TW200930723A - Water-soluble titanium oligomer composition - Google Patents

Abstract

This invention provides a titanium oligomer composition stable to and soluble in water, and also a water-soluble titanium oligomer composition used as a crosslinking agent of an aqueous resin which has a high crosslinking ability, when used as a surface treating agent to perform coating on a plastic film to produce no crack when drying and having an excellent wetting ability to obtain an uniform coating surface. The approach of this invention is a water-soluble titanium oligomer composition comprising a titanium composite composition, in which the titanium composite composition includes at least a chemical structure and constitution by reacting and/or mixing a titanium compound oligomer (a), an amine compound (b), and a diol compound (c).

Description

200930723 6. Technical Field of the Invention The present invention relates to a water-soluble titanium oligomer composition. More specifically, it relates to a water-soluble titanium oligomer containing a titanium composite composition having a specific chemical structure and composition. Polymer composition. [Prior Art] A titanium chelate compound obtained by reacting a titanium oxide oxide or a titanium oxide oxide as a starting material with a/5-diketone oxime or the like is widely used as a surface treatment agent for a plastic film. A crosslinking agent of an organic resin, a raw material of a titanium oxide synthesis by a sol-gel method, a catalyst for esterification, and the like. However, these compounds are highly hydrolyzable, and the calcined oxide is hydrolyzed by moisture contained in the air, and the titanium chelate compound is also hydrolyzed by long-term exposure to water vapor. Therefore, in order to improve the hydrolysis resistance of the titanium compound or the coating property, there is a case where a titanium compound which is oligomerized with water is used. However, when the oligomer is only oligomerized, the effect of inhibiting hydrolysis is insufficient, and if it is exposed to water vapor or the like for a long period of time, there is a problem of white turbidity or white precipitate. On the other hand, in order to improve the stability to water, a titanium chelate compound belonging to triethanolamine or lactic acid using a water-soluble substituent or a compound in which a titanium alkoxide is reacted or mixed with a diol or an amine is known. However, these compounds are water-soluble compounds of a monomer, and the surface treatment agent used for a plastic film has a problem that the wettability is inferior and cracks are likely to occur, and a film of a thick film cannot be formed due to cracking in a single coating. Further, when the titanium chelate compound of the triethanolamine 97140612 _ 200930723 is used, since the ethanolamine remains, the adhesive remains on the surface at the time of low-temperature drying, and the adhesion phenomenon occurs in the plastic film. (Patent Document 1) Japanese Laid-Open Patent Publication No. 2004-256505 (Non-Patent Document 1) Sugiyama Iwaji "Metal-containing Organic Compounds and Their Utilization" ' MR Machine Month Biomass Series N〇. 5, p. 112~p. 116 (CMI Japan Co., Ltd.) [Disclosure] The present invention has been made in view of the above prior art, and its object is to provide titanium which is stable to water or water vapor and soluble in water. When the oligomer composition is used as a crosslinking agent for a water-based resin, the crosslinking property is high, and when a plastic film or the like is applied and dried as a surface treatment agent, cracking or the like is not caused, and the wettability is good and uniform A water-soluble titanium oligomer composition coated on the surface. (Means for Solving the Problem) The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a titanium oligomer compound obtained by oligomerizing a titanium alkoxide or a titanium chelate compound with water is used together with an amine compound. The titanium composite composition of the "chemical structure and the mixed composition" obtained by reacting or mixing the diol compound is stable to water and soluble in water, and is found to solve the above problems. . That is, the present invention is a water-soluble titanium oligomer composition characterized by containing a compound composition containing at least a titanium compound oligo 97160412 4 200930723 polymer (a), an amine compound (b) And the chemical structure and composition of the diol compound (c) reacted and/or mixed. Further, the present invention is a crosslinking agent for an aqueous resin characterized by comprising the above-mentioned water-soluble titanium polymer composition. Further, the present invention is a surface treating agent characterized by containing the above-mentioned water-soluble oligo oligomer composition. (Effect of the Invention) The water-soluble titanium oligomer composition of the present invention is extremely water-soluble, but is extremely stable against water or water vapor. Moreover, when using a crosslinking agent as a water-based resin, the water-based resin can be cross-linked to improve the heat resistance and water resistance of the water-based resin, and it can be obtained by coating, drying, and hardening of a plastic film. A uniform coated surface such as cracks does not occur. Further, when the water-soluble titanium oligomer composition of the present invention is used as a surface treatment agent, it can be used for polyethylene terephthalate (hereinafter abbreviated as "PET") or biaxially stretched polypropylene film (below A viscous material such as a plastic film such as "〇pp") can improve the adhesion of an organic resin or the like, and can produce a film which does not cause cracks or the like. Further, since it is excellent in wettability, uniform film-forming property, adhesiveness, surface modification property, and the like of various adherends, it is possible to bond the adhesive to the adherend which is difficult to adhere. [Embodiment] The present invention will be described below, but the present invention is not limited to the following embodiments, and can be carried out with any changes. [Chin composite composition] 97140612 5 200930723 The water-soluble titanium oligomer composition of the present invention contains a titanium composite composition having a "at least a titanium compound oligomer (a), an amine compound (b) And "diol structure (c)" "chemical structure and composition" by "reaction and / or mixing". [[Titanium compound oligomer (a)]] The titanium compound polymer (a) is not particularly limited. It is preferred to have a titanium oxide oxide represented by the following formula (1) or have the following formula ( 1) A structure in which a titanium chelate compound having a structure of a titanium alkoxide ruthenium complex chelating agent is condensed. (1) OR1 R20—Ti—OR4 (1) I 3 OR3 [In the formula (1), R1 to R4 each independently represent 18 carbon atoms of the carbon number. It is a "titanium alkoxide represented by the formula (1)" which is a starting material before condensation, and RL is independently an alkyl group having a carbon number of M8 in the formula (1), and is preferably independently The alkyl group having 1 to 8 carbon atoms is particularly preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of the "titanium oxide oxide represented by the formula (1)" include tetradecyloxy sulfonium, tetraethoxytitanium, tetra-n-propoxy phthalate, tetraisopropoxy cis, and tetra-n-butoxy. Titanium, titanium tetraisobutoxide, titanium diisopropoxide di-n-butoxide, titanium di-t-butoxydiisopropoxide, titanium tetra-butoxide, titanium tetraisooctyloxy, tetra Titanium stearate and the like. These may be used alone or in combination of two or more. 97140612 6 200930723 In addition to the above-mentioned "titanium-sintered oxide of the formula (1)", it is preferable to have a sound-matching coordination on the titanium oxide oxide represented by the formula (1), for example. A titanium chelate compound constructed as a chemical. The chelating agent is not particularly limited, but is preferably selected from the group consisting of a bis(tetra)avian polyol: an alkanolamine and an oxycarboxylic acid, from the (4) which enhances the characterization of the water of the titanium compound. At least one. ❹ Ο The /3-diindole compound is not particularly limited as long as it is carried out in the form of a chelating agent, and specific examples thereof include 2,4_red_, 2,4~2,4-heptanedion, and The base is 曱垸, 嗟 醢 醢 三氟 trifluoropropane m-ketone 1 base u, D: _ and so on. These may be used alone or in combination of two or more. As the point 峨 ', if the type of chelating agent is used for the coordination, it can be reduced, such as acetic acid, acetic acid, acetic acid, acetic acid, TMS, methyl neopentyl B, Methyl acetate vinegar, hexylmercaptoacetic acid methyl vinegar, and erythrodyl acetate are used alone or in combination of two or more. Such can

As the oxime alcohol, the right one is a group of a chelating agent, such as I 1' 2 n 2' 3 to butanediol, 2,3-butanediol, glycerin or diethylene glycol. These may be used alone or in combination of two or more. —,

The calcination-amine is particularly limited to those which are coordinated in the form of a chelating agent, and examples thereof include N'N-dimethylethanolamine, N, NN-p-aminoethylethanolamine, and N-methyl. Ethanolamine, N-methyldiethylammoniumamine, 97140612 200930723 Ν-ethylethanolamine, Ν-n-butylethanolamine, Ν-n-butyldiethanolamine, ν—third: isopropylamine, Ν~t-butyl Diethanolamine, triethanolamine, diethanolamine, monoethanolamine, and the like. These may be used alone or in combination of two or more. The oxynon is not particularly limited as long as it is a conjugate of the hydrazine, and examples thereof include glycolic acid, lactic acid, tartaric acid, sucrose acid, frequency acid, and gluconic acid. These may be used alone or in combination of two or more.钛 The titanium compound filament can be obtained by condensing the above-mentioned "titanium oxide" represented by the formula (1) or "a titanium chelate compound having a structure in which the chelating agent is coordinated with a chelating agent" ( a). Here, the method for performing the condensation is not particularly limited, and a method of reacting the titanium alkoxide or the titanium chelate compound with water in an alcohol solution, or the alcohol solution is used. A method of reacting a state in which an amine compound (b) described later is coexisted with water. The amount of water used for oligomerization for condensation is based on the total amount of titanium alkoxide and/or titanium chelate compound, ie, 1 mol relative to titanium atom, and stability to water. 5〜1. γ莫耳,特佳为0. 5〜 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 1. 6莫耳,更更更为1· 〇~1. 5莫耳. In addition, the above-described method for producing the titanium compound oligomer (a) of the present invention is not limited to the production method of the chemical structure such as the degree of condensation of the titanium compound oligomer (a) by a condensation method or the like. Since the titanium compound oligomer (a) has a chemical structure of two or three dimensions, its chemical structure can only be specified by a manufacturing method, and therefore, it is manufactured by a different manufacturing method, and has a 97140612 8 200930723 The compound chemical oligomer (4) of the same chemical structure can also be used in the present invention. 9 ^ (4)-form surface of the objective compound (a), the titanium compound oligomer (4) which is not in the formula (2) in comparison with the atomic moth Obtained by condensation.

Ti0x/2(0R)4-X (2) [Formula (2) A' R represents any of r1 to r4 in the formula (1). ] ❹ When the reaction is carried out for 1 mol of the titanium atom and 1 mol of the titanium atom, that is, when the water 2 mol is reacted with respect to the titanium atom 2, the formula (2) becomes:

Ti0i(0R)2 (3) In the case of titanium atoms! When Mohr reacts with water, that is, when the reaction is carried out with respect to the hydrogen atom 3 for the titanium atom 2, since χ = 3, the formula (2) becomes:

Ti〇3/2(OR)i (4) It is preferred to substitute the X value corresponding to the above-mentioned "preferred amount of water for condensing to be condensed" into the formula of the formula (2). The degree of condensation of the titanium compound polymer (a). The titanium compound oligomer (a) of the present invention is not particularly limited as long as it is an oligomer, and is preferably 1.5 to 20 parts by weight, more preferably 2 to 15 parts by weight, particularly preferably 4 to 13 parts by weight. More preferably, it is a 5 to 12 polymer. The degree of condensation is preferably larger from the viewpoints of stability to water, film forming properties, coating properties, and the like. In principle, the above formula (3) does not show an infinite degree of condensation in the 1st dimension, but the actually produced titanium compound has a limited degree of condensation. The titanium compound oligomer (a) of the present invention is more preferably a chemical structure produced by using an amount of water having an infinite degree of condensation in principle. * ❹ ❹ Butanol When condensed, a titanium oxide or a titanium chelating compound may be used as a solvent, and the titanium cerium oxide or the titanium chelating compound may be subjected to heat treatment by reflux or the like to obtain a titanium cerium aroma polymer. (a). The alcohol to be used in this case is not particularly limited, and from the viewpoint of not changing the reactivity of the titanium compound oligomer (a), it is preferred to have the alkyl group in the above formula (1); for example, methanol, Ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexanol, and the like. These may be used alone or in combination of two or more. The amount of the alcohol to be used is not particularly limited, and from the viewpoint of suppressing the occurrence of white turbidity or white precipitate of the chemical liquid, it is preferred to use the amount of water for performing condensation-polymerization with respect to water and the alcohol. When the total amount is 〇5 and the concentration of oligo% is used, it is diluted with the alcohol, and it is more preferably diluted to a concentration of 〇7 mass%, and it is particularly preferable to be a concentration of 1 〇~ι 〇. The way to dilute.

The titanium compound oligomer (a) preferably has a structure in which the above-mentioned titanium compound is oligo-stepped to form a chelating agent. That is, it is preferred that the following structure is used to condense a titanium chelate compound having a structure of (10) oxysulphate or a coordination chelating agent of the above formula (1); The structure in which the chelating agent is coordinated. That is, from the viewpoint of stability and qualitative hydrolysis of the titanium compound oligomer (4), the drum H 97140612 10 200930723 is a structure in which the chelating agent is reacted before and/or after condensation. The chelating agent to be used after the condensation is not particularly limited, and the above chelating agent can be suitably used. Particularly preferred are gluten-dione, beta ester or stearylamine. [[Amine compound (b)]] The amine compound (b) ' used for obtaining the titanium composite composition and reacting and/or mixing with the above-mentioned titanium compound oligomer (a) is not particularly limited, and the titanium compound is promoted. From the viewpoint of stability of hydrolysis of the polymer (a) and the like, and melting of water, it is preferable to use a substituted or unsubstituted aliphatic amine or a quaternary hydroxide. The substituent in the "substituted or unsubstituted aliphatic amine" is preferably an alcoholic trans group. As the substituted aliphatic amine, a cocoamine is particularly preferred. Specific examples of the non-substituted aliphatic amines include methylamines, ethylamines, n-propylamines, isopropylamines, n-butylamines, isobutylamines, and second butyl groups which are aliphatic alkylamines. Alkylamine, tert-butylamine, amylamine, second amylamine, didecylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, tridecyl Amine, triethylamine, tripropylamine, tributylamine; a piperidine, pyrrolidine or the like which is an aliphatic ring. These may be used alone or in combination of two or more. Specific examples of the alkanolamines include N,N-dimethylethanolamine, -ethylethanolamine, N_(/5-aminoethyl)ethanolamine, N-methylethanolamine, shamemethyldiethanolamine, and N-B. Ethanolamine, μ~n-butylethanolamine, N-n-butanol monoethanolamine, N-second butylethanolamine, N-t-butyldiethanolamine, triethanolamine, diethanolamine, monoethanolamine, and the like. These may be used alone or in combination of two or more. As the quaternary ammonium hydroxide, for example, tetramethylammonium hydroxide, tetra 97140612 11 200930723 ethyl hydroxide, tetrapropyl hydrazine, tetrabutylammonium hydroxide, tridecylbenzyl hydroxide Ammonium, 2-hydroxyethyltrimethylammonium hydroxide, and the like. These may be used alone or in combination of two or more. [[diol compound (c)]] The diol compound (c) which is used for the reaction and/or mixing with the above-mentioned compound oligomer (a) for the composition of the composition of the composition is not particularly limited. Preferably, the diol compound having a hydroxyl group on the adjacent carbon atom, specifically, for example, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentane Alcohol, 2'3_Dingyi drunk, 2,3-mercaptool, glycerin, etc. From the viewpoint of improving the stability of the hydrolysis of the oligopolymer compound or the like and water-solubilizing, it is particularly preferably styrene glycol, 1,2-propanediol or 2,3-butanediol. By using the diol compound (c), the stability of the titanium compound oligomer (a) against hydrolysis or the like can be enhanced to melt the water. [[Ratio of each component of the titanium composite composition]] ® "The ratio of the titanium compound oligomer (a)" to the "amine compound (b)" and the "diol compound (c)" is not particularly limited, b) Better than (a) Moh (b) / (a) = 0.1 / 1 (Μ 0 / 0. 1 ' Better (b) / (a) = 0.3 / 1 (Μ〇 / ,. 3, especially good 0. 5/10~10/0. 5. Right (a) relative to the total amount of (a) and (b_) is too small, it will make cross-linking, film forming, bonding On the other hand, if (a) is too large, there is a case where the stability to water solubility or hydrolysis is insufficient. (0 is better than (&) Moh (0/( &)=〇.1/1〇~1〇/〇.1, better 97140612 12 200930723 Department (c)/(a)=〇· 5/10~io/ο. 5, especially good 1/1 〇~1〇/1. If the total amount of (a) and (c) is too small, the crosslinkability, film formability, adhesion, and the like are lowered. On the other hand, if (a) is excessive There is a case where the stability to water solubility or hydrolysis is insufficient. Regarding the titanium compound oligomer, the amine compound (b) and the diol compound in the titanium composite composition The chemical structure of the compound of the structure obtained by the reaction of (c) (hereinafter simply referred to as "compound A") is not limited to those produced by a specific production method if it has a structure obtained by the above-described production method. The chemical structure of the compound A is preferably an ethanol chelate compound or a amine of a titanium compound oligomer obtained by reacting the titanium compound oligomer (a) with the amine compound (b) and the diol compound (c). a structure based on titanium. The alkoxy group at the end of the titanium compound oligomer (a) is reacted with the amine compound (b) and/or the diol compound (c) to be chelated. The structure in which the hydroxyl group of the amine compound or the diol compound of the amine compound is coordinated to the titanium atom. The titanium composite composition of the present invention contains the above compound A, the titanium compound condensed polymer (a), and the amine compound (b) And/or diol compound (c). Titanium composite composition• may have a composition for mixing the amine compound (b) and the diol compound (c) at room temperature for the titanium compound polymer (a) Occasionally The component (a) is obtained by heating and refluxing the amine compound (b) and the diol compound (c), and the composition is the same as the above-mentioned "mixed composition", and also includes the reaction in the unreacted state without performing the total amount of the reaction. In the case of the case, or only a part of the reaction is carried out. 97140612 13 200930723 The titanium composite yarn of the present invention is not particularly limited as long as it is composed of the above-mentioned ones. It is preferably the following five forms. (1) Compound A (2) a mixture of compound A and titanium compound oligomer (a); (3) a mixture of compound A and diol compound (c); (4) compound A, titanium compound condensate (a) and diol a mixture of the compound (c); ❹ (5) a mixture of the titanium compound oligomer (a) and the amine compound (b) and the diol compound (c); wherein 'from the viewpoint of suitably obtaining the effects of the present invention described above, Preferably, it is a form (1) and a form (5). [矽 compound (d)] The water-soluble titanium oligomer composition of the present invention may be formed only of the above titanium composite composition, or may have the titanium composite composition further to have "1 in the branching tweezers" The chemical structure and composition of the compound (d) of the above-mentioned calcined base compound (d) (hereinafter referred to as "crushed compound (d)") are reacted and/or mixed. The ruthenium compound (d) is not particularly limited, and is preferably a decane coupling agent or a ruthenium compound in which four alkoxy groups are bonded to a ruthenium atom from the viewpoint of improving film formability. Among them, those having an amine group, a mercapto group or an epoxy group are more preferable from the viewpoint of improving the moldability. Further, from the viewpoint of improving the film formability, it is preferred that the structure in which the alkyl group is directly bonded to the ruthenium atom is the alkyl group at this time, and is preferably a fluorenyl group. Further, it is also suitable to use the partially hydrolyzed 97140612 lyl 200930723 condensate of the above compound. Specific examples of the hydrazine compound (d) include tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, r-aminopropylaminoethyltrimethoxydecane, and aminopropylamine. Ethyl ethyl dimethyl decyl oxane, 7-aminopropyl aminoethyl triethoxy decane, r-aminopropylaminoethyl decyl diethoxy decane, r-aminopropyl Tris-methoxydecane, τ-aminopropyltriethoxydecane, r-ureidopropyltrimethoxydecane, r-ureidopropyltriethoxynonane, N-styl-7-amine Propyltriethoxydecane, r-glycidoxypropyltrimethoxydecane, 7-glycidoxypropylmethyldimethoxydecane, -r-cycloJipropoxypropyl Triethoxy ox, r-cyclopropoxypropylmethyldiethoxy decane, /9-(3,4-epoxycyclohexyl)ethyltriethoxydecane, r-fluorenyl Propyltriethoxydecane, r-mercaptopropyltrimethoxy decane, 7-mercaptopropyl decyldiethoxy decane, decylpropyl decyl decyloxydecane, r-mercaptopropene Nonyl propyl decyl dimethoxy decane, το decyl propylene propyl propyl trimethoxy decane . These may be used alone or in combination of two or more. 'In the above titanium composite composition, when the ruthenium compound (d) is used in combination to obtain a water-soluble titanium oligomer composition, it is preferred to have the ruthenium compound (d) reacted by the titanium composite composition and/or Or a mix of constructors. Here, the reaction method is not particularly limited, and it is preferred to mix the titanium composite composition with the ruthenium compound (d) and then reflux and react at the boiling point of the solvent to be used. Also, there is no regulation on the order of deployment. 97140612 15 200930723 The ratio of use of the titanium composite composition to the ruthenium compound (d) is not particularly limited, and the quality of the titanium composite composition and the ruthenium compound (d) is preferably 0·1/ΙίΜΟ/Ο. 1. More preferably 〇 · 5/10~10/0. 5 , especially good for 1/1〇1〇/1. When the amount of the titanium composite composition is too small, the film forming property is lowered, and the film forming property is lowered. The case where the stability of hydrolysis or the like is insufficient. The water-soluble titanium oligomer composition of the present invention is not limited to those produced by the above-described method for producing a crucible, and if it is a composition having a chemical structure and composition produced by the above-described production method, even if the manufacturing method is different, In the present invention, the water-soluble titanium polymer composition of the present invention is preferably produced by the above production method. In other words, the method for producing a titanium composite composition and the method for producing a water-soluble titanium oligomer composition are preferably at least a titanium compound oligomer (a), an amine compound (b), and a diol compound (c). Carry out the reaction and/or mix. Further, as a method for producing a water-soluble titanium oligomer composition, it is preferable to use a titanium complex composition to form a ruthenium compound having one or more alkoxy groups in the molecule (resonance reaction and/or mixing). The crosslinking agent] The water-soluble titanium oligomer composition of the present invention can be suitably used as a water-based crosslinking agent in an aqueous resin. Further, it is suitably used for a surface treatment agent, that is, it is preferably a water-based paint or surface. The water-soluble titanium oligomer composition of the present invention is added to the treatment agent or the like. In the present invention, the term "aqueous resin" means dissolved or suspended dispersion or emulsification in a solvent or a dispersion medium mainly composed of water. 200930723 The resin of the knife is scattered. In addition to the water-soluble resin coating, it also includes water-based resin coatings for water-insoluble resins. Water-based resins are not water-soluble resins. For example, a polyvinyl alcohol, a polyethylene material, a polyacetate, a hydrolyzate, and the like may be mentioned. Further, as a resin suspended or emulsified in a water towel, for example, (meth)acrylic resin or acetic acid B may be mentioned. The resin is not particularly limited as long as it is used for the crosslinking of the coating material, and is preferably O 3 when it is subjected to heat curing (MGG ° C, more preferably 4 G to 8 GI hardening time). It is 1 () second or more, and more preferably 1 minute or more. [Surface treatment agent] In addition, since the surface treatment agent can be diluted with water without using an organic solvent, it is coated from the viewpoint of the working environment. Preferably, the surface suitable for use as the water-soluble titanium oligomer composition of the present invention is not particularly resistant, and may be, for example, a plastic surface such as ruthenium, ruthenium, or polyethylene; a metal surface; L-ene propylene rubber, styrene A rubber surface or the like of a diene rubber or the like. The surface treatment agent containing the water-soluble titanium oligomer composition of the present invention is preferably a film having a dry film thickness of 0.01 "m~, especially good 〇〇2em~〇 (5) Coating is carried out in the form of a field. Thereafter, the surface is dried by a usual method. (Examples) Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples, but the present invention does not exceed the gist of the present invention. , not limited to this (Production Example 1) 97140612 17 200930723 After dissolving 28.4 g (0.10 mol) of tetraisopropoxy oxime in 50.0 g of isopropyl alcohol, 2.7 g (0.15 mol) of water and 5 异丙 of isopropanol were added dropwise. Mixture of 〇g. After dripping... bunch, stir; hrs to get "titanium compound oligomer (4)a". After adding N, N-methyl monoethanolamine 8 moles, after adding 1 hour, add L 2~2 diol 30. 4g (0. 40m) 'scrambled! hours, and then enter the lamp for U hours to get "titanium composite composition ^". The compound composition A (4) is composed of "water soluble titanium wire".驰 (Production Example 2) / 28.4 g of titanium isopropoxide (〇.i〇m) dissolved in 5 〇〇g of isopropanol and then dropped water 7 7 g ((U5 Mo) Mixed with different (four) 5Q. Qg. Drip, ° bunch ♦, 1 hour to get "titanium compound silk (a) B" times, add N, π π 甘, -, butyl ethanolamine 5.9g (〇. 〇 5 Mo), stir 1 small = after 'adding glycerin 36.8g (0.40 mol), _H hours, then back

Serving the titanium composite composition Β". The titanium composite composition Β / is referred to as "a water-soluble titanium polymer composition". (Production Example 3) Butadiene-based titanium 34.0 g (0. 丨〇mol) was dissolved in n-butanol 30. 〇g, 钤 drops of water 2. 7g (0·15 moles) and n-butanol 6〇. 〇 a mixture of g. After the bundle, the mixture was stirred for 1 hour to obtain "titanium compound polymer (a) c". Next 5 'add ~~ 7 ο* A „ , ' 〜 ethylamine 3. 7g (〇. 05 摩尔), after stirring for 丨 hours, add 1 2~"Γ _ no, diol 36.0g (0.40 Moer), stir for a few hours, and then go back to the temple to get "titanium composite composition C". The one formed by the titanium composite composition c 97140612 200930723 is referred to as "water-soluble titanium oligomer composition c". (Production Example 4) After dissolving 28.4 g of titanium tetraisopropoxide (0.10 mol) in 5 〇〇g of isopropyl alcohol, 'drop 2.7 g of water (〇.i5 mol) and isopropyl alcohol 5 § Mixture. After the completion of the dropwise addition, "titanium compound oligomer (4) D" was obtained by stirring. Secondly, adding N,N dimethyl dimethylethanolamine 8·9g (〇. 1〇莫耳) and then stirring 1 ❹

After the hour, add 2' 3~butanediol 讥0g (0. 40 moles) and stir! In the hour, the mixture was further refluxed for 1 hour to obtain "titanium composite composition D". The one formed of the titanium composite composition D is referred to as "water-soluble titanium wire composition D". (Manufacturing Example 5). Except for the amount of water of 2. 4 g (〇·1〇莫耳) of titanium tetraisopropoxide, the amount of water was 2. 2 g (G. 12 mol), and the rest was In the same manner as in Production Example 4, "titanium compound polymer (4) E" and "titanium composite composition" were obtained. 4克((乌摩尔) was dissolved in isopropanol 5 as a "water-soluble oxime oligomer composition (manufacturing example 6). _中后'Drip water 2.7g (G.15 mol) and isopropanol._ Mixture. After the end of the drop, 'stir 1 hour, 1 day, and then reflux for 1 hour and 4! to the titanium compound Polymer (a)F". Its +,%" re-added diethylamine 5.1g (0.0i mole) after 'steaming for 1 hour, bearing capacity〗 9 $ Adding 1,2-diol 3〇4g(〇4〇莫耳)' was given for 1 hour, and then the appropriate 1f卩Ten plague machine was used for 1 hour to obtain “titanium composite composition F.” It will be formed by the compound composition ρ. The test is referred to as "water-soluble titanium oligomer 97140612 200930723 composition F". (Production Example 7) After dissolving 28.4 g of titanium tetraisopropoxide (〇.10 mol) in isopropyl alcohol 5 〇〇 A mixture of 2.7 g (〇.15 mol) and 5 μg of isopropanol was added dropwise. After the completion of the dropwise addition, "titanium compound oligomer (a) G" was obtained in one hour (four). Second, N, N- was added. After dimethyl monoethanolamine 8 _.1 〇 Mo ear), Lin, ^ small After that, 1,2-propanediol 3〇. 4g (〇. 4〇莫耳) was added, and the mixture was refluxed for 1 hour to obtain "Qin Composite Composition G". Add 4,4g of T-aminopropylaminoethyldiethyloxy (L2Q Mo) to Yuqin Composite Composition G, and mix it for a few hours, then reflux (hours). Titanium oligomer composition G". (Production Example 8); isopropyl milk based titanium 28.4 g (〇. 10 mol) added N,N-dimethyl monoethanolamine 9 g (〇. 1〇莫耳) After the addition, the search was carried out for an hour. Then 1,2 g of propanol was added to 3 〇.4 g (0·40 mol), and when H was scrambled, reflux was further carried out for 1 hour to obtain "titanium compound a". Production Example 9) Addition of triethylamine 20 to tetra-n-butoxytitanium 34 〇g (〇1〇莫耳) 200930723 to tetraisopropoxytitanium 28 4&n, # ^ln wn '4g (0.l Mole) added triethylamine l〇.lg (0.l mole) for 30 minutes. Add γ-(2-aminoethyl)aminopropylmethyldiethoxy residue 46 g (Q2 mol), followed by the addition of 12-glycol 49.6 g (0.8 mol), and the mixture was stirred for 1 hour, and refluxed for 1 hour to obtain "chin compound c". (Example 1~ 7 'Comparative Examples 1 to 13' ❹ [Evaluation of Stability and Solubility of Water] "Titanium compound oligomers (4) A to G" and "water-soluble titanium ruthenium poly-agglomerates A to G" manufactured by Production Examples 1 to 7 of tetra-n-butoxytitanium and tetra-n-butoxy-dimer, and production examples δ, the "conduct 2 Π mass part" produced was added to the water 9 G f portion, and the stability to water and the solubility in water were confirmed. The results are shown in Table i. ❹ 97140612 21 200930723 (Table 1)

No. Preparation Example Titanium Compound Stability and Solubility in Water Comparative Example 1 - Tetrapropoxy Oxygen White Sinking Comparative Example 2 - Tetra-n-Butyloxy Titanium White Precipitation Comparative Example 3 - Tetra-n-butoxytitanium Dioxide Polymer white precipitate Comparative Example 4 Production Example 1 Titanium compound oligomer (a) A White precipitate Comparative Example 5 Production Example 2 Qin compound oligomer (a) B White precipitate Comparative Example 6 Production Example 3 Titanium compound oligomer ( a) C White precipitate Comparative Example 7 Production Example 4 Titanium compound oligomer (a) D White precipitate Comparative Example 8 Production Example 5 Titanium compound oligomer (a) E White precipitate Comparative Example 9 Production Example 6 Bismuth compound oligomer (a) F White precipitate Comparative Example 10 Production Example 7 Titanium compound oligomer (a) G White precipitate Example 1 Production Example 1 Water-soluble titanium oligomer composition A Transparent liquid Example 2 Production Example 2 Water-soluble titanium oxide Polymer Composition B Transparent Liquid Example 3 Production Example 3 Water-Soluble Titanium Oligomer Composition C Transparent Liquid Example 4 Production Example 4 Water-Soluble Titanium Oligomer Composition D Permeable Liquid Example 5 Production Example 5 Water-Soluble Titanium oligomer composition E transparent liquid Example 6 Production Example 6 Water-soluble titanium oligomer composition F Transparent liquid Example 7 Production Example 7 Water-soluble titanium oligomer composition G Transparent liquid Comparative Example 11 Production Example 8 Compound a transparent liquid Comparative Example 12 Production Example 9 Titanium compound b Transparent liquid Comparative Example 13 Production Example 10 Titanium compound C Transparent liquid

97140612 22 200930723 The water-soluble titanium oligomer compositions A to G produced in Production Examples 1 to 7 are obtained from the results of Examples 1 to 7 of Table 1 above, and are soluble in water and stable to water. Also superior. On the other hand, in the compound of Comparative Examples 1 to 3, the titanium compound oligomers (a) A to G before the addition of the amine compound (b) and the diol compound (c) (Comparative Examples 4 to 10) When it occurs, white precipitation occurs, and the stability to water and the solubility in water are inferior. (Examples 8 to 14 and Comparative Example 14) ❹ [Evaluation of Crosslinking Property of Polyvinyl Alcohol] 2 parts by mass of the water-soluble titanium oligomer composition manufactured in Production Example W, as a water-based resin A 5 mass% aqueous solution of polyvinyl alcohol (rG〇HS£N〇Lj N_3〇〇 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)) was mixed in an amount of 1 part by mass to obtain a resin solution. Further, in place of 2 parts by mass of the water-soluble titanium oligomer composition A to G, monoisopropoxy titanium bis(triethanolamine (aminat) was used (Matsum〇t Fine Chemical Co., Ltd.) The resin solution of Comparative Example 14 was obtained in the same manner as in Examples 8 to 14 except that RGATIX TC_4 was used in an amount of 2 parts by mass. The resin solutions of Examples 8 to 14 and Comparative Example 4 were weighed to 5 g to a bottom area of 70 cm 2 . The aluminum cup was dried for 4 hours in a hot air circulation dryer of 4 Torr. The dried film was placed in a 100 mL beaker, 1 mL of water was added, and boiled for 1 hour. Thereafter, filtered using a filter paper. Insoluble, at 1 〇 5. (: Dry for 2 hours, weigh the amount of filter paper and insoluble parts, calculate the insolubilization rate (% by mass) from the following formula. The results are not shown in Table 2. 97140612 23 200930723 Insolubilization rate (% by mass) = [((: Β)/Α]χ100 Here, A=the mass of the film before the test (g) the mass of the B filter paper (g) C=the mass of the filter paper+insoluble (g) (Table 2)

No. Production Example Titanium compound insolubilization ratio (%) Example 8 Production Example 1 Water-soluble titanium oligomer composition A 70 Example 9 Production Example 2 Water-soluble titanium oligomer composition B 70 Example 10 Production Example 3 Water-soluble Titanium Polymer Concentrate Composition C 70 Example 11 Production Example 4 Water-Soluble Titanium Oligomer Composition D 70 Example 12 Production Example 5 Water-Soluble Titanium Oligomer Composition E 70 Example 13 Production Example 6 Water-Soluble Titanium Oligomer Composition F 70 Example 14 Production Example 7 Water-soluble titanium oligomer composition G 70 Comparative Example 14 - Diisopropoxytitanium bis(triethanolamine) 55

97140612 24 200930723 The "water-soluble oligo oligomer composition A to G" of the present invention in Examples 8 to 14 showed high crosslinkability to polyvinyl alcohol. On the other hand, the titanium compound of Comparative Example 14 showed no high crosslinkability to polyvinyl alcohol. [Evaluation of the sputum-forming property and the sclerosing property] The water-soluble titanium oligomer composition (A to G 5 parts by mass) manufactured in Production Examples 1 to 7 was added and mixed into 95 parts by mass of water to obtain Examples 15 to 21. Surface treatment agent. Further, as a comparative example 15, the titanium ruthenium compound a produced in Production Example 8 was used as Comparative Example 16'. The titanium compound b' produced in Production Example 9 was used to obtain a surface treatment agent in the same manner as in Production Examples 1 to 7. The surface treatment agents of Examples 15 to 21 and Comparative Examples 15 to 16 were applied to the surface of an untreated pET (poly(ethylene terephthalate) film having a thickness of 50 μm by a bar coater No. 4. Dry with a hot air circulation dryer of 15 (TC for 3 sec.) Observe the presence or absence of cracks on the surface of the dried film by a laser microscope, and evaluate the occurrence of cracks in those who have not cracked. The crack is evaluated as A and at the same time, After rubbing the face with the money, the surface was visually observed, and the film of (4) was used as the 〇, and the film was whitened after the wiping. The results are shown in the following buckle 97140612 200930723 (Table 3)

No. Production Example Titanium compound with or without cracks After film wiping Example 15 Production Example 1 Water-soluble titanium oligomer composition A 〇〇 Example 16 Production Example 2 Water-soluble titanium oligomer composition B 〇〇 Example 17 Production Example 3 Water-soluble titanium oligomer composition C 〇〇 Example 18 Production Example 4 Water-soluble titanium oligomer composition D 〇〇 Example 19 Production Example 5 Water-soluble titanium oligomer composition E 〇〇 Example 20 Production Example 6 Water-soluble oligo oligomer composition F 〇〇 Example 21 Production Example 7 Water-soluble oligo oligomer composition G 〇〇 Comparative Example 15 Production Example 8 Compound a XX Comparative Example 16 Production Example 9 Titanium compound b XX Comparative Example 17 Production Example 10 Titanium compound CXX ❹ 97140612 26 200930723 The water-soluble titanium oligomer composition A to G of the present invention produced in Production Examples 1 to 7 was carried out according to Examples 15 to 21 of Table 3 above. As a result, it was found that a uniform film which did not crack even after drying at 150 ° C for 30 seconds was produced. Further, a film which maintains a transparent state even when rubbed with a finger can be obtained. On the other hand, in the production examples 8 to 10, the titanium compounds a to c obtained by reacting and/or mixing the amine compound (b) with the diol compound (c) in the titanium compound were evaluated in the same manner and cracked. The film was whitened after rubbing (Comparative Examples 15 to 17).产业 (Industrial Applicability) The water-soluble titanium oligomer composition of the present invention can be imparted with water resistance or solvent resistance by being added to a water-based paint or resin for crosslinking. By using a surface treatment agent, a uniform surface can be obtained, so that it can be widely used in industrial fields such as the field of coatings or surface treatment.

97140612 27

Claims (1)

200930723 VII. Patent application scope: 1. A water-soluble titanium oligomer composition characterized by containing a titanium composite composition containing at least a titanium compound polymer (a) and an amine compound (b) And the chemical structure and composition of the diol compound (c) reacted and/or mixed. 2. The water-soluble titanium oligomer composition according to claim 1, wherein the titanium compound oligomer (a) has a titanium alkoxide or titanium chelate as shown in the following formula (1) a structure in which a compound is condensed; the titanium chelate compound has a structure in which a chelating agent is coordinated to a cerium oxide represented by the following formula (1); (Chemical Formula 1) OR1 (1) R20-Ti-OR4 OR3 [Formula (1) The 'RLR4 independently represents an alkyl group having 1 to 18 carbon atoms. 3. The water-soluble titanium oligomer composition according to the first aspect of the invention, wherein the titanium compound oligomer (a) has a titanium alkoxide represented by the following formula (1), or a chemical structure having a structure in which a titanium chelate compound having a structure of a chelating agent on a titanium alkoxide represented by the following formula (1) is condensed, and a nutrient agent is further coordinated; (Chemical 2) OR1 R2〇—Ti—OR4 OR3 97140612 28 (1) 200930723 [In the formula (1), R1 to R4 each independently represent a carbon number of 18 alkyl groups]. 4. The water-soluble titanium oligomer composition according to claim 2, wherein the condensation is carried out by reacting the titanium alkoxide or the titanium chelate compound with water in an alcohol solution. . 5. The water-soluble titanium oligomer composition according to claim 2 or 3, wherein the above condensation is caused by water in an alcohol solution for a titanium alkoxide and/or a titanium chelate compound 1 molar 0. 2~2 Moore reaction was carried out. 6. The water-soluble titanium oligomer composition according to claim 2 or 3, wherein the chelating agent is from a cold-diketone, a cold-ketoester, a polyol, an alkanolamine, and an oxy group. At least one of the selected groups of tannins. 7. The water-soluble titanium oligomer composition as claimed in any one of claims 1 to 3 wherein 'the amine compound (b) is a substituted or unsubstituted aliphatic amine or a quaternary phoenix oxide. 8. The water-soluble titanium oligomer oxime composition according to any one of claims 1 to 3, wherein the diol compound (c) is 1,2-ethanediol, iota, 2-propanediol or 2, 3-butanediol. 9. The water-soluble occult polymer composition of any one of claims 1 to 3, wherein the titanium compound has a ruthenium compound having one or more alkoxy groups in the molecule. (d) The chemical structure and composition of the reaction and/or mixing. A cross-linking agent characterized by comprising the water-soluble titanium oligomer composition of any one of claims 1-3. 97140612 29 200930723 U, a kind of cross-linking agent' is characterized by containing a water-soluble titanium oligomer composition of item 9 of the patent scope. A surface treatment agent characterized by comprising the water-soluble titanium oligomer composition of any one of claims 1 to 3. A surface treatment agent characterized by comprising the water-soluble titanium oligomer composition of claim 9 of the patent application. 〇 〇 97140612 30 200930723 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) Simple description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Chemical 1] OR1 R20—Ti—OR4 (1) I 3 OR3 97140612 2