JP2011111482A - Deodorizing effect-imparting coating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent that exhibits high adhesive properties to an adherend by a simple method, can be applied to an adherend by a simple method and excellently deodorizes particularly acetic acid and ammonia. <P>SOLUTION: The deodorizing effect-imparting coating agent comprises at least a deodorizing composite composition that has a chemical structure and a composition, obtained by reacting and/or mixing (A) a titanium alkoxide or a zirconium alkoxide represented by formula (2) or a compound having a structure where a chelating agent coordinates to those alkoxides and (B) a solvent, and is applied to an adherend to impart a deodorizing effect to the adherend. In the formula, M is Ti or Zr; R<SB>5</SB>to R<SB>10</SB>are each independently a 1-18C alkyl group; and n is an integer of at least 0. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a deodorizing effect-imparting coating agent, and more specifically, a deodorizing effect-imparting coating containing a chemical structure and composition obtained by reacting and / or mixing a specific titanium compound or zirconium compound and a solvent. Plant fibers, animal fibers, polyester synthetic fibers, polyamide synthetic fibers, cellulosic semisynthetic fibers, protein semisynthetic fibers, regenerated fibers, glass fibers, carbon fibers, metal fibers, and The present invention relates to a deodorant formed by coating yarn, cloth, paper, plastic film, plastic molded body and the like made of these fibers.

  For coating agents that give deodorizing effects, photocatalysts using porous inorganic oxides and anatase-type titanium oxide are known, and they deodorize malodorous components such as acetic acid, ammonia, aldehydes, nonenal, and isovaleric acid. It has been known.

  For porous inorganic oxides, deodorized wallpaper obtained by impregnating at least one of porous silicon dioxide supporting polyamine, hydrated zirconium oxide, zirconium oxide, hydrotalcite compound or hydrotalcite fired product into the wallpaper. Is disclosed (Patent Document 1).

  However, in the case of such a technique, the deodorizing performance of the odor gas in room air is inferior, and the sustainability of the deodorizing performance is short, which is not satisfactory. In addition, when a coating material using a porous inorganic oxide is used, it is difficult to obtain the problem of changing the texture of the adherend and the adhesion between inorganic particles and cloth, plastic film, paper, etc. Further, there was a problem that the film was removed by simple rubbing, and the deodorizing effect was impaired by the removal.

  On the other hand, in the deodorization by the photocatalyst with anatase type titanium oxide, a method using a hard-to-decompose binder such as a fluorine-based resin or a silicone-based resin as a fixing agent for titanium oxide (Patent Document 2), or porous titanium oxide fine particles. A method of supporting the material (Patent Document 3) is adopted.

  However, when using anatase-type titanium oxide having photocatalytic performance, it is highly degradable to organic matter, so inexpensive acrylic resins and urethane resins cannot be used as binders, and should be handled in the same way as ordinary pigments. I could not. In addition, ultraviolet rays are indispensable for developing photocatalytic performance, and it takes time to decompose organic matter, so it can withstand use in a state where the gas in the atmosphere circulates for a long time. There was a problem that the deodorizing effect could not be expressed.

Japanese Patent Laid-Open No. 11-028689 JP-A-7-171408 Japanese Patent Laid-Open No. 3-157125

  The present invention has been made in view of the above-described background art, and the problem is that even if it is applied to the surface by a simple method, the adherend is a plant fiber, animal fiber, polyester-based synthetic fiber, or polyamide-based material. High adhesion to synthetic fibers, cellulosic semi-synthetic fibers, protein-based semi-synthetic fibers, recycled fibers, glass fibers, carbon fibers, metal fibers, and yarns, cloths, paper, plastic films, plastic moldings, etc. made of these fibers It is an object of the present invention to provide a coating agent that can be coated by a simple method and that is particularly excellent in deodorizing acetic acid and ammonia.

  As a result of intensive studies to solve the above problems, the present inventor has found that a deodorant composite composition having a composite compound obtained by mixing or reacting a specific titanium or zirconium compound and a solvent solves the above problems. As a result, the present invention has been completed.

［式（１）中、ＭはＴｉ又はＺｒを示し、Ｒ_１〜Ｒ_４は、それぞれ独立に炭素数１〜１８個のアルキル基を示す。］ That is, the present invention includes at least
(A) "Titanium alkoxide or zirconium alkoxide represented by the following formula (1)", or
“A compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide represented by the following formula (1)”;
(B) A “deodorant composite composition that coats an adherend to give a deodorizing effect to the adherend” and has a chemical structure and composition obtained by reacting and / or mixing a solvent.
The present invention provides a deodorizing effect-imparting coating agent comprising:

[In Formula (1), M represents Ti or Zr, and R _{1 to} R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms. ]

［式（２）中、ＭはＴｉ又はＺｒを示し、Ｒ_５〜Ｒ_１０は、それぞれ独立に炭素数１〜１８個のアルキル基を示し、ｎは１以上の整数を示す。］ The present invention also includes at least
(A) "Titanium alkoxide or zirconium alkoxide represented by the following formula (2)", or
“A compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide represented by the following formula (2)”;
Solvent (B)
And a chemical structure and a composition obtained by reacting and / or mixing the "deodorant composite composition that coats the adherend and gives a deodorizing effect to the adherend"
The present invention provides a deodorizing effect-imparting coating agent comprising:

[In Formula (2), M represents Ti or Zr, R _{5 to} R ₁₀ each independently represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 1 or more. ]

  Moreover, this invention provides the deodorizing film | membrane characterized by being formed into a film using said deodorizing effect provision coating agent.

  Moreover, this invention provides the deodorizing body characterized by having said deodorizing film on a to-be-adhered body.

  In the present invention, the adherend is made of plant fiber, animal fiber, polyester-based synthetic fiber, polyamide-based synthetic fiber, cellulose-based semi-synthetic fiber, protein-based semi-synthetic fiber, regenerated fiber, glass fiber, carbon fiber, and metal. At least one type of fiber selected from the group consisting of fibers, a non-woven fabric having these fibers, a yarn formed by spinning these fibers, a woven fabric formed by woven these yarns, and a knitted fabric formed by knitting these yarns The present invention provides the deodorant body which is paper, a plastic film or a plastic molded body.

  The present invention also provides a method for producing a deodorizing film, which comprises a step of coating the adherend with the deodorizing effect-imparting coating agent.

  According to the deodorizing effect imparting coating agent of the present invention, the above-mentioned problems and problems are solved, the deodorizing performance and deodorizing sustainability are high, the deodorizing effect is exhibited in a short time, and the adhesion to the adherend. Can provide an excellent deodorizing effect-imparting coating agent.

  In particular, from the group consisting of plant fibers, animal fibers, polyester-based synthetic fibers, polyamide-based synthetic fibers, cellulose-based semi-synthetic fibers, protein-based semi-synthetic fibers, recycled fibers, glass fibers, carbon fibers and metal fibers, which are adherends At least one selected fiber, non-woven fabric having these fibers, yarn formed by spinning these fibers, woven fabric obtained by weaving these yarns, knitted fabric obtained by knitting these yarns, paper, plastic film Or it has high adhesiveness with respect to a plastic molding etc., and can be coated by a simple method.

  In addition, it is excellent in deodorizing performance of odorous gases in the air such as indoors, has a long duration of the deodorizing performance, and has a low degree of changing the texture of the adherend, such as fiber, thread, cloth, plastic film, A deodorizing film having particularly high adhesion to paper or the like can be provided. Further, since the deodorizing active ingredient is not inorganic particles, a dispersion step is not necessary, and ultraviolet rays are not essential for exhibiting catalytic performance, and the deodorizing effect can be exhibited in a short time.

  In particular, it can be cured at a low temperature of 200 ° C. or lower, and a titanium compound or a zirconium compound having a deodorizing effect is firmly bonded to various adherends by reaction, van der Waals force, or the like. be able to. In particular, a high adhesive effect can be exerted on an adherend having a hydroxyl group, a carboxyl group, an amino group, or the like.

  In addition, when the coating agent for imparting deodorizing effect of the present invention is used, the deodorizing ability for acetic acid and ammonia is particularly high, and these compounds can be deodorized in a short time. In addition, due to the high adhesive performance, resistance to washing, rubbing, etc. can be expressed.

  Hereinafter, the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented.

The deodorant effect-imparting coating agent of the present invention contains at least a deodorant composite composition having a chemical structure and composition obtained by reacting and / or mixing the following component (A) and component (B).
(A) “titanium alkoxide or zirconium alkoxide” or “compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide”
(B) Solvent

［式（１）中、ＭはＴｉ又はＺｒを示し、Ｒ_１〜Ｒ_４は、それぞれ独立に炭素数１〜１８個のアルキル基を示す。］ The “titanium alkoxide or zirconium alkoxide” in the component (A) is represented by the following formula (1) or the following formula (2).

[In Formula (1), M represents Ti or Zr, and R _{1 to} R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms. ]

［式（２）中、ＭはＴｉ又はＺｒを示し、Ｒ_５〜Ｒ_１０は、それぞれ独立に炭素数１〜１８個のアルキル基を示し、ｎは１以上の整数を示す。］

[In Formula (2), M represents Ti or Zr, R _{5 to} R ₁₀ each independently represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 1 or more. ]

In the “titanium alkoxide or zirconium alkoxide” represented by the above formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms, preferably each independently having 1 carbon atom. 10 to 10 alkyl groups, particularly preferably each independently an alkyl group having 1 to 8 carbon atoms.

The “titanium alkoxide or zirconium alkoxide represented by the above formula (1)” is not limited to the following specific examples. For example, tetramethyl titanate, tetraethyl titanate, tetranormal propyl titanate, tetraisopropyl titanate, tetranormal butyl Titanium alkoxides such as titanate, tetraisobutyl titanate, diisopropyl dinormal butyl titanate, ditertiary butyl diisopropyl titanate, tetratertiary butyl titanate, tetraisooctyl titanate, tetrastearyl titanate;
Tetramethyl zirconate, tetraethyl zirconate, tetranormal propyl zirconate, tetraisopropyl zirconate, tetranormal butyl zirconate, tetraisobutyl zirconate, diisopropyl dinormal butyl zirconate, ditertiary butyl diisopropyl zirconate, tetratertiary butyl zirconate , Zirconium alkoxides such as tetraisooctyl zirconate, tetrastearyl zirconate;
Is mentioned. These can be used alone or in admixture of two or more.

  In addition to “titanium alkoxide or zirconium alkoxide represented by the above formula (1)”, “titanium having a structure in which a chelating agent is coordinated to“ titanium alkoxide or zirconium alkoxide represented by the above formula (1) ”. The chelate compound or zirconium chelate compound "" (A) is also reacted and / or mixed with the solvent (B) to produce the deodorant composite composition of the present invention.

  The chelating agent is not particularly limited, but may be at least one selected from the group consisting of β-diketone, β-ketoester, polyhydric alcohol, organic fatty acid, oxycarboxylic acid, phosphate ester and alkanolamine. In view of improving stability against hydrolysis of titanium alkoxide or zirconium alkoxide.

  Specific examples of the β-diketone include 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, dibenzoylmethane, thenoyltrifluoroacetone, 1,3-cyclohexanedione, Examples thereof include 1-phenyl 1,3-butanedione. These can be used alone or in combination of two or more.

  Specific examples of the β-ketoester include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyroyl acetate, methyl caproyl acetate, and methyl lauroyl acetate. Can be mentioned. These can be used alone or in combination of two or more.

  Specific examples of the polyhydric alcohol include 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2, Examples include 3-pentanediol, diethylene glycol, glycerin, hexylene glycol and the like. These can be used alone or in combination of two or more.

  Specific examples of the organic fatty acid include formic acid, acetic acid, valeric acid, octylic acid, oxalic acid, adipic acid, maleic acid and the like. These can be used alone or in combination of two or more.

  Specific examples of the oxycarboxylic acid include glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, and gluconic acid. Moreover, salts, such as ammonium salt, amine salt, alkali metal salt, etc. of these acids are also mentioned. These can be used alone or in combination of two or more.

  Specific examples of the phosphate ester include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, mononormal propyl phosphate, dinormal propyl phosphate, monoisopropyl phosphate, and diisopropyl phosphate. , Mono-normal butyl phosphate, di-normal phosphate, mono-tertiary butyl phosphate, di-tertiary butyl phosphate and the like. These can be used alone or in combination of two or more.

  Specific examples of the alkanolamine include N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N- Examples thereof include normal butyl ethanolamine, N-normal butyl diethanol amine, N-tertiary butyl ethanol amine, N-tertiary butyl diethanol amine, triethanol amine, diethanol amine, monoethanol amine and the like. These can be used alone or in combination of two or more.

  Even if the said chelating agent is a different kind of chelating agent, they can use 2 or more types together.

  The manufacturing method of "the compound which has the structure which the chelating agent coordinated to the titanium alkoxide or zirconium alkoxide represented by said Formula (1)" mixes and reacts a titanium alkoxide or a zirconium alkoxide, and a chelating agent. Is preferably obtained by Here, the method of mixing and reacting is not particularly limited, but the above-mentioned chelating agent is added to “titanium alkoxide or zirconium alkoxide represented by the above formula (1)” and mixed or refluxed. Is preferred. After mixing the solvents, it is also preferable to reflux at the boiling point of the solvent used to advance the reaction. The order of blending the above “titanium alkoxide or zirconium alkoxide”, chelating agent and solvent is not specified.

Although there are no particular limitations on the blending ratio when the chelating agent is blended and reacted with respect to “titanium alkoxide or zirconium alkoxide represented by the above formula (1)”,
[Chelating agent]
/ [Titanium alkoxide or zirconium alkoxide represented by the above formula (1)]
= 0.05 / 1.0 to 25 / 1.0 (molar ratio)
Is preferable in terms of controlling the hydrolysis of the compound, more preferably 0.1 / 1.0 to 20 / 1.0 (molar ratio), and 1.0 / 1.0 to 10 /. 1.0 (molar ratio) is particularly preferable.

The “titanium alkoxide or zirconium alkoxide represented by the above formula (2)” is obtained by condensing the “titanium alkoxide or zirconium alkoxide represented by the above formula (1)”. Accordingly, the range of R _{5 to} R ₁₀ in Formula (2), the preferred range, specific examples and the like are the same as those of R _{1 to} R _{4 in} Formula (1). The method for condensing is not particularly limited, but it is preferable to carry out the “titanium alkoxide or zirconium alkoxide represented by the above formula (1)” by reacting water in an alcohol solution.

  With respect to the amount of water used for condensing and oligomerizing, “titanium alkoxide or zirconium alkoxide, or compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide” (A) per mole, That is, it is preferable that the number of moles of water is 0.5 to 2 moles with respect to 1 mole of titanium atom or zirconium atom from the viewpoint of improving the film forming property and controlling the hydrolysis, and 0.7 to 1.7. More preferably, it is mol, and it is especially preferable that it is 1.0-1.5 mol.

At the time of condensation by hydrolysis, it is preferable to obtain a titanium compound oligomer or a zirconium compound oligomer by using a solvent such as an alcohol, and optionally through a heat treatment such as reflux. Alcohols used at this time are not particularly limited, but alcohols in which a hydroxyl group is bonded to the same alkyl group as the alkyl groups R ^{1 to} R ⁴ in the formula (1) actually used are a titanium compound oligomer or This is preferable in that the reactivity of the zirconium compound oligomer is not changed. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexanol and the like.

  The amount of such alcohols used is not particularly limited, but may be diluted with such alcohols so that the amount of water used for condensation and oligomerization is 0.5 to 20% by mass. Preferably, it is diluted to a concentration of 0.7 to 15% by mass, particularly preferably 1.0 to 10% by mass.

  The compound of the above formula (2) obtained by condensing by oligomerization by hydrolysis is a 2 to 20 mer in weight average, the adhesiveness is improved, the hydrolyzability is controlled, etc. From 4 to 15 mer is particularly preferable. That is, in said formula (2), n = 1-19 are preferable and 3-14 are especially preferable.

In the “titanium alkoxide or zirconium alkoxide” represented by the above formula (2), R _{5 to} R ₁₀ each independently represent an alkyl group having 1 to 18 carbon atoms, preferably each independently a carbon. It is a C1-C10 alkyl group, Especially preferably, it is a C1-C8 alkyl group each independently.

R _{5 to} R ₁₀ , type of chelating agent, mixing ratio, reaction method, production method, etc. in “a compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide represented by formula (2)” Including the preferred range, R _{1 to} R ₄ in the “compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide represented by the formula (1)”, and the kind of chelating agent , The mixing ratio, the reaction method, the production method and the like.

The compounding ratio when the chelating agent is mixed and reacted with respect to “titanium alkoxide or zirconium alkoxide represented by the above formula (2)” is not particularly limited.
[Chelating agent]
/ [Titanium alkoxide or zirconium alkoxide represented by the above formula (2)]
= 0.05 / 1.0 to 25 / 1.0 (molar ratio)
Is preferable in terms of controlling the hydrolysis of the compound, more preferably 0.1 / 1.0 to 20 / 1.0 (molar ratio), and 1.0 / 1.0 to 10 /. 1.0 (molar ratio) is particularly preferable. However, the compounding molar ratio is a molar ratio when the “monomer represented by the structure as in the formula (1)” in the formula (2) is defined as one unit.

  Even when the chelating agent is coordinated to the “titanium alkoxide or zirconium alkoxide represented by the formula (1) and then oligomerized, it is obtained by first oligomerizing“ the titanium alkoxide represented by the formula (2) or A chelating agent may be coordinated to “zirconium alkoxide”, and any of them may be used.

  Regarding the structure of component (A), whether it is represented by formula (1) or formula (2), a chelating agent is coordinated. As long as it has the chemical structure and composition obtained by the above production method, it is not limited to those produced by a specific production method. However, it is preferable to manufacture using the above-described manufacturing method.

  As the structure of component (A), an alkoxide compound having a Ti—O—C bond or a Zr—O—C bond via oxygen to a titanium atom or a zirconium atom, a carbonyl group to a titanium atom or a zirconium atom, A chelate compound in which atoms such as nitrogen are coordinated and a condensate structure of these compounds are preferable. The component (A) has a structure in which the acid group or alkali group of the chelating agent is in the form of a salt such as an ammonium salt, an amine salt, or an alkali metal salt as in Example 6 described later. Also mentioned.

  The solvent as the component (B) is not particularly limited, but water, alcohols, esters, ketones or hydrocarbons are preferable.

  Water, alcohols, esters, ketones or hydrocarbons are not limited to the following specific examples. For example, alcohols include methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, Tertiary butanol, etc .; as esters, methyl acetate, ethyl acetate, isopropyl acetate, etc .; as ketones, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; as hydrocarbons, normal hexane, normal heptane, normal octane, normal And aliphatic hydrocarbons such as decane, aromatic hydrocarbons such as toluene and xylene, and the like. These can be used alone or in combination of two or more.

  The use ratio of component (A) and component (B) is not particularly limited, but the mass ratio of component A and component B is component (A) / component (B) = 0.05 / 99.95 to 99.95. /0.05, preferably component (A) / component (B) = 0.5 / 99.5 to 99.5 / 0.5, and component (A) / component (B) = 1. 0.0 / 99.0 to 99.0 / 1.0 is particularly preferable. If the ratio of the component (A) is too small, the deodorizing effect may be lowered. On the other hand, if the component (B) is too little, the adhesiveness of the film is lowered, the hydrolyzability is increased, and the stability is increased. May be insufficient.

The “deodorant composite composition of component (A) and component (B)” includes at least the following four forms, and any of them may be used.
“A chemical structure and composition obtained by the reaction of component (A) and component (B)”
“Chemical structure and composition obtained by mixing component (A) and component (B)” and “mixture of component (A) and component (B)” Having "
“A chemical structure and composition obtained by mixing component (A) and component (B)” and a reaction product of component (A) Among these, “chemical structure obtained by mixing (A) and (B)” And those having a composition ”,“ one having a chemical structure and composition obtained by mixing component (A) and component (B) ”and a reaction product with component (A) are preferred.

  In addition, the said form shows the form of the deodorizing composite composition in this invention, The unreacted material, a by-product, etc. may be further mixed with the form of the said deodorizing composite composition. . For example, the component (B) may be used in excess, and in that case, a mixture in which the component (B) is mixed in all the above forms is contained in the deodorizing effect-imparting coating agent. Further, unreacted substances such as a chelating agent and component (A) may be mixed. Therefore, “the compound having a chemical structure and composition obtained by mixing component (A) and component (B)” and The “mixture with the component (A)” may be contained in the deodorizing effect-imparting coating agent of the present invention.

  It is also possible to obtain a deodorant composite composition by blending the same or different solvents (B) in two stages. For example, the deodorant composite composition can be obtained by using the solvent (B) used in the condensation as it is, or the same or different solvent (B) can be added again thereafter to obtain the deodorant composite composition. It is. In addition, for example, it is possible to obtain a deodorant composite composition by using the solvent (B) used as a solvent for the chelating agent when coordinating the chelating agent, and then use the same or different solvent (B). It can be added again to obtain a deodorant composite composition.

  The deodorant composite composition in the present invention has a chemical structure and composition obtained by the above production method, and is a specific production method as long as it is coated on the adherend and gives a deodorizing effect to the adherend. It is not limited to what was manufactured with. However, the deodorant composite composition in the present invention is preferably manufactured using the above-described manufacturing method, and the deodorant composite composition in the present invention is manufactured using the above-described manufacturing method. It is preferable.

  The deodorizing effect-imparting coating agent of the present invention is characterized by containing the above deodorizing composite composition. The above-mentioned deodorant composite composition can be used as it is as the coating agent for imparting the deodorizing effect of the present invention. However, the above-mentioned deodorizing composite composition is further blended with “another compound” as a deodorizing effect-imparting coating agent. Also good.

  Such “other blends” are not particularly limited, and include antibacterial agents, antifoaming agents, leveling agents, fillers, antistatic agents and the like.

  The deodorizing effect-imparting coating agent of the present invention preferably contains an antibacterial agent for the purpose of imparting antibacterial properties. Since fermentation by bacteria can cause malodor, a synergistic effect is obtained by combination with an antibacterial agent. The antibacterial agent is not particularly limited, and examples thereof include a compound containing at least one metal element selected from the group consisting of silver, platinum, copper, zinc, nickel, cobalt, molybdenum, and chromium. Other antibacterial agents include cyclodextrins, quaternary ammonium salts, catechins and the like. These can be used alone or in combination of two or more.

  The deodorizing effect-imparting coating agent of the present invention is formed into a deodorizing film. The deodorant effect-imparting coating agent of the present invention is excellent in coating performance and can be coated by a simple method, and since the deodorant active ingredient is not inorganic particles, it is easy to form a film, and is obtained by forming a film. Since the deodorizing film exhibits the catalyst performance as it is, ultraviolet irradiation or the like is not essential, and the deodorizing effect can be exhibited in a short time.

  Further, the deodorant having the above-mentioned deodorant film on the surface of the adherend, the deodorant film in the present invention has high adhesiveness to the adherend, so that the deodorant performance and deodorant sustainability In addition, the deodorizing effect is manifested in a short time, and it has resistance to physical forces such as washing and rubbing.

  When the deodorizing effect-imparting coating agent of the present invention is applied to an adherend to form a film, it can be applied by diluting with water or an organic solvent as necessary. Although there is no limitation in particular about the water and organic solvent which are used for dilution, A solvent with high wettability with respect to various adherends is preferable. Preferred solvents include water, hydrocarbon solvents, ester solvents, alcohol solvents and the like. Specifically, as alcohols, methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, tertiary butanol, etc., as esters, methyl acetate, ethyl acetate, isopropyl acetate, etc., as ketones, Examples of aliphatic hydrocarbons such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone include normal hexane, normal heptane, normal octane, normal decane, toluene, xylene and the like. Solvents can be used alone or in combination of two or more in consideration of wettability to the adherend and stability of the coating solution.

  The adherend is not particularly limited, but includes plant fibers, animal fibers, polyester-based synthetic fibers, polyamide-based synthetic fibers, cellulose-based semi-synthetic fibers, protein-based semi-synthetic fibers, regenerated fibers, glass fibers, carbon fibers and At least one type of fiber selected from the group consisting of metal fibers, nonwoven fabrics having these fibers, yarns made by spinning these fibers, woven fabrics made by woven these yarns, knitting made by knitting these yarns Cloth, paper, plastic film or plastic molding is preferred. As the fibers, those described above are preferable to vinyl fibers from the viewpoint of fiber elasticity and ease of dyeing.

  Examples of plant fibers include cotton and hemp, examples of animal fibers include silk, wool, and cashmere. Examples of polyester synthetic fibers include fibers such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. Examples of the polyamide-based synthetic fiber include nylon 6, nylon 66, nylon 46, nylon MXD66, and the like. Examples of the cellulose-based semi-synthetic fiber include fibers such as acetate and triacetate, and a protein-based semi-synthetic fiber. Examples of fibers include fibers such as promix, examples of recycled fibers include fibers such as rayon, cupra, and tencel. Examples of glass fibers include glass wool that is short fibers and glass fibers that are long fibers. Examples of the carbon fiber include acrylic fiber. Use, using synthesized PAN or pitch, include fibers such as synthesized PITCH is, the metal fibers are stainless steel, iron, gold, silver, and fibers made of metal such as aluminum.

  As the adherend, a nonwoven fabric having the above-described fibers, a yarn formed by spinning these fibers, a woven fabric formed by weaving these yarns, and a knitted fabric formed by knitting these yarns are also preferable. The “yarn” may be one in which the inside is uniformly packed, or one in which the above fibers are aligned and twisted. Even if the raw short fibers are twisted by spinning and stretched long to make a single spun yarn (spun yarn, staple yarn), the raw long fibers are twisted or made difficult to separate, The yarn may be spun into a single yarn (filament yarn).

  Examples of the paper include fine paper, recycled paper, coated paper, art paper, and the like, and the plastic film or plastic molding includes polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polypropylene, polyethylene, polystyrene, chloride. Examples thereof include films made of vinyl, vinylidene chloride, fluororesin, acrylic resin, polyamide resin, polycarbonate, polyphenylene oxide, polyimide and the like, or plastic moldings.

  There is no particular limitation on the coating method when the adherend is treated with the deodorizing effect-imparting coating agent of the present invention, but in the case of a plastic film or a plastic molded body, roll coating represented by gravure coating, spin coating, A dip coat or the like is preferable, and in the case of yarn, cloth, or paper, it is preferable to apply the film by squeezing the coating agent as necessary after being immersed in the deodorizing effect-imparting coating agent of the present invention.

Although there is no limitation in particular about the application quantity in the case of processing the deodorizing effect imparting coating agent of this invention to a to-be-adhered body, as an application quantity after drying, 0.01-5 g / m < ² > is preferable, 0.05 ˜3 g / m ² is more preferable, and 0.1 to ² g / m ² is particularly preferable. When the coating amount is too small, the above-described deodorizing effect may not be obtained, and when the coating amount is too large, poor curing may occur.

  There are no particular limitations on the curing conditions for treating the adherend with the deodorant effect-imparting coating agent of the present invention, but the curing temperature is preferably 0 to 200 ° C, more preferably 5 to 170 ° C, and more preferably 10 -150 ° C is particularly preferred. The curing time is preferably 1 second to 30 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 1 minute. Furthermore, it is preferably cured at 200 ° C. or less for 30 minutes or less, more preferably at 170 ° C. or less for 10 minutes or less, and particularly preferably at 150 ° C. or less for 1 minute or less.

  The deodorizing effect imparting coating agent of the present invention can be used for the purpose of forming a deodorizing film on an adherend to obtain a deodorant. The deodorant is not particularly limited, and examples thereof include clothing, wallpaper, a deodorizing film, and a deodorizing filter that require a deodorizing effect.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples. However, the present invention is not limited to these unless it exceeds the gist.

Production Example 1
[Synthesis of Compound A1 having a structure in which a chelating agent is coordinated to titanium alkoxide represented by Formula (1)]
10 g of a 90% by mass aqueous lactic acid solution (0.10 mol as lactic acid) was dissolved in 50 g of ethanol, and 28.4 g (0.10 mol) of tetraisopropyltitanium was added dropwise. After completion of dropping, the mixture was refluxed for 1 hour to obtain a compound having a structure in which a chelating agent was coordinated to titanium alkoxide. This is designated as “Compound A1”.

Production Example 2
[Synthesis of Compound A2 having a structure in which a chelating agent is coordinated to titanium alkoxide represented by Formula (1)]
Citric acid monohydrate (21 g, 0.10 mol) was dissolved in ethanol (50 g), and tetraisopropyltitanium (28.4 g, 0.10 mol) was added dropwise. After completion of dropping, the mixture was refluxed for 1 hour to obtain a compound having a structure in which a chelating agent was coordinated to titanium alkoxide. This is designated as “Compound A2”.

Production Example 3
[Synthesis of Titanium Alkoxide A3 Represented by Formula (2)]
Tetranormal butoxytitanium (34.0 g, 0.10 mol) was dissolved in normal butanol (12.0 g), and then a mixture of 2.7 g (0.15 mol) of water and normal butanol (24.0 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour, and further refluxed for 1 hour to obtain a condensed titanium alkoxide represented by the formula (2). This is designated as “Compound A3”.

Production Example 4
[Synthesis of Compound A4 having a structure in which a chelating agent is coordinated to zirconium alkoxide represented by Formula (1)]
After dissolving 31.4 g of 90 mass% lactic acid aqueous solution (0.31 mol as lactic acid) in 180 g of normal propanol, a mixed solution of 43.7 g (0.10 mol) of normal propylzirconium and 100 g of normal propanol was added dropwise. After completion of the dropwise addition, the mixture was refluxed for 1 hour, and then 18.8 g of 28% by mass aqueous ammonia (0.31 mol as ammonia) and a compound having a structure in which a chelating agent was coordinated to zirconium alkoxide were obtained. This is designated as “Compound A4”.

Example 1
The compound A1 synthesized in Production Example 1 was diluted with water to a 10% by mass solution to obtain a deodorizing effect-imparting coating agent. The deodorizing effect imparting coating agent used as a coating liquid, as dry residue is 0.5 g / m ^2, cotton fabric 10cm square, nylon cloth ( "nylon" is a registered trademark), a polyester cloth and paper And dip-coated respectively. Then, it heat-hardened at 120 degreeC for 30 second, and obtained the processing cloth which is a deodorizing film and a deodorizing body. In addition, this deodorizing effect-imparting coating agent was used as a coating solution, and applied on a PET film with a bar coater so as to be applied at about 6 g / m ² . Then, it heat-hardened at 120 degreeC for 30 second, and the processed film which is a deodorizing film and a deodorizing body was obtained.

Examples 2-9
In Example 1, deodorization was carried out in the same manner as in Example 1 except that “Compound A1” and “Ethanol and water as solvent (B)” were changed to the types and amounts shown in Tables 1 and 2. A treated cloth and treated film were obtained as a membrane and deodorant.

表１中、オルガチックスＴＣ−３１０、オルガチックスＴＣ−３００、オルガチックスＴＣ−４００、オルガチックスＴＡ−２２、オルガチックスＴＡ−１０は、実施例で使用したものであり、何れもマツモトファインケミカル社製（何れも商品名）である。

In Table 1, ORGATICS TC-310, ORGATICS TC-300, ORGATICS TC-400, ORGATICS TA-22, ORGATICs TA-10 are those used in the examples, and all are manufactured by Matsumoto Fine Chemical Co., Ltd. (Both are trade names).

Comparative Example 1
After dispersing 5 g of anatase-type titanium oxide (trade name: ST-21, manufactured by Ishihara Sangyo Co., Ltd.) having a particle size of 20 nm in 95 g of water, a 10 cm square cotton cloth or nylon cloth so that the dry residue becomes 0.5 g / m ^2. Each was applied by dipping to a polyester cloth and paper. Thereafter, it was cured at 120 ° C. for 30 seconds to obtain a treated cloth. Moreover, it apply | coated with the bar coater so that a coating liquid might be apply | coated about 6 g / m < ² > on PET film. Thereafter, it was cured at 120 ° C. for 30 seconds to obtain a treated film.

Comparative Example 2
Disperse 1 g of zeolite pulverized to a particle size of 1 μm or less in 90 g of water, then dip coat it on 10 cm square cotton cloth, nylon cloth, polyester cloth and paper so that the dry residue becomes 0.5 g / m ^2. did. Then, it hardened | cured for 30 second at 120 degreeC, and produced the process cloth. Moreover, it apply | coated with the bar coater so that a coating liquid might be apply | coated about 6 g / m < ² > on PET film. Thereafter, it was cured at 120 ° C. for 30 seconds to obtain a treated film.

Evaluation Example 1
[Confirmation of deodorizing effect of acetic acid or ammonia]
The treatment cloth and the treatment film obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were put in a 5 L Tedlar bag, and 3 L of odorless air was put therein. Then, 10 mass% acetic acid aqueous solution or 3 mass% ammonia water was inject | poured with the 10 microliter micro syringe, and it left still in 25 degreeC and 65% RH environment. Immediately after injection and 30 minutes later, the acetic acid concentration or ammonia concentration in the tedlar bag is measured using a detector tube (manufactured by Gastec Corporation, acetic acid No. 81, ammonia No. 3LA), and judged according to the following criteria. It was. The results are shown in Table 3.

○: Decreased to a concentration of 10 ppm or less after standing for 30 minutes Δ: Decreased to a concentration in the range of 10 ppm to 50 ppm after standing for 30 minutes ×: No change from initial concentration after standing for 30 minutes.

Evaluation example 2
[Washing resistance evaluation]
Each of the treated cloths obtained by washing the cotton cloth, the nylon cloth and the polyester cloth obtained in Examples 1 to 9 and Comparative Examples 1 and 2 10 times with a detergent (attack made by Kao Corporation) and drying was used in 5 L. Placed in a tedlar bag with 3 L of odorless air. Then, 10 mass% acetic acid aqueous solution or 3 mass% ammonia water was inject | poured with the 10 microliter micro syringe, and it left still in 25 degreeC and 65% RH environment. The acetic acid concentration and the ammonia concentration in the Tedlar bag immediately after the injection and 30 minutes after the measurement were measured using the above-mentioned detector tube, and judged according to the following criteria. The results are shown in Table 4.

○: Decreased to a concentration of 10 ppm or less after standing for 30 minutes Δ: Decreased to a concentration in the range of 10 ppm to 50 ppm after standing for 30 minutes ×: No change from initial concentration after standing for 30 minutes.

Evaluation Example 3
[Adhesion evaluation]
The remaining of the film | membrane when a cellophane tape was affixed on the process film obtained in Examples 1-9 and Comparative Examples 1-2, and was peeled off was determined on the following references | standards. The results are shown in Table 5 together with the deodorizing effect.

○: The film remains in the entire area where cellophane tape is applied.
Δ: A film of 50% or more and less than 100% of the total area on which the cellophane tape has been applied remains. × ... A film of 30% or less of the total area on which the cellophane tape has been applied remains or no film remains.

  As can be seen from Tables 3 and 4, each of the deodorant bodies obtained in Examples 1 to 9 using the deodorizing effect-imparting coating agent of the present invention has a remarkable deodorizing effect on acetic acid and ammonia. However, in the same evaluation, in Comparative Examples 1 and 2, no deodorizing effect on acetic acid and ammonia was observed.

  Moreover, as can be seen from Table 5, all of the deodorizing films obtained using the deodorizing effect-imparting coating agents of Examples 1 to 9 of the present invention were excellent in adhesion to the adherend. On the other hand, in Comparative Examples 1-2, the adhesiveness with respect to a to-be-adhered body was inferior by the same evaluation.

  The deodorizing effect-imparting coating agent of the present invention can impart a deodorizing effect to cloth, paper, plastic film, etc. by a simple method, and particularly has high deodorizing ability of acetic acid and ammonia, and these can be used in a short time. The compound can be deodorized. In addition, since it can exhibit resistance to washing and rubbing due to its high adhesive performance, it is widely used in industrial fields such as the fiber processing field and the paint field.

Claims (8)

At least “a compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide represented by the following formula (1) or titanium alkoxide or zirconium alkoxide represented by the following formula (1)” (A) And a deodorant composite composition having a chemical structure and composition obtained by reacting and / or mixing the solvent (B) and coating the adherend to give a deodorizing effect to the adherend. A deodorizing effect-imparting coating agent.

[In Formula (1), M represents Ti or Zr, and R _{1 to} R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms. ] At least “a compound having a structure in which a chelating agent is coordinated to titanium alkoxide or zirconium alkoxide represented by the following formula (2) or titanium alkoxide or zirconium alkoxide represented by the following formula (2)” (A) And a deodorant composite composition having a chemical structure and composition obtained by reacting and / or mixing the solvent (B) and coating the adherend to give a deodorizing effect to the adherend. A deodorizing effect-imparting coating agent.

[In Formula (2), M represents Ti or Zr, R _{5 to} R ₁₀ each independently represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 1 or more. ]   The chelating agent is at least one selected from the group consisting of β-diketone, β-ketoester, polyhydric alcohol, organic fatty acid, oxycarboxylic acid, phosphate ester and alkanolamine. Deodorizing effect-imparting coating agent described in 1.   The deodorant according to any one of claims 1 to 3, wherein the solvent (B) is at least one selected from the group consisting of water, alcohols, esters, ketones and hydrocarbons. Effect-imparting coating agent.   A deodorizing film formed by using the deodorizing effect-imparting coating agent according to any one of claims 1 to 4.   A deodorizing body comprising the deodorizing film according to claim 5 on an adherend.   The adherend is selected from the group consisting of plant fibers, animal fibers, polyester-based synthetic fibers, polyamide-based synthetic fibers, cellulose-based semi-synthetic fibers, protein-based semi-synthetic fibers, regenerated fibers, glass fibers, carbon fibers and metal fibers. At least one kind of fibers, a non-woven fabric having these fibers, a yarn formed by spinning these fibers, a woven fabric obtained by weaving these yarns, a knitted fabric obtained by knitting these yarns, paper, plastic film or The deodorant body according to claim 6, which is a plastic molded body.   A method for producing a deodorant film, comprising a step of coating the adherend with the deodorizing effect-imparting coating agent according to any one of claims 1 to 4.