound (b), and a glycol compound (c) in a titanium composite composition, it is the said manufacturing method It will not be limited to what was manufactured by the specific manufacturing method as long as it has a structure obtained by these.

As a chemical structure of the compound A, the structure in which a titanium compound oligomer (a) reacts with an amine compound (b) and glycol (c), and the glycol chelate and the amino group of a titanium compound oligomer are coordinated with titanium is preferable. In particular, the alkoxyl group which is the terminal of a titanium compound oligomer (a), and the amine compound (b) and / or glycol compound (c) react, and the hydroxyl group which exists in the chelated structure and the amino group which exists in an amine compound, or a glycol compound exists Preference is given to structures coordinated with titanium atoms.

The titanium composite composition in this invention contains the said compound A, a titanium compound oligomer (a), an amine compound (b), and / or glycol (c). The titanium composite composition may have a composition in which the amine compound (b) and the glycol compound (c) are mixed at room temperature with respect to the titanium compound oligomer (a), and the amine compound (b) and glycol with respect to the titanium compound oligomer (a). What has a composition obtained by heating and refluxing a compound (c) may be sufficient. The above-mentioned "mixed composition" includes a case in which the entire amount of the reaction does not proceed and the one remaining unreacted is mixed, or the case in which only a part is reacted.

Although the titanium composite composition in this invention will not be specifically limited if it is a composition obtained by the said method, The following 5 forms are preferable.

(1) Compound A;

(2) a mixture of compound A and titanium compound oligomer (a);

(3) a mixture of compound A and glycol compound (c);

(4) a mixture of compound A, titanium compound oligomer (a) and glycol compound (c);

(5) a mixture of a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c);

Among these, Form (1) and Form (5) are preferable at the point that the effect of this invention described above is obtained preferably.

[Silicon Compound (d)]

Although the water-soluble titanium oligomer composition of this invention should just consist of the said titanium composite composition, "Titanium composite composition further contains" the silicone compound (d) which has one or more alkoxy groups in a molecule "(hereinafter," silicone compound (d) ") It may have a chemical structure and composition formed by reacting and / or mixing.

Although there is no limitation in particular as a silicone compound (d), A silicone compound etc. which four alkoxy groups couple | bonded with the silane coupling agent, a silicon atom, etc. are preferable at the point which improves film | membrane manufacturability. Among these, containing an amino group, a mercapto group, or an epoxy group is preferable at the point which further improves film | membrane productivity. It is also preferable to have a structure in which an alkyl group is directly bonded to a silicon atom in terms of enhancing film manufacturability. As the alkyl group at this time, a methyl group is preferable. Moreover, the partial hydrolysis-condensation product of the said compound can also be used preferably.

Specific examples of the silicone compound (d) include tetramethoxysilane, tetraethoxysilane, tetranormal propoxysilane, γ-aminopropylaminoethyltrimethoxysilane, and γ-aminopropylaminoethylmethyldimethoxy Silane, γ-aminopropylaminoethyltriethoxysilane, γ-aminopropylaminoethylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltrimethoxy Silane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-gly Cidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercapto Propyltrimethoxysilane, γ- Le mercapto propyl and methyl diethoxy silane, γ- mercaptopropyl methyl dimethoxysilane, γ- methacryloxypropyl methyl dimethoxysilane, γ- methacryloxypropyl trimethoxysilane. These can be used individually or in mixture of 2 or more types.

When obtaining a water-soluble titanium oligomer composition by using together a silicone compound (d) to the titanium composite composition mentioned above, it is preferable to have a structure obtained by reacting and / or mixing a silicone compound (d) with the titanium composite composition. Do. Although there is no limitation in particular in a reaction method, after mixing a titanium composite composition and a silicone compound (d), it is preferable to reflux at the boiling point of the solvent used and to advance reaction. In addition, there is no regulation in the order of formulation.

Although the use ratio of the said titanium composite composition and the said silicone compound (d) does not have limitation in particular, It is preferable that the mass ratio of a titanium composite composition and a silicone compound (d) is 0.1 / 10-10 / 0.1, and is 0.5 / 10-10 / It is more preferable that it is 0.5, and it is especially preferable that it is 1/10-10/1. When the titanium composite composition is too small with respect to the total amount of the titanium composite composition and the silicone compound (d), the film manufacturability is deteriorated. On the other hand, when the titanium composite composition is too large, the film manufacturability is reduced, and the stability such as hydrolysis property is insufficient. There is.

The water-soluble titanium oligomer composition of the present invention is not limited to that produced by the above-described manufacturing method, and is included in the present invention even if the manufacturing method is different as long as the composition has a chemical structure and composition produced by the above-described manufacturing method. . However, it is preferable that the water-soluble titanium oligomer composition of this invention was manufactured by the manufacturing method mentioned above. That is, it is preferable to react and / or mix a titanium compound oligomer (a), an amine compound (b), and a glycol compound (c) at least as a manufacturing method of a titanium composite composition, and a manufacturing method of a water-soluble titanium oligomer composition. Moreover, it is preferable as a manufacturing method of a water-soluble titanium oligomer composition to make a titanium composite composition react and / or mix the silicone compound (d) which has one or more alkoxy groups in a molecule | numerator.

[Cross-linking system]

The water-soluble titanium oligomer composition of this invention can be mix | blended with aqueous resin, and can be used suitably as an aqueous crosslinking agent. Moreover, it can use preferably as a surface treating agent. That is, it is preferable to add the water-soluble titanium oligomer composition of this invention to water-based coating materials and surface treating agents. In this invention, "aqueous resin" means resin melt | dissolved, suspended dispersion, or emulsion dispersion in the solvent or dispersion medium which mainly consists of water. In addition, the "water-based paint" includes the water-emulsion paint of resin which is not water-soluble, etc. other than the paint of water-soluble resin.

Although it does not specifically limit as water-soluble resin among water-based resin, Polyvinyl alcohol, polyvinylpyrrolidone, the hydrolyzate of polyvinyl acetate, etc. are mentioned. Moreover, (meth) acrylic resin, a vinyl acetate resin, etc. are mentioned as resin suspended or emulsified in water. There are no particular limitations on the crosslinking conditions as long as the conditions are usually used for the crosslinking of the coating material. In the case of heat curing, 30 to 100 ° C is preferable, and 40 to 80 ° C is particularly preferable. 10 second or more is preferable and 1 minute or more of hardening time is especially preferable.

[Surface Treatment Agent]

Moreover, about a surface treating agent, since it can dilute with water and apply | coat without using an organic solvent, it is preferable at the point of a work environment. Although it does not specifically limit as a surface on which the water-soluble titanium oligomer composition of this invention is used preferably, Plastic surfaces, such as PET, OPP, polyethylene; Metal surface; Rubber surfaces, such as ethylene propylene rubber and styrene butadiene rubber, etc. are mentioned. The surface treatment agent containing the water-soluble titanium oligomer composition of this invention is apply | coated so that a dry film thickness may become 0.01 micrometer-1 micrometer, Especially preferably, it is 0.02 micrometer-0.5 micrometer. Thereafter, it is dried according to a conventional method to obtain a treated surface.

Example

Although an Example and a comparative example are given to the following and this invention is demonstrated to it further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.

Preparation Example 1

After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of isopropanol, a mixture of 2.7 g (0.15 mol) of water and 50.0 g of isopropanol was added dropwise. After completion of dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligomer (a) A". Subsequently, after adding 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine, the mixture was stirred for 1 hour, then 30.4 g (0.40 mol) of 1,2-propanediol was added and stirred for 1 hour, and further refluxed for 1 hour. "Titanium composite composition A" was obtained. What consists of titanium composite composition A is called "water-soluble titanium oligomer composition A."

Preparation Example 2

After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of isopropanol, a mixture of 2.7 g (0.15 mol) of water and 50.0 g of isopropanol was added dropwise. After completion of dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligomer (a) B". Subsequently, after adding 5.9 g (0.05 mol) of Nn-butylethanolamine, after stirring for 1 hour, 36.8 g (0.40 mol) of glycerin was added, it stirred for 1 hour, it was refluxed again for 1 hour, and "Titanium composite composition B" was added. Got it. What consists of titanium composite composition B is called "water-soluble titanium oligomer composition B."

Preparation Example 3

After dissolving 34.0 g (0.10 mol) of tetra-n-butoxy titanium in 30.0 g of n-butanol, the liquid mixture of 2.7 g (0.15 mol) of water and 60.0 g of n-butanol was dripped. After completion of dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligomer (a) C". Subsequently, after adding 3.7 g (0.05 mol) of diethylamine, after stirring for 1 hour, 36.0 g (0.40 mol) of 1,2-butanediol was added, the mixture was stirred for 1 hour, and further refluxed for 1 hour to give “titanium composite composition C Was obtained. What consists of titanium composite composition C is called "water-soluble titanium oligomer composition C."

Preparation Example 4

After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of isopropanol, a mixture of 2.7 g (0.15 mol) of water and 50.0 g of isopropanol was added dropwise. After completion of dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligomer (a) D". Subsequently, after adding 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine, after stirring for 1 hour, 26.0-butanediol 36.0 g (0.40 mol) was added, the mixture was stirred for 1 hour, and further refluxed for 1 hour. "Titanium composite composition D" was obtained. Ê * consisting of the titanium composite composition D is referred to as "water-soluble titanium oligomer composition D".

Preparation Example 5

The titanium compound oligomer (a) was prepared in the same manner as in Production Example 4, except that the amount of water to 28.4 g (0.10 mol) of tetraisopropoxytitanium was 2.2 g (0.12 mol) of water.

E "and" titanium composite composition E "were obtained. Ê * consisting of the titanium composite composition E is referred to as "water-soluble titanium oligomer composition E".

Preparation Example 6

After dissolving 36.4 g (0.1 mol) of diisopropoxybisacetylacetonate titanium in 50.0 g of isopropanol, the liquid mixture of 2.7 g (0.15 mol) of water and 100.0 g of isopropanol was dripped. After completion of the dropwise addition, the mixture was stirred for 1 hour, and further refluxed for 1 hour to obtain "titanium compound oligomer (a) F". Subsequently, after adding 5.1 g (0.05 mol) of triethylamines, the mixture was stirred for 1 hour, and then 30.4 g (0.40 mol) of 1,2-propanediol was added and stirred for 1 hour. F ”was obtained. What consists of titanium composite composition F is made into "water-soluble titanium oligomer composition F."

Preparation Example 7

After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of isopropanol, a mixture of 2.7 g (0.15 mol) of water and 50.0 g of isopropanol was added dropwise. After completion of dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligomer (a) G". Subsequently, after adding 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine, the mixture was stirred for 1 hour, then 30.4 g (0.40 mol) of 1,2-propanediol was added and stirred for 1 hour, and further refluxed for 1 hour. "Titanium composite composition G" was obtained.

44.4 g (0.20 mol) of (gamma) -aminopropylaminoethylmethyl diethoxysilane was added to the titanium composite composition G, and it stirred for 1 hour, and it refluxed again for 1 hour. Let this be "water-soluble titanium oligomer composition G."

Preparation Example 8

8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine was added to 28.4 g (0.10 mol) of tetraisopropoxycitane. After addition, the mixture was stirred for 1 hour. Further, 30.4 g (0.40 mol) of 1,2-propanediol was added thereto, stirred for 1 hour, and further refluxed for 1 hour to obtain "titanium compound a".

Preparation Example 9

After adding triethylamine 5.1g (0.05mol) to 34.0g (0.10mol) of tetran-butoxy titanium, it stirred for 1 hour. Thereafter, 30.4 g (0.40 mol) of 1,2-propanediol was added thereto, stirred for 1 hour, and further refluxed for 1 hour to obtain "titanium compound b".

Preparation Example 10

To 28.4 g (0.1 mol) of tetraisopropoxycitane, 10.1 g (0.1 mol) of triethylamine was added over 30 minutes. Subsequently, 46.8 g (0.2 mol) of (gamma)-(2-aminoethyl) aminopropylmethyl diethoxysilane were added, after that, 49.6 g (0.8 mol) of 1,2-ethanediol were added, and it stirred for 1 hour, It was refluxed again for 1 hour to obtain "titanium compound c".

Examples 1-7, Comparative Examples 1-13

[Evaluation of Stability and Solubility in Water]

Tetraisopropoxytitanium, tetran-butoxytitanium, tetran-butoxytitanium dimer, "titanium compound oligomers (a) A-G" manufactured by Production Examples 1-7, "water-soluble titanium oligomer composition A-G" 10 parts by mass of the "titanium compounds a to c" produced in Production Examples 8 to 10 were added to 90 parts by mass of water, respectively, to confirm stability to water and solubility in water. The results are shown in Table 1.

The water-soluble titanium oligomer compositions A-G manufactured by Production Examples 1-7 were melt | dissolved in water, and were excellent also in water stability, as can be seen from the result of Examples 1-7 of the said Table 1. In addition, the titanium compound oligomer (a) A-G (Comparative Examples 4-10) before adding the amine compound (b) and the glycol compound (c) in the titanium compound of Comparative Examples 1-3 and Production Examples 1-7. In all cases, white precipitation occurred, and the stability to water and the solubility in water were inferior.

Examples 8-14, Comparative Example 14

[Evaluation of Crosslinking Performance for Polyvinyl Alcohol]

100 mass of 5 mass% aqueous solution of polyvinyl alcohol ("Gosenol" N-300 (made by Nippon Synthetic Chemical Co., Ltd.)) as 2 mass parts and water-based resin of the water-soluble titanium oligomer composition A-G manufactured by manufacture examples 1-7. The parts were mixed to obtain a resin solution.

Moreover, it replaces 2 mass parts of water-soluble titanium oligomer compositions A-G, and replaces 2 mass parts of diisopropoxy citabis bis (triethanol aluminate) ("Orgatics TC-400" by Matsumoto Fine Chemicals Co., Ltd.) In the same manner as in 14, a resin solution of Comparative Example 14 was obtained.

5g of the resin solutions of Examples 8-14 and Comparative Example 4 were weighed into an aluminum cup with a bottom area of 70 cm 2, and dried in a hot air circulation dryer at 40 ° C for 12 hours. The dried membrane was placed in a 100 ml beaker, and 100 ml of water was added for 1 hour. Then, the insoluble content was filtered using filter paper, it dried at 105 degreeC for 2 hours, the mass of the filter paper and an insoluble content was weighed, and the insolubility rate (mass%) was computed from the following formula. The results are shown in Table 2 below.

Insolubilization rate (mass%) = [(C-B) / A] × 100

Where A = mass of membrane before test (g)

        B = mass of filter paper (g)

        C = filter paper + mass of insoluble matter (g)

"Water-soluble titanium oligomer composition A-G" of this invention of Examples 8-14 showed high crosslinkability with respect to polyvinyl alcohol. On the other hand, the titanium compound of the comparative example 14 did not show high crosslinkability with respect to polyvinyl alcohol.

[Evaluation of film manufacturability and curability]

5 parts by mass of the water-soluble titanium oligomer compositions A to G prepared in Production Examples 1 to 7 were added and mixed to 95 parts by mass of water to obtain the surface treating agents of Examples 15 to 21. As the comparative example 15, the titanium compound a manufactured in the manufacture example 8 was used, and the titanium compound b manufactured in the manufacture example 9 was used as the comparative example 16, and it carried out similarly to manufacture examples 1-7, and obtained the surface treating agent.

The surface treatment agents of Examples 15 to 21 and Comparative Examples 15 to 16 were coated with a bar coater No. 4 on the surface of an untreated PET (polyethylene terephthalate) film having a thickness of 50 µm, and then dried for 30 seconds with a hot air circulation dryer at 150 ° C. I was. The presence of cracks was observed on the surface of the dried film by a laser microscope, and evaluation of the absence of cracks as (circle) and the presence of cracks were evaluated as x. Moreover, after rubbing the film surface dried at the same time with a finger, the surface was visually observed and evaluated as a transparent film (circle) and what was whitened after rubbing was made into x. The results are shown in Table 3 below.

As can be seen from the results of Examples 15 to 21 of Table 3, the water-soluble titanium oligomer compositions A to G of the present invention prepared in Production Examples 1 to 7 are uniform even after drying for 30 seconds at 150 ° C. The membrane could be prepared. Moreover, even if it rubs with a finger, the film | membrane which remains transparent is obtained. On the other hand, in the titanium compounds a to c obtained by reacting and / or mixing the amine compound (b) and the glycol compound (c) with the titanium compound monomer in Production Examples 8 to 10, cracks were generated in the same evaluation, and the film was scratched after abrasion. Whitening was carried out (Comparative Examples 15 to 17).

The water-soluble titanium oligomer composition soluble in water of the present invention can be crosslinked by adding to water-based paints or resins to impart water resistance, solvent resistance, and the like, and can be used as a surface treatment agent to obtain a uniform surface. It is widely used in industrial fields such as the paint field and surface treatment field.

Claims (13)

A water-soluble titanium oligomer composition comprising a titanium composite composition having a chemical structure and composition formed by reacting and / or mixing at least a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c). The method of claim 1, The titanium compound oligomer (a) has a structure in which a titanium chelate compound having a structure in which a chelating agent is coordinated with titanium alkoxide represented by the following formula (1) or titanium alkoxide represented by the following formula (1) Water soluble titanium oligomer composition. [Formula 1]

[In formula (1), R <^1> -R <^4> represents a C1-C18 alkyl group each independently.] The titanium compound oligomer (a) has a structure in which a titanium chelate compound having a structure in which a chelating agent is coordinated with titanium alkoxide represented by the following formula (1) or titanium alkoxide represented by the following formula (1), Furthermore, the titanium compound of Claim 1 which has a chemical structure which coordinates a chelating agent. [Formula 2]

[In formula (1), R <^1> -R <^4> represents a C1-C18 alkyl group each independently.] The method of claim 2 or 3, The water-soluble titanium oligomer composition wherein the condensation is carried out by reacting the titanium alkoxide or the titanium chelate compound with water in an alcohol solution. The method of claim 2 or 3, The said water condensation is performed by making 0.2-2 mol of water react in an alcohol solution with respect to 1 mol of titanium alkoxides and / or a titanium chelate compound. The method of claim 2 or 3, The water-soluble titanium oligomer composition whose chelating agent is at least 1 sort (s) chosen from the group which consists of (beta) -diketone, (beta) -ketoester, polyhydric alcohol, alkanolamine, and oxycarboxylic acid. The method according to any one of claims 1 to 3, The water-soluble titanium oligomer composition whose amine compound (b) is a substituted or unsubstituted aliphatic amine or quaternary ammonium hydroxide. The method according to any one of claims 1 to 3, The water-soluble titanium oligomer composition whose glycol compound (c) is 1,2-ethanediol, 1,2-propanediol, or 2,3-butanediol. The method according to any one of claims 1 to 3, A water-soluble titanium oligomer composition having a chemical structure and composition formed by reacting and / or mixing a silicon compound (d) having at least one alkoxy group in a molecule with the titanium composite composition. The water-soluble titanium oligomer composition as described in any one of Claims 1-3 is contained, The crosslinking agent of water-based resin characterized by the above-mentioned. The water-soluble titanium oligomer composition of Claim 9 is contained, The crosslinking agent of water-based resin characterized by the above-mentioned. The water-soluble titanium oligomer composition as described in any one of Claims 1-3 is contained, The surface treating agent characterized by the above-mentioned. The surface treating agent containing the water-soluble titanium oligomer composition of Claim 9.