JP2013177587A - Gelling agent for aqueous liquid, aqueous liquid gel, deodorant and/or fragrance and process for producing aqueous liquid gel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gelling agent for an aqueous liquid which can provide an aqueous liquid gel having a shape retainability at room temperature and a high temperature, excellent transparency and storage stability at a low temperature.SOLUTION: A gelling agent for an aqueous liquid (D) includes a polymer (A) and a water soluble transition metal compound (B). The polymer (A) includes a radically polymerizable monomer (a1) containing a carboxyl group and/or a 1,3-dioxo-2-oxapropylene group and a radically polymerizable monomer (a2) as essential components, in which the radically polymerizable monomer (a2) is a carboxylate having a proton of the carboxyl group in (a1) being substituted with an onium cation.

Description

  The present invention relates to an aqueous liquid gelling agent, an aqueous liquid gel, a deodorant and / or fragrance, and a method for producing an aqueous liquid gel.

Conventionally, as a gel-type deodorant and / or fragrance, water as a solvent, water-based fragrance (Patent Documents 1 to 4) formed using agar, carrageenan or the like as a gelling agent, and as a solvent Oily gel type fragrances (Patent Documents 5 to 8) in which terpene hydrocarbons and the like are formed using metal soap as a gelling agent are known, and water-based types are the mainstream commercially available. Accounted for.
However, such water-based fragrances have the disadvantage that the absorption capacity of organic solvents (for example, a mixed solvent of alcohol and water) is extremely low, or the gel strength after absorption is low.
As a solution to the above problem,
(1) A transparent gel fragrance obtained by gelling a liquid mainly composed of a mixture of a fragrance and water and / or ethanol by neutralization with a carboxyl vinyl polymer and an alkali (see Patent Document 9)
(2) Cationic thickener obtained by copolymerizing N, N-dimethylaminoethyl methacrylate with N-vinylpyrrolidone, stearyl acrylate and a crosslinkable monomer (see Patent Document 10)
(3) Cross-linked product of N-vinylacetamide copolymer (see Patent Document 11)
(4) Diacetone acrylamide copolymer-modified polyvinyl alcohol crosslinked with a crosslinking agent (see Patent Document 12)
(5) A transparent gel composition containing a crosslinked N, N-dimethylacrylamide (co) polymer, a volatile substance and water and / or a water-soluble solvent (see Patent Document 13) is known. ing.

Japanese Patent Publication No.55-1812 JP 50-70532 A JP 56-57451 A Japanese Patent Laid-Open No. 10-226749 JP-A-53-91149 JP 56-89261 A JP 60-53148 A Japanese Patent Laid-Open No. 61-4310 Japanese Patent Laid-Open No. 1-119258 JP-A-9-66095 JP 2002-80681 A JP 2003-3029 A JP 2005-8832 A

However, the above (1), (2), and (5) have problems such as deformation of the gel or spillage of the gel when the container is moved or tilted, and the above (3), (4) Has the problem of causing liquid separation at low temperatures.
The present invention provides an aqueous liquid gelling agent, an aqueous liquid gel, a deodorant and an aqueous liquid gel that have high shape retention at room temperature and high temperature, excellent transparency, and excellent storage stability at low temperature. Another object is to provide a method for producing a fragrance and an aqueous liquid gel.

As a result of intensive studies to obtain a gelling agent for aqueous liquid, an aqueous liquid gel, a deodorizing and / or fragrance, and an aqueous liquid gel that have improved the above problems, the present inventors have reached the present invention.
That is, the gelling agent for aqueous liquid of the present invention is a gelling agent containing the polymer (A) and the following water-soluble transition metal compound (B), wherein the polymer (A) is a carboxyl group and / or 1, Gelling agent for aqueous liquid (D), which is a polymer having a radical polymerizable monomer (a1) having a 3-dioxo-2-oxapropylene group and the following radical polymerizable monomer (a2) as essential constituent units It is.
(A2): A carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation.
(B): A compound in which a ligand is bonded to one metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
The aqueous liquid gel of the present invention is an aqueous liquid gel obtained by gelling the aqueous liquid (D) with the aqueous liquid gelling agent of the present invention.
Further, the deodorant and / or fragrance of the present invention comprises the gelling agent for aqueous liquid of the present invention, the deodorant and / or aromatic substance (F) and the aqueous liquid (D). And / or fragrance.
Furthermore, the manufacturing method of the aqueous liquid gel of this invention is a manufacturing method of the aqueous liquid gel including the process of carrying out the crosslinking reaction of a polymer (A) and the following water-soluble transition metal compound (B) in an aqueous liquid (D). The polymer (A) essentially comprises a radical polymerizable monomer (a1) having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group and the following radical polymerizable monomer (a2). It is the manufacturing method of the aqueous liquid gel which is a polymer made into a unit.
(A2): A carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation.
(B): A compound in which a ligand is bonded to one metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.

The method for producing an aqueous liquid gelling agent, aqueous liquid gel, deodorant and / or fragrance, and aqueous liquid gel of the present invention has the following effects.
(1) An aqueous liquid gel obtained by gelling an aqueous liquid with the aqueous liquid gelling agent of the present invention, a deodorant and / or fragrance, and an aqueous liquid gel obtained by the production method of the present invention are kept at room temperature and high temperature. Since the shape is good, when the container is moved or tilted, the gel is not deformed or the gel does not spill and is easy to handle.
(2) The aqueous liquid gel obtained by gelling the aqueous liquid with the aqueous liquid gelling agent of the present invention, the deodorant and / or fragrance, and the aqueous liquid gel obtained by the production method of the present invention are highly transparent and aesthetic. Excellent.
(3) The aqueous liquid gel obtained by gelling the aqueous liquid with the aqueous liquid gelling agent of the present invention, the deodorizing and / or fragrance, and the aqueous liquid gel obtained by the production method of the present invention are gels even at low temperatures. No liquid separation phenomenon or cracking of the gel occurs, resulting in excellent storage stability at low temperatures.

In the present invention, the polymer (A) essentially comprises a radical polymerizable monomer (a1) having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group and the following radical polymerizable monomer (a2). It is a polymer as a structural unit.
(A2): A carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation.
In the present invention, the polymer (A) may be a polymer obtained by polymerizing a mixture of (a1) and (a2). Ammonia or onium cation hydroxide is obtained by polymerizing (a1). Further, a polymer having (a1) and (a2) as essential constituent units may be obtained by reacting an onium salt or the like. From the viewpoint of ease of reaction of the monomer, (a1) and (a2) are made the essential constituent units by reacting ammonia, onium cation hydroxide, onium salt or the like with the polymerized (a1). A polymer is preferred.

In the present invention, examples of the radical polymerizable monomer (a1) having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene (—CO—O—CO—) group include unsaturated monocarboxylic acid [ (Meth) acrylic acid, maleic acid monoalkyl (carbon number 1-9) ester, fumaric acid monoalkyl (carbon number 1-9) ester, crotonic acid, sorbic acid, itaconic acid monoalkyl (carbon number 1-9) ester , Itaconic acid glycol monoether, cinnamic acid and citraconic acid monoalkyl (carbon number 1 to 9) ester], poly (divalent to hexavalent) carboxylic acid [maleic acid, fumaric acid, itaconic acid, citraconic acid and phthalate] Acid etc.] and polycarboxylic acid anhydrides [maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, etc.] That.
(Meth) acrylic acid means methacrylic acid and / or acrylic acid, and "(meth) acryl ..." means "methacryl ..." and / or "acryl ...". The same applies hereinafter.
Among the radical polymerizable monomers (a1), (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and maleic anhydride are preferred from the viewpoint of polymerizability, more preferably (meth) acrylic acid, Maleic acid and maleic anhydride.

  In the present invention, (a2) is a carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation. In (a2), the carboxyl group includes a group in which a 1,3-dioxo-2-oxapropylene group is substituted with two carboxyl groups.

As the onium cation, a group consisting of ammonium ion (NH ₄ ⁺ ), quaternary ammonium cation (I), tertiary sulfonium cation (II), quaternary phosphonium cation (III) and tertiary oxonium cation (IV) And at least one cation selected from the group consisting of:
Examples of the quaternary ammonium cation (I) include the following (I-1) to (I-11) (hereinafter the term “cation” is omitted).
(I-1) a quaternary ammonium having an alkyl having 1 to 30 or more carbon atoms and / or an alkenyl group having 1 to 30 or more carbon atoms;
Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethylpropylammonium, dimethylpropylammonium, ethylmethyldipropylammonium, tetrapropylammonium, butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium and the like;

(I-2) quaternary ammonium having an aromatic hydrocarbon group having 6 to 30 or more carbon atoms;
Trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium and the like;

(I-3) Quaternary ammonium having an alicyclic hydrocarbon group having 3 to 30 or more carbon atoms;
N, N-dimethylpyrrinium, N-ethyl-N-methylpyrrolidinium, N, N-diethylpyrrolidinium, N, N dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N diethylmorpholinium, N, N dimethylpiperidinium, N, N-diethylpiperidinium and the like;

(I-4) an imidazolinium having 3 to 30 or more carbon atoms;
1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2,4- Diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1,2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1-methyl-3- Ethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 2-cyanomethyl-1, 3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, -Methylcarboxymethyl-1,2,3-trimethylimidazolinium, 3-methoxy-1,2-dimethylimidazolinium, 4-formyl-1,2,3-trimethylimidazolinium, 4-formyl-1, 2-dimethylimidazolinium, 3-hydroxyethyl-1,2,3-trimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium and the like;

(I-5) an imidazolium having 3 to 30 or more carbon atoms;
1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3 -Triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethyl Imidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazole 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-carboxymethyl-1,2,3-trimethylimidazolium, 3-methylcarboxymethyl- 1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3 -Hydroxyethyl-1,2-dimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium, N, N'-dimethylbenzimidazolim, N, N'-diethylbenzimidazolium and N-methyl -N'-ethylbenzimidazolium and the like;

(I-6) tetrahydropyrimidinium having 4 to 30 or more carbon atoms;
1,3-dimethyltetrahydropyrimidinium, 1,2,3-trimethyltetrahydropyrimidinium, 1,2,3,4-tetramethyltetrahydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4 , 0] -7-undecenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 4-cyano-1,2,3-trimethyltetrahydropyrimidinium, 3-cyanomethyl-1 , 2-dimethyltetrahydropyrimidinium, 4-acetyl-1,2,3-trimethyltetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyltetrahydropyrimidinium, 4-methylcarboxymethyl-1,2, 3-trimethyl-tetrahydropyrimidinium, 4-methoxy-1,2,3-trimethyltetrahydro Rimijiniumu, 3-methoxymethyl-1,2-dimethyl-tetrahydropyrimidinium chloride, 4-hydroxy-1,2,3-trimethyl-tetrahydroisoquinoline pyrimidinium and 4-hydroxy-1,3-dimethyl-tetrahydropyrimidinium bromide and the like;

(I-7) Dihydropyrimidinium having 4 to 30 or more carbon atoms;
1,3-dimethyl-2,4- or -2,6-dihydropyrimidinium [these are expressed as 1,3-dimethyl-2,4, (6) -dihydropyrimidinium, and the same expressions are used hereinafter. Use. 1,2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-2,4, (6) -dihydropyrimidinium, 1,2 , 3,5-tetramethyl-2,4, (6) -dihydropymidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9 (10) -undecanedienium, 5 -Methyl-1,5-diazabicyclo [4,3,0] -5,7 (8) -nonadienium, 2-cyanomethyl-1,3-dimethyl-2,4, (6) -dihydropyrimidinium, 3- Acetylmethyl-1,2-dimethyl-2,4, (6) -dihydropyrimidinium, 4-methylcarboxymethyl-1,2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 4 -Methoxy-1,2,3-trimethyl-2,4 6) -Dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-2,4, (6 ) -Dihydropyrimidinium and 2-hydroxyethyl-1,3-dimethyl-2,4, (6) -dihydropyrimidinium;

(I-8) Guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms;
2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2- Dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino-1,3,4-triethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1 1,3-dimethylimidazolinium, 2-diethylamino-1,3-diethylimidazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolinium, , 5,6,7-Tetrahydro1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihy B-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 2-dimethyl-3-cyanomethyl-1-methylimidazolinium, 2-dimethylamino-3-methylcarboxymethyl-1-methylimidazole Linium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-hydroxyethyl-1- Methylimidazolinium and 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium, etc .;

(I-9) Guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms;
2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-diethylamino-1 -Methyl-3,4-diethylimidazolium, 2-diethylamino-1,3,4-triethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 2-dimethylamino-1-ethyl-3-methyl Imidazolium, 2-diethylamino-1,3-diethylimidazolium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5,6,7- Tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 1,5-dihydro-1,2 Dimethyl-2H-pyrimido- [1,2a] imidazolium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolium, 2-dimethylamino-acetyl-1,3-dimethylimidazolium, 2-dimethylamino-4 -Methylcarboxymethyl-1,3-dimethylimidazolium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium, 2-dimethylamino -3-formylmethyl-1-methylimidazolium and 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium, etc .;

(I-10) Guanidium having a tetrahydropyrimidinium skeleton having 4 to 30 or more carbon atoms;
2-dimethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyltetrahydropyrimidinium 2-diethylamino-1-methyl-3,4-diethyltetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyltetrahydropyrimidinium, 2-diethylamino-1,3-dimethyltetrahydropyrimidinium, 2- Diethylamino-1,3-diethyltetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6 7,8-Hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrim Dinium, 2,3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-3-cyanomethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino- 4-acetyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-3-methylcarboxymethyl-1-methyltetrahydro Pyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl -1-methyltetrahydropyrimidinium And 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-tetrahydropyrimidinium bromide and the like;

(I-11) Guanidium having a dihydropyrimidinium skeleton having 4 to 30 or more carbon atoms;
2-dimethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2 -Dimethylamino-1-methyl-3,4-diethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-2,4 (6) -dihydropyrimidi 2-diethylamino-1,3,4-triethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2- Diethylamino-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-2,4 (6) -dihydropyrimidinium, 1,6,7 8-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1, 2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-acetyl- 1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3 -Methylcarboxymethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-2,4 (6) -di Dropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-2,4 ( 6) -dihydropyrimidinium and 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-2,4 (6) -dihydropyrimidinium;

Examples of the tertiary sulfonium cation (II) include the following (II-1) to (II-3).
(II-1) An aliphatic tertiary sulfonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms;
Trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium, diethylmethylsulfonium, etc .;
(II-2) Aromatic tertiary sulfonium having 6 to 30 or more carbon atoms;
Phenyldimethylsulfonium, phenylethylmethylsulfonium, phenylmethylbenzylsulfonium, etc .;
(II-3) an alicyclic tertiary sulfonium having 3 to 30 or more carbon atoms;
Methylthiolanium and phenylthiolanium, etc .;

Examples of the quaternary phosphonium cation (III) include the following (III-1) to (III-3).
(III-1) an aliphatic quaternary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms;
Tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyltripropylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldipropylphosphonium, dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium and trimethyl Butylphosphonium, etc .;
(III-2) Aromatic quaternary phosphonium having 6 to 30 or more carbon atoms;
Triphenylmethylphosphonium, diphenyldimethylphosphonium, triphenylbenzylphosphonium, etc .;
(III-3) an alicyclic quaternary phosphonium having 3 to 30 or more carbon atoms;

Examples of the tertiary oxonium cation (IV) include the following (IV-1) to (IV-3).
(IV-1) an aliphatic tertiary oxonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms;
Trimethyloxonium, triethyloxonium, ethyldimethyloxonium, diethylmethyloxonium and the like;
(IV-2) Aromatic tertiary oxonium having 6 to 30 or more carbon atoms;
Phenyldimethyloxonium, phenylethylmethyloxonium, phenylmethylbenzyloxonium and the like;
(IV-3) an alicyclic tertiary oxonium having 3 to 30 or more carbon atoms;
Methyl oxolanium and phenyl oxolanium, etc .;

Among these, (I) is preferable from the viewpoint of gel transparency after gelation, low-temperature stability of the gel, gel shape retention and gel strength, and more preferably (I-1), (I- 4) and (I-5), particularly preferably (I-4) and (I-5).
These onium cations may be used alone or in combination of two or more.

The polymer (A) having (a1) and (a2) as essential constituent units is selected from the group consisting of ammonia, onium hydroxide and onium salt in the polymer (X) having (a1) as essential constituent units. It can be prepared by adding at least one selected from the above, neutralization reaction and / or salt exchange. Specifically, at least one selected from the group consisting of ammonia, an onium hydroxide and an onium salt in which a solid powder of the polymer (X) having (a1) as an essential constituent unit is dispersed in a slurry in a solvent. A method in which seeds are contacted while being added to a solvent, or a powder of polymer (X) having (a1) as an essential constituent unit is at least one selected from the group consisting of ammonia, onium hydroxides and onium salts A method of dissolving in a solvent solution is preferably employed.
Further, at least one selected from the group consisting of ammonia, onium hydroxide and onium salt is added to the monomer solution containing (a1), and neutralization reaction and / or salt exchange are performed, and (a1) and ( It is also possible to prepare a polymer solution (A) by polymerizing the monomer solution using a monomer solution containing a2).

The onium salt is a salt of the onium cation and a counter anion. Examples of the counter anion include a halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), a carboxylate anion {carbonic acid or carbon number 1 to 1 Ions of 10 carboxyl group-containing compounds (—COO ⁻ )}, phosphate ions {phosphoric acid or ions of phosphate group-containing compounds having 1 to 10 carbon atoms (—OPO ₃ ²⁻ )} and sulfonate ions {sulfonic acid or ions having 1 to 10 sulpho groups-containing compound carbon (-SO ₃ ^-)} and the like.
Among ammonia, onium hydroxide and onium salt, from the viewpoints of gel transparency after gelation, low temperature stability of gel, shape retention of gel and gel strength, carbonate of onium hydroxide and onium cation Salts are preferred.

In the present invention, the polymer (A) can add a radical polymerizable monomer (E) other than the radical polymerizable monomers (a1) to (a2) to the structural unit.
The radical polymerizable monomer (E) includes a hydroxyl group-containing radical polymerizable monomer (E-1), an alkoxy group-containing radical polymerizable monomer (E-2), and an acrylamide group-containing radical polymerizable monomer. (E-3) Tertiary amino group-containing radical polymerizable monomer (E-4), epoxy group-containing radical polymerizable monomer (E-5), sulfo group-containing radical polymerizable monomer (E- 6), a phosphate group-containing radical polymerizable monomer (E-7), an unsaturated hydrocarbon (E-8), and other radical polymerizable monomers (E-9).

Examples of (E-1) include hydroxyalkyl mono (meth) acrylates having 2 to 3 carbon atoms in the alkyl group, polyethylene glycol (weight average molecular weight (hereinafter abbreviated as Mw): 100 to 4,000) mono (meth). Acrylate, polypropylene glycol (Mw: 100-4,000) mono (meth) acrylate, etc. are mentioned.
As (E-2), methyl vinyl ether and a compound in which the hydroxyl group of (E-1) is substituted with an alkoxy group having 1 to 10 carbon atoms {methoxy polyethylene glycol (Mw: 100 to 4000) mono (meth) acrylate, etc.} Etc.
Examples of (E-3) include (meth) acrylamide and N-alkyl (C 1 -C 3) substituted (meth) acrylamide (N-methylacrylamide and N, N-dimethylacrylamide etc.).
Examples of (E-4) include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylamide.
Examples of (E-5) include glycidyl (meth) acrylate.
(E-6) includes aliphatic or aromatic vinyl sulfonic acids (vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, etc.), 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid , Sulfoalkyl (meth) acrylate [2-sulfoethyl (meth) acrylate and 3-sulfopropyl (meth) acrylate, etc.] and (meth) acrylamide alkyl sulfonic acid [2-acrylamido-2-methylpropanesulfonic acid, etc.] Etc. In addition, the sulfo group in (E-6) may be neutralized with a metal (alkali metal and / or alkaline earth metal) hydroxide or the like. Specifically, acrylamide-2-methylpropanesulfonic acid (salt) may be used. Here, "... acid (salt)" means "... acid" and / or "... acid salt".
Examples of (E-7) include (meth) acrylic acid hydroxyalkyl phosphate monoesters [2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate and the like] and the like. Further, the phosphate ester group in (E-7) may be neutralized with a metal (alkali metal and / or alkaline earth metal) hydroxide or the like.
Examples of (E-8) include unsaturated hydrocarbons having 2 to 30 carbon atoms, and specific examples include ethylene, propylene, butene (such as α-butylene, β-butylene, and isobutene).
Examples of (E-9) include 4-vinylpyridine, vinylimidazole, N-vinylpyrrolidone and N-vinylacetamide.

Among the above-mentioned radical polymerizable monomers (E), from the viewpoint of polymerizability, an alkyl group having 2 to 3 carbon atoms is a hydroxylalkyl mono (meth) acrylate, polyethylene glycol (Mw: 100 to 4000) mono ( (Meth) acrylate, polypropylene glycol (Mw: 100 to 4000) mono (meth) acrylate, methyl vinyl ether, methoxypolyethylene glycol (Mw: 100 to 4000) mono (meth) acrylate, (meth) acrylamide, N-alkyl (1 carbon number) 3) Substituted (meth) acrylamide, N-vinylacetamide, acrylamide-2-methylpropanesulfonic acid (salt), sulfoalkyl (meth) acrylate, styrenesulfonic acid and isobutene are preferred, and (meth) acrylamide, more preferably Alkyl The carbon atoms 2-3 hydroxyalkyl mono (meth) acrylate, methyl vinyl ether and isobutene.
A monomer (E) may be used independently and may be used together 2 or more types.

The polymer (A) is (a1) when the radical polymerizable monomer (a) {(a1) is reacted with the onium salt after polymerization to contain (a2), and (a1) and (a1) and ( In the case of polymerizing a monomer containing a2), radically polymerizable monomer (E) is added to (a1) and (a2)} as necessary, and thermal radical polymerization is carried out in the presence or absence of a solvent. It can be obtained by polymerizing by a known method such as radical photopolymerization or anionic polymerization. Polymerization is performed, for example, at 0 to 200 ° C. under normal pressure or under pressure.
In the case of thermal radical polymerization, a polymerization catalyst such as an azo compound (such as azobisisobutyronitrile) or peroxide (such as t-butylperoxybenzoate) is used. In the case of photoradical polymerization, a photoradical initiator (benzoin alkyl ether). Etc.) and, if necessary, sensitizers (anthraquinone, etc.), Ziegler-Natta catalysts, metallocene catalysts, etc. can be used as polymerization initiators in the case of anionic polymerization. The obtained (co) polymer may be used after removing the solvent, or may be used in the presence of the solvent. From the viewpoint that an arbitrary aqueous liquid can be gelled, the solvent is preferably removed.

  Mw (measured by gel permeation chromatography (hereinafter referred to as GPC)) of the polymer (A) is preferably 2,000 to 2,000 from the viewpoint of the shape retention and gel strength of the gel after gelation. 5,000,000, more preferably 3,000 to 3,000,000.

In the polymer (A), the neutralization molar ratio (Q) in (A) determined by the following mathematical formula (1) is from the viewpoint of gel transparency after gelation, gel shape retention and gel strength. 0.05-1.0 is preferable, More preferably, it is 0.1-0.9, Most preferably, it is 0.1-0.7.
Neutralization molar ratio (Q) = V / (S + T × 2) (1)
[In formula (1), S is the total number of moles of carboxyl groups and carboxylates in (A), T is the total number of moles of 1,3-dioxo-2-oxapropylene groups in (A), V represents the total number of moles of the onium cation in (A)]

  The viscosity at 25 ° C. of the aqueous solution of the polymer (A) (concentration of 5% by weight) is 5 to 100,000 mPa · s from the viewpoint of gel transparency after gelation, gel shape retention and gel strength. More preferably, it is 10-10,000 mPa * s, Especially preferably, it is 15-5,000 mPa * s.

The water-soluble transition metal compound (B) is a compound having a dissolution rate in water of 50% by weight or more (5 g or more dissolves) when 10 g of (B) is mixed with 90 g of water at 25 ° C. with stirring. Say.
In the present invention, the water-soluble transition metal compound (B) may be an organic metal compound that reacts with the polymer (A) to form a crosslinked structure in the polymer (A), and is an organic titanium compound, an organic zirconium compound, an organic Zinc compounds, organic chromium compounds, organic nickel compounds, organic vanadium compounds and the like are included.
Among these water-soluble transition metal compounds (B), from the viewpoints of gel transparency after gelation, low-temperature stability of gel, shape retention of gel, gel strength and ease of gelation, An organic zirconium compound is preferable, and an organic titanium compound is more preferable.

  The water-soluble transition metal compound (B) is a compound in which a ligand (organic compound) is bonded to one metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond. . (B) preferably has a chelate-type ligand capable of coordinating in bidentate or more. Since (B) has a chelate-type ligand, the crosslinking reaction rate of the polymer (A) is moderately adjusted, so the time until gelation is several minutes to several days, and it is suitable for processing. It becomes speed.

The chelate-type ligand includes dicarboxylic acid or a salt thereof, aminocarboxylic acid or a salt thereof, hydroxycarboxylic acid or a salt thereof, diol, diamine, amino alcohol, and β-diketone. The chelate-type ligand is not limited to these.
Examples of the dicarboxylic acid include dicarboxylic acids having 4 to 10 carbon atoms, and specific examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, and phthalic acid. Examples of the salt include alkali metal salts such as potassium, sodium and lithium, and alkaline earth metal salts such as calcium.
Examples of the aminocarboxylic acid include compounds having an amino group and a carboxyl group having 1 to 20 carbon atoms, specifically, glycine, alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, histidine, isoleucine, leucine, Examples include methionine, lysine, phenylalanine, serine, threonine, tryptophan, tyrosine, valine, cysteine and proline. Examples of the salt include alkali metal salts such as potassium, sodium and lithium, and alkaline earth metal salts such as calcium.
Examples of the hydroxycarboxylic acid include compounds having a hydroxyl group and a carboxyl group having 1 to 10 carbon atoms, and specific examples include glycolic acid, lactic acid, malic acid, citric acid, tartaric acid, and salicylic acid. Examples of the salt include alkali metal salts such as potassium, sodium and lithium, and alkaline earth metal salts such as calcium.
Diols having 1 to 20 carbon atoms are included as the diol, and specific examples include ethylene glycol and diethylene glycol.
Examples of diamines include divalent primary diamines having 1 to 20 carbon atoms, divalent secondary amines having 3 to 20 carbon atoms, and divalent tertiary amines having 5 to 20 carbon atoms. Specifically, ethylenediamine, hexamethylenediamine and the like can be mentioned.
The amino alcohol includes a primary amine having one hydroxyalkyl group having 1 to 10 carbon atoms, a secondary amine having one or more hydroxyalkyl groups having 1 to 10 carbon atoms, and a hydroxyalkyl having 1 to 10 carbon atoms. A tertiary amine having one or more groups is included, and specific examples include trimethanolamine and triethanolamine.
Examples of the β-diketone include β-diketone having 5 to 10 carbon atoms, and specific examples include acetylacetone.
In (B), you may have 2 or more types of the said chelate type | mold ligands. Moreover, you may have chelate type ligands other than the above, and you may have a ligand which is not a chelate type ligand.
As said (B), from the viewpoint of the transparency of the gel after gelation, the low-temperature stability of the gel, the shape retention of the gel, the gel strength, and the gelation speed, the water-soluble solution having the above chelate-type ligand The transition metal compound is preferably a water-soluble transition metal compound having at least one selected from the group consisting of hydroxycarboxylic acid, aminocarboxylic acid and aminoalcohol as a chelate-type ligand.

The organic titanium compound is a compound in which a ligand is bonded to one titanium atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
As an organic titanium compound, from the viewpoint of gel transparency after gelation, low-temperature stability of gel, gel shape retention, gel strength and gelation speed, titanium lactate, dihydroxy titanium bis (lactate), titanium lactate ammonium salt, Titanium diammonium, di-n-butoxytitanium bis (triethanolamate), diisopropoxytitanium bis (triethanolamate) and titanium tetrakis (acetylacetonate) are preferred, and titanium lactate and titanium (triethanolaminate) are more preferred. ).

The organic zirconium compound is a compound in which a ligand is bonded to one zirconium atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
As organozirconium compounds, zirconylaminocarboxylic acid chloride, monohydroxytris (lactate) zirconium ammonium and tetrakis (lactate) from the viewpoint of gel transparency after gelation, low temperature stability of gel, shape retention of gel and gel strength ) Zirconium ammonium is preferred.

The organic titanium compound is obtained by reacting the above-mentioned chelate type ligand (dicarboxylic acid or salt thereof, aminocarboxylic acid, hydroxycarboxylic acid, diol, diamine, aminoalcohol and β-diketone) with titanium tetraalkoxide. Can do. As organic titanium compounds, ORGATIX (registered trademark) TC-310 (titanium lactate), TC-400 (titanium diisopropoxybis (triethanolaminate)) and the like are commercially available from Matsumoto Fine Chemical Co., Ltd.
Further, the organic zirconium compound includes the above-mentioned chelate-type ligand (dicarboxylic acid or salt thereof, aminocarboxylic acid, hydroxycarboxylic acid, diol, diamine, aminoalcohol and β-diketone) and zirconium tetraalkoxide, zirconium carbonate or zirconium carbonate. It can be obtained by reacting with ammonium or the like. As an organic zirconium compound, ORGATICS (registered trademark) ZB-126 (a zirconyl chloride compound aminocarboxylic acid) is commercially available from Matsumoto Fine Chemical Co., Ltd.

  One type of water-soluble transition metal compound (B) may be used, or two or more types may be used.

In the gelling agent of the present invention, the content of the water-soluble transition metal compound (B) is based on the weight of the gelling agent, the transparency of the gel after gelation, the low temperature stability of the gel, and the shape retention of the gel. From the viewpoint of gel strength, it is preferably 1 to 45% by weight, more preferably 3 to 40% by weight, further preferably 4 to 40% by weight, particularly preferably 5 to 25% by weight.
Further, the content of the polymer (A) is not particularly limited because it can be variously changed depending on the crosslinking condition, the target performance, etc., but the gel after gelation is based on the weight of the gelling agent. From the viewpoint of transparency, low-temperature stability of the gel, shape retention of the gel and gel strength, 55 to 99% by weight is preferable, more preferably 60 to 97% by weight, and still more preferably 60 to 96% by weight, particularly Preferably it is 75 to 95 weight%.

  The weight ratio {content of (B) / content of (A)} of the content of (B) and the content of (A) based on the weight of the gelling agent in the gelling agent of the present invention is gel From the viewpoint of the transparency of the gel after conversion, the low temperature stability of the gel, the shape retention of the aqueous liquid gel and the gel strength, 0.01 to 0.82 is preferable, and 0.03 to 0.70 is more preferable. More preferably, it is 0.04-0.67, Most preferably, it is 0.05-0.33.

Aqueous liquid (D) is water alone, a water-soluble compound that can be mixed with water, and a mixture of water-soluble compound that can be mixed with water and water, from the viewpoint of excellent transparency of the aqueous liquid gel, What can melt | dissolve both a polymer (A) and the water-soluble transition metal compound (B) to be used is preferable.
Examples of water-soluble compounds that can be mixed with water include water-soluble alcohols, water-soluble ethers, N-methyl-2-pyrrolidone, and γ-butyrolactone.
The water-soluble alcohol is an alcohol that is stirred and mixed in 90 g of water at 25 ° C. to dissolve 5 g or more.
The water-soluble alcohol is preferably an aliphatic alcohol having 1 to 6 carbon atoms and 1 to 5 valences, more preferably methanol, ethanol, n-propanol, or i-propanol, from the viewpoint of ease of dissolution in water. N-butanol, i-butanol, s-butanol, t-butanol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and 3-methoxy-3-methyl-1-butanol.
The water-soluble ether is an ether that is stirred and mixed in 90 g of water at 25 ° C. to dissolve 5 g or more.
Specific examples of the water-soluble ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether and dipropylene glycol monomethyl ether.
From the viewpoint of solubilizing hydrophobic compounds (such as deodorants and / or fragrances), methanol, ethanol, i-propanol, propylene glycol, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether, propylene At least one selected from the group consisting of glycol monoethyl ether, dipropylene glycol monomethyl ether and N-methyl-2-pyrrolidone is preferred.

In the aqueous liquid (D), the weight ratio of water-soluble compound to water (weight of water-soluble compound / weight of water) can dissolve both the polymer (A) and the water-soluble transition metal compound (B) used. The weight ratio to be an aqueous liquid is preferable. Easiness of dissolution of hydrophobic compound (deodorant and / or fragrance) and fragrance of hydrophobic compound (deodorant and / or fragrance) after gelation 0/100 to 100/0 is preferable, more preferably 10/90 to 99/1, still more preferably 30/70 to 98.5 / 1.5, and particularly preferably 50/50. ~ 95/5.
The weight ratio of water-soluble compound to water (weight of water-soluble compound / weight of water) is preferably 0/100 to 50/50 from the viewpoint of the reactivity of (B) and shape retention at high temperature. Yes.

  The gelling agent of the present invention may be prepared by mixing (A) and (B) in advance, and each may be stored in the form of two components and mixed when preparing an aqueous liquid gel. Moreover, in the gelatinizer of this invention, it is preferable to use (B) as an internal crosslinking agent instead of a surface crosslinking agent from a viewpoint of shape retention property.

As a method of using the gelling agent of the present invention, a method similar to a known method (Japanese Patent Laid-Open No. 2000-192011) for preparing an aqueous liquid gel using a gelling agent and an aqueous liquid is used. Specifically, the following methods (i) to (iv) for producing an aqueous liquid gel are included.
(I) A method of reacting (A) and (B) after mixing a gelling agent containing (A) and (B) and (D) (ii) One component of the gelling agent A method of mixing (A) and (B) after mixing the second component (B) in a solution obtained by dissolving (A) in an aqueous liquid (D) (iii) One component of a gelling agent A method in which (A) and (B) are reacted after mixing the second component (A) in a solution obtained by dissolving (B) in the aqueous liquid (D). (Iv) One component of the gelling agent. A solution prepared by dissolving (A) in the aqueous liquid (D) and a solution prepared by dissolving (B), which is one component of the gelling agent, in the aqueous liquid (D) are prepared in advance. Method of reacting A) and (B) As a method of using the gelling agent of the present invention, (iv) is preferred from the viewpoint of easily obtaining a uniform gel.

The aqueous liquid gel of the present invention is an aqueous liquid gel obtained by gelling the aqueous liquid (D) with the gelling agent. The aqueous liquid gel of the present invention is an aqueous liquid gel containing the polymer (A), the water-soluble transition metal compound (B), and the aqueous liquid (D).
The content of the polymer (A) in the aqueous liquid gel is 2.3 to 19.8 wt. From the viewpoints of gel transparency after gelation, gel shape retention and gel strength, and gel odor suppression. %, More preferably 3.5 to 19.4% by weight, particularly preferably 3.75 to 19.2% by weight.
The content of the water-soluble transition metal compound (B) in the aqueous liquid gel is the gel strength, the aesthetics of the aqueous liquid gel (the amount of residual gel remaining after the water and volatile components are scattered from the gel increases) From the viewpoint of aesthetics) and the odor of the remaining crosslinking agent, 0.05 to 9.0% by weight is preferable, more preferably 0.15 to 6.0% by weight, and particularly preferably 0.25 to 5.0%. % By weight.
The content of the aqueous liquid (D) in the aqueous liquid gel is the gel strength, the aesthetics of the aqueous liquid gel (the aesthetic appearance of the remaining gel is poor when the amount of gel remaining after the water and volatile components are scattered from the gel increases) In view of the above, the content is preferably 71.2 to 97.65% by weight, more preferably 74.6 to 96.35% by weight, and particularly preferably 75.8 to 96% by weight.

  As the aqueous liquid gel, in addition to the polymers (A), (B) and the aqueous liquid (D), a deodorant and / or aromatic substance (F) and other additives (G) are mixed. And can be gelled.

In the present invention, the substance (F) having deodorant properties and / or fragrances may be those generally used as substances having deodorant properties, fragrances or deodorant and fragrances, and are particularly limited. Not.
Examples of the deodorizing substance include substances extracted from plants such as rice, pine, hinoki and cocoon, and acid or alkaline aqueous liquids. These can also be used as an aqueous liquid diluted with water or an aqueous solution partially containing a solvent.
Examples of aromatic substances include natural fragrances and synthetic fragrances. If these are water-soluble, they can be used as an aqueous solution thereof, and if they are water-insoluble, they can be used as an aqueous emulsion or aqueous liquid comprising water, an emulsifier and, if necessary, a solvent. Here, since the substance which has aromaticity also has a masking effect, it may be said that it has deodorizing property practically.

  Natural fragrances include animal fragrances such as fragrances, ghost cat fragrances, and dragon scents, abies oil, aziyokun oil, almond oil, angelica root oil, basil oil, bergamot oil, birch oil, bore bellows oil, cabbage oil, cananga oil Oil, kabushi cam, caraway oil, cardamom oil, cassia oil, celery oil, cinnamon oil, citronella oil, cognac oil, coriander oil, cubebu oil, cumin oil, camphor oil, jill oil, estgolan oil, eureka oil, fennel oil, Garlic oil, ginger oil, grapefruit oil, hop oil, juniper berry oil, laurel leaf oil, lemon oil, lemongrass oil, lobe oil, mace oil, nutmeg oil, mandarin oil, tangerine oil, mustard oil, plaster oil, camellia oil , Onion oil, pepper oil, orange oil, sage oil, star anise Include turpentine oil, vegetable perfumes such as worm wood oil and Wanira bean extract.

  Synthetic fragrances include hydrocarbons such as pinene and limonene, linalool, geraniol, citronole, menthol, borneol, benzyl alcohol, anis alcohol, β-phenylethyl alcohol, phenols such as anenol and eugenol, n-butyraldehyde, Isobutyraldehyde, hexyl aldehyde, heptyl aldehyde, n-nonyl aldehyde, nonadienal, citral, citronellal, benzaldehyde, aldehydes such as cinnamic aldehyde, heliotropin and vanillin, methyl amyl ketone, methyl nonyl ketone, diacetyl, acetylpropionyl, acetyl butyrate Ketones such as phosphorus, carvone, menthone, camphor, acetophenone, P-methylacetophenone and ionone, amylbe Lactone or oxide such as lolactone, ethyl methylphenylglycidate, γ-nonyllactone, coumarin, cineol, methyl formate, isopropyl formate, linalyl formate, ethyl acetate, octyl acetate, menthyl acetate, benzyl acetate, cinnamyl Acetate, butyl propionate, isoamyl acetate, isopropyl isobutyrate, geranyl isovalerate, allyl caproate, butyl heptylate, octyl caprylate, methyl heptine carboxylate, ethyl verajagonate, methyl octynecarboxylate, isoacyl caprate, lauryl Methyl acid, ethyl myristate, ethyl benzoate, benzyl benzoate, methyl phenylacetate, butyl phenylacetate, methyl cinnamate, cinnamyl cinnamate, methicyl sartinate , Ethyl anisate, methyl anthranilate, esters such as ethyl building pyruvate and ethyl α- butyl butyrate.

  Only one type of deodorant and / or aromatic substance (F) may be used, or two or more types may be used.

  The content of the substance (F) having deodorant and / or fragrance in the aqueous liquid gel is somewhat different depending on the type, but from the viewpoint of deodorizing performance and / or scent persistence, the weight of the aqueous liquid gel From 0.1 to 15% by weight is preferable.

  Along with the deodorant and / or aromatic substance (F) described above, a volatile retention agent such as batch oil, a modulator such as eugenol, a solubilizing solvent such as ethylene glycol alkyl ether and propylene glycol alkyl ether, or volatilization regulator In addition, various components used in the other perfume industry may be added to obtain the substance (F).

In this invention, another additive (G) can be mix | blended with aqueous liquid gel as needed. Examples of the additive (G) include pigments (including fluorescent pigments and phosphorescent pigments), dyes, anti-aging agents, ultraviolet absorbers, ultraviolet shielding agents, antiseptics, antifungal agents, antifoaming agents, and oxygen scavengers. , Antioxidants, surfactants, alcohols, repellents, fillers and extenders.
The content of (G) in the aqueous liquid gel varies depending on the type, but from the viewpoint of the aesthetics of the aqueous liquid, 0.001 to 5% by weight is preferable based on the weight of the aqueous liquid gel.

  When the other additive (G) is insoluble in the aqueous liquid, the transmittance decreases if an insoluble additive is added to the aqueous liquid. From the viewpoint of the transparency of the aqueous liquid gel, It is preferable to mix the aqueous liquid gel so that the transmittance of the aqueous liquid gel is 70% or more.

The deodorant and / or fragrance of the present invention contains the gelling agent, the substance (F) and the aqueous liquid (D).
The preferred gelling agent, substance (F) and aqueous liquid (D) are the same as described above.
The content of the polymer (A) in the deodorant and / or fragrance of the present invention is from the viewpoint of gel transparency, gel shape retention, gel low temperature stability, gel strength, and gel odor control. It is preferably 2.3 to 19.8% by weight, more preferably 3.5 to 19.4% by weight, and particularly preferably 3.75 to 19.2% by weight.
The content of the water-soluble transition metal compound (B) in the deodorant and / or fragrance of the present invention is as follows: gel strength, gel transparency, gel low temperature stability, gel shape retention, and aqueous liquid gel aesthetics. From the viewpoint of the odor of the remaining crosslinking agent, it is preferably 0.05 to 9.0% by weight, more preferably 0.15 to 6.0% by weight, and particularly preferably 0.25 to 5.0% by weight.
The content of the aqueous liquid (D) in the deodorant and / or fragrance of the present invention is preferably 56.2 to 97.55% by weight, more preferably 59, from the viewpoint of gel strength and aesthetics of the aqueous liquid gel. .6 to 96.25% by weight, particularly preferably 60.8 to 95.9% by weight.
The content of the substance (F) in the deodorant and / or fragrance of the present invention is somewhat different depending on the type, but from the viewpoint of deodorant performance and / or scent persistence, based on the weight of the aqueous liquid gel 0.1 to 15% by weight is preferable.

The method for producing an aqueous liquid gel of the present invention is a method for producing an aqueous liquid gel comprising a step of crosslinking a polymer (A) and a water-soluble transition metal compound (B) in an aqueous liquid (D), The polymer (A) includes a radical polymerizable monomer (a1) having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group and the following radical polymerizable monomer (a2) as essential constituent units. It is the manufacturing method of the aqueous liquid gel which is a polymer.
(A2): A carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation.
(B): A compound in which a ligand is bonded to one metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.

The method for producing an aqueous liquid gel of the present invention includes the following methods (i) to (iv).
(I) A method in which (A), (B) and (D) are mixed and reacted (ii) A method in which (B) is mixed and reacted in a solution obtained by dissolving (A) in an aqueous liquid (D) ( iii) A method in which a solution in which (B) is dissolved in an aqueous liquid (D) is mixed and reacted in (A) (iv) A solution in which (A) is dissolved in an aqueous liquid (D), and (B) is an aqueous liquid ( A method in which the solutions dissolved in D) are respectively prepared in advance, and the two are mixed and reacted. Of these, (iv) is preferred from the viewpoint of obtaining a uniform gel.
Moreover, in the manufacturing method of the aqueous liquid gel of this invention, it is preferable to use (B) not as a surface crosslinking agent but as an internal crosslinking agent from a viewpoint of gel strength and gel shape retention.

As the reaction between (A) and (B) proceeds, the viscosity of the reaction system increases. When it further proceeds, it gels. Although the temperature and reaction time when reacting (A) and (B) are not particularly limited, the reaction temperature is from 5 to 60 from the viewpoint that the aqueous liquid does not evaporate and the crosslinking reaction is easy. The temperature is preferably 15 to 58 ° C, more preferably 20 to 55 ° C, and particularly preferably 30 to 50 ° C.
As the reaction time, the aqueous liquid (D) does not volatilize, and from the viewpoint of easy crosslinking reaction, when reacting at 5 to 39 ° C., the reaction is preferably completed in 1 minute to 10 days, When the reaction is carried out at 40 to 60 ° C., it is preferably completed in 1 minute to 1 day.

  According to the production method of the present invention, a highly transparent aqueous liquid gel is obtained. The transparency of the aqueous liquid gel can be measured by the transmittance (%). The transmittance (%) of the aqueous liquid gel is preferably 70 to 100, more preferably 75 to 100, from the viewpoint of the aesthetics and interior properties of the aqueous liquid gel (particularly when used as a deodorant and / or fragrance). Especially preferably, it is 80-100.

In addition, the transmittance | permeability (%) of aqueous liquid gel is measured with the following measuring method.
(Measurement method of transmittance)
An aqueous liquid gel before cross-linking (pre-reaction solution in the examples described later) is charged in a glass optical path length 10 mm cell with a sealed stopper and sealed, and cross-linked at 50 ° C. for 24 hours to prepare an aqueous liquid gel. Furthermore, after temperature-controlling at 25 degreeC for 6 hours, the transmittance | permeability of visible light (700 nm) is measured with a spectrophotometer (the Shimadzu Corporation make, UV-1200). Ion exchange water is used for the blank.

  The aqueous liquid gel obtained by gelling an aqueous liquid with the aqueous liquid gelling agent of the present invention and the aqueous liquid gel obtained by the production method of the present invention are only excellent in shape retention, transparency and storage stability. And excellent gel stability at low and high temperatures. Moreover, since the gelling agent for aqueous liquids of the present invention and the production method of the present invention can mix a fragrance and a repellent with an aqueous liquid containing a high concentration of alcohol, the resulting aqueous liquid gel is Even when the temperature in winter is low, it excels in the volatility of chemicals such as fragrances and repellents. Moreover, the gelling agent for aqueous liquids of the present invention is capable of gelation by proceeding with a crosslinking reaction even at room temperature, has a short gelation time, and is excellent in gel production. Furthermore, since the method for producing an aqueous liquid gel of the present invention can produce a gel at a low temperature, volatilization of chemicals such as fragrances and repellents during the production and alteration of chemicals such as fragrances and repellents hardly occur.

  The aqueous liquid gel of the present invention and the aqueous liquid gel obtained by the production method of the present invention can be widely used for deodorization and / or fragrance.

  Hereinafter, the present invention will be further described with reference to production examples and examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, parts represent parts by weight and% represents% by weight.

<Production Example 1> Preparation of polymer (A1) Polyacrylic acid 250,000 (7.4 parts) with ethanol (71.1 parts), 1,2,3,4-tetramethylimidazolinium monomethyl carbonate When a 48% methanol solution (21.5 parts) of (molecular weight: 204) was added and stirred at 50-60 ° C., it was uniformly dissolved in 4 hours. The solution thus obtained was dried for 3 hours at a drying temperature of 80 ° C. and a reduced pressure of 5 kPa using a vacuum dryer, and then pulverized with a cooking mixer to have a volume average particle size of 350 μm (trade name: manufactured by Nikkiso Co., Ltd.). The polymer (A1) having a neutralization molar ratio (Q) of 0.49 was obtained.
In addition, the following were used for polyacrylic acid 250,000.
Polyacrylic acid 250,000: Polyacrylic acid, Mw of about 250,000, manufactured by Wako Pure Chemical Industries, Ltd. The neutralization molar ratio (Q) in Production Example 1 is as follows because T in Formula (1) is 0: It calculated from Numerical formula (2).
Neutralization molar ratio (Q) = V / S (2)
S: Number of moles of acrylic acid in polyacrylic acid used for production of polymer (A1) (polyacrylic acid usage / 72.06)
V: Number of moles of 1,2,3,4-tetramethylimidazolinium monomethyl carbonate used for the production of the polymer (A1)

<Production Example 2> Preparation of polymer (X1) and polymer (A2) In a 5-liter beaker, 504 g (7 mol) of acrylic acid, 426 g (3 mol) of 50% aqueous acrylamide solution and 1950 g of water were added and cooled to 5 ° C. did. This solution was put into an adiabatic polymerization tank, and the dissolved oxygen amount of the solution was adjusted to 0.1 ppm through nitrogen. Then, 0.0005 g of 35% hydrogen peroxide solution, 0.00025 g of L-ascorbic acid and 4,4′-azobis 0.125 g of (4-cyanovaleric acid) was added. After about 30 minutes, the polymerization started, and after about 5 hours, the maximum temperature reached about 75 ° C., the polymerization was completed, and a hydrogel polymer was obtained. After this gel was subdivided with a meat chopper, it was dried at 120 ° C. for 1 hour using a band dryer (air-permeable dryer, manufactured by Inoue Metal Co., Ltd.), pulverized, and a polymer having an average particle size of 350 microns ( X1) was obtained.
In Production Example 1, 7.4 parts of the polymer (X1) was replaced with 250,000 (7.4 parts) of polyacrylic acid, and 65.0 parts, 1,2,3 instead of 71.1 parts of ethanol. , 4-tetramethylimidazolinium monomethyl carbonate (molecular weight: 204) 48% methanol solution in the same manner except that 27.6 parts were used instead of 21.5 parts, neutralization molar ratio (Q) A polymer (A2) having an A of 0.90 was obtained. The neutralization molar ratio (Q) was calculated by the same method as in Production Example 1.

<Production Example 3> Preparation of polymer (A3) In Production Example 1, the polyacrylic acid 250,000 (7.4 parts) was replaced with Isoban-18 (8.1 parts) and ethanol was replaced with 71.1 parts. 72.6 parts, TEAH-40W (19.3 parts) instead of 48% methanol solution (21.5 parts) of 1,2,3,4-tetramethylimidazolinium monomethyl carbonate (molecular weight: 204) The polymer (A3) having a neutralization molar ratio (Q) of 0.50 was obtained by the same method except that was used.
Isoban-18: isobutylene / maleic anhydride copolymer, molar ratio (isobutylene / maleic anhydride) = 1/1, Mw 3.0 × 10 ^{5 to} 3.5 × 10 ⁵ , Kuraray TEAH-40W: tetraethylammonium 40% aqueous solution of hydroxide (molecular weight: 147), manufactured by Lion Akzo.
The neutralization molar ratio (Q) in Production Example 3 was calculated from the following formula (3) because S is 0 in the formula (1).
Neutralization molar ratio (Q) = (V) / (T × 2) (3)
T: Number of moles of maleic anhydride in isoban-18 used for production of polymer (A3) (amount of isoban-18 used / 154.17)
V: Number of moles of TEAH-40W used for the production of the polymer (A3)

<Production Example 4> Preparation of polymer (A4) In Production Example 1, isoban-18 (8.1 parts) was substituted for polyacrylic acid 250,000 (7.4 parts), and ethanol was replaced with 71.1 parts. TEAH-40W (3.9 parts) instead of a 48% methanol solution (21.5 parts) of 88.0 parts, 1,2,3,4-tetramethylimidazolinium monomethyl carbonate (molecular weight: 204) ) Was used to obtain a polymer (A4) having a neutralization molar ratio (Q) of 0.10 by the same method. The neutralization molar ratio (Q) was calculated by the same method as in Production Example 3.

<Production Example 5> Preparation of polymer (A5) In Production Example 1, GANTREZ AN139 (8.1 parts) was used instead of polyacrylic acid 250,000 (7.4 parts), and ethanol was replaced with 71.1 parts. 61.7 parts instead of 48% methanol solution (21.5 parts) of 1,2,3,4-tetramethylimidazolinium monomethyl carbonate (molecular weight: 204) 1-ethyl-3-methylimidazolium A polymer (A5) having a neutralization molar ratio (Q) of 0.70 was obtained in the same manner except that a 45% methanol solution (30.2 parts) of monomethyl carbonate (molecular weight: 187) was used.
GANTREZ AN139: Methyl vinyl ether / maleic anhydride copolymer, molar ratio (methyl vinyl ether / maleic anhydride) = 1/1, Mw 6.90 × 10 ⁵ , neutralization molar ratio in Production Example 5 manufactured by ASP Japan (Q) was calculated from the following mathematical formula (1).
Neutralization molar ratio (Q) = (V) / (T × 2) (1)
T: Number of moles of maleic anhydride in GANTREZ AN139 used for production of polymer (A5) (Amount of GANTREZ AN139 used / 156.14)
V: Number of moles of 1-ethyl-3-methylimidazolium monomethyl carbonate used in the production of the polymer (A5)

<Production Example 6> Preparation of aqueous liquid (D1) Ethanol (40 parts) was added to ion-exchanged water (60 parts) to prepare a uniform and transparent aqueous liquid (D1).

<Production Example 7> Preparation of aqueous liquid (D2) Propylene glycol monomethyl ether (10 parts) was added to ion-exchanged water (90 parts) to prepare a uniform and transparent aqueous liquid (D2).

<Manufacture example 8> Preparation of aqueous liquid (D3) Add ion-exchange water (85.2 parts) and ethanol (9.8 parts) to Epolion SK-500 (5 parts) as a deodorant substance and dissolve uniformly. An aqueous liquid (D3) was prepared.
In addition, the following were used for Epolion SK-500.
Epolion SK-500: aqueous solution of a mixture of betaine compound, alcohol amine, organic acid salt compound and phosphoric acid (pure content 40%), manufactured by New Epolion Co., Ltd.

<Production Example 9> Preparation of aqueous liquid (D4) Nonipol 120 (0.5 parts), ethanol (9.9 parts) and ion-exchanged water (89.1 parts) were added to a floral fragrance (0.5 parts). It melt | dissolved uniformly and the aqueous liquid (D4) was prepared.
In addition, the floral fragrance | flavor and nonipol 120 used the following.
Floral fragrance: Product name “Lavender”, product number “OFR-2321”, Hasegawa fragrance nonipol 120: Polyoxyethylene nonylphenyl ether nonionic surfactant, manufactured by Sanyo Chemical Industries

<Manufacture example 10> Preparation of aqueous liquid solution (A6) of polymer TEAH-40W (16.7 parts) and ethanol (82.1 parts) are added to isoban-18 (10.0 parts) at 50-60 degreeC. When stirred, the polymer was uniformly dissolved in 4 hours to obtain a polymer aqueous liquid solution (A6) having a neutralization molar ratio (Q) of 0.35.

<Example 1> Preparation of aqueous liquid gel (G1) (A1) prepared in Production Example 1 was dissolved in 19.2 parts by adding 79.8 parts of ion-exchanged water and stirring at 25 ° C for 5 minutes. Thereafter, ORGATICS TC-400 (1.0 part) was further added as a water-soluble transition metal compound (B1), and the mixture was stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (1). The pre-reaction solution (1) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G1). The gelation time of the pre-reaction solution (1) was 2 hours. The gelation time was set in a half amount (6 cm from the bottom) of the pre-reaction solution (1) in a container (a glass container with a diameter of 3.5 cm and a height of 12 cm), and then placed in a thermostatic bath at 50 ° C. The container was taken out every 30 minutes and laid down beside (90 degrees), and it was defined as the time when the solution was not flowing 5 seconds after laying down (the same applies hereinafter). The aqueous liquid gel (G1) has a polymer (A1) content of 19.2%, a water-soluble transition metal compound (B1) content of 0.8%, a water-soluble transition metal compound (B1) / polymer (A1). ) Ratio 0.042 and alcohol / water ratio 0.3 / 99.7.
In addition, the following were used for ORGATICS TC-400.
ORGATICS TC-400: Isopropanol solution of titanium diisopropoxybis (triethanolamate), solid content 80%, manufactured by Matsumoto Fine Chemical Co., Ltd.

<Example 2> Preparation of aqueous liquid gel (G2) (A1) prepared in Production Example 1 was dissolved in 19.2 parts by adding 79.5 parts of ion-exchanged water and stirring at 25 ° C for 5 minutes. Thereafter, ORGATICS TC-400 (1.32 parts) was further added as a water-soluble transition metal compound (B1), and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (2). The pre-reaction solution (2) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G2). The gel time of the aqueous liquid gel (G2) was 2 hours. The aqueous liquid gel (G2) has a polymer (A1) content of 19.2%, a water-soluble transition metal compound (B1) content of 1.1%, a water-soluble transition metal compound (B1) / polymer (A1). ) Ratio 0.055 and alcohol / water ratio 0.3 / 99.7.

<Example 3> Preparation of aqueous liquid gel (G3) Add 94.2 parts of (D1) prepared in Production Example 6 to 4.4 parts of (A2) prepared in Production Example 2 and stir at 25 ° C for 5 minutes. Then, ORGATICS TC-310 (1.4 parts) is further added as a water-soluble transition metal compound (B2) and stirred at 25 ° C. for 5 minutes to obtain a uniform and transparent pre-reaction solution (3). Prepared. The pre-reaction solution (3) thus obtained was reacted for 24 hours in a 50 ° C. constant temperature bath to obtain a uniform and transparent aqueous liquid gel (G3). The gel time of the aqueous liquid gel (G3) was 6 hours. The aqueous liquid gel (G3) has a polymer (A2) content of 4.4%, a water-soluble transition metal compound (B2) content of 0.62%, a water-soluble transition metal compound (B2) / polymer (A2). ) Ratio of 0.14 and alcohol / water ratio of 40.2 / 59.8.
In addition, the following were used for ORGATICS TC-310.
ORGATICS TC-310: Isolactol / water mixed solution of titanium lactate, solid content 44%, isopropanol 40%, water 16%, manufactured by Matsumoto Fine Chemical Co., Ltd.

<Example 4> Preparation of aqueous liquid gel (G4) Add 10.7 parts of (A1) prepared in Production Example 1 to 70.7 parts of (D2) prepared in Production Example 7 and stir at 25 ° C for 5 minutes. Then, ORGATIZ ZB-126 (14.3 parts) is further added as a water-soluble transition metal compound (B3), and the mixture is stirred at 25 ° C. for 5 minutes to obtain a uniform and transparent pre-reaction solution (4). Prepared. The pre-reaction solution (4) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G4). The gel time of the aqueous liquid gel (G4) was 7 hours. This aqueous liquid gel (G4) has a polymer (A1) content of 15.0%, a water-soluble transition metal compound (B3) content of 4.3%, a water-soluble transition metal compound (B3) / polymer ( A1) The ratio was 0.29, and the alcohol / water ratio was 8.8 / 91.2.
In addition, the following were used for ORGATICS ZB-126.
Olgatics ZB-126: Zirconyl chloride compound aminocarboxylic acid aqueous solution, solid content 30%, manufactured by Matsumoto Fine Chemical Co., Ltd.

<Example 5> Preparation of aqueous liquid gel (G5) 70.7 parts of (D2) prepared in Production Example 7 was added to 15.0 parts of (A2) prepared in Production Example 2 and stirred at 25 ° C for 5 minutes. Then, ORGATIZ ZB-126 (14.3 parts) is further added as a water-soluble transition metal compound (B3), and the mixture is stirred at 25 ° C. for 5 minutes to obtain a uniform and transparent pre-reaction solution (5). Prepared. The pre-reaction solution (5) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G5). The gel time of the aqueous liquid gel (G5) was 7 hours. This aqueous liquid gel (G5) has a polymer (A2) content of 15.0%, a water-soluble transition metal compound (B3) content of 4.3%, a water-soluble transition metal compound (B3) / polymer ( A2) The ratio was 0.29, and the alcohol / water ratio was 8.8 / 91.2.

<Example 6> Preparation of aqueous liquid gel (G6) (A4) prepared in Production Example 4 was added to 6.3 parts of 92.2 parts of ethanol and stirred at 25 ° C for 5 minutes to dissolve uniformly. Olgatics TC-400 (1.5 parts) was added as a water-soluble transition metal compound (B1) and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (6). The pre-reaction solution (6) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G6). The gel time of the aqueous liquid gel (G6) was 2.5 hours. This aqueous liquid gel (G6) is composed of 6.3% of polymer (A4), 1.2% of water-soluble transition metal compound (B-1), water-soluble transition metal compound (B1) / polymer ( A4) The ratio was 0.19, and the alcohol / water ratio was 100/0.

<Example 7> Preparation of aqueous liquid gel (G7) After 91.0 parts of ethanol was added to 6.3 parts of (A4) prepared in Production Example 4, the mixture was stirred at 25 ° C for 5 minutes to uniformly dissolve, and further Olgatics TC-310 (2.7 parts) was added as a water-soluble transition metal compound (B2) and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (7). The pre-reaction solution (7) thus obtained was reacted in a 50 ° C. constant temperature bath for 24 hours to obtain a uniform and transparent aqueous liquid gel (G7). The gel time of the aqueous liquid gel (G7) was 5 hours. This aqueous liquid gel (G7) is composed of 6.3% of polymer (A4), 1.2% of water-soluble transition metal compound (B-1), water-soluble transition metal compound (B2) / polymer ( A4) The ratio was 0.19, and the alcohol / water ratio was 99.5 / 0.5.

<Example 8> Preparation of aqueous liquid gel (G8) After adding 89.7 parts of ethanol to 6.3 parts of (A4) prepared in Production Example 4, the mixture was stirred at 25 ° C for 5 minutes to uniformly dissolve, and further Olgatics ZB-126 (4.0 parts) was added as a water-soluble transition metal compound (B3) and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (8). The pre-reaction solution (8) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G8). The gel time of the aqueous liquid gel (G8) was 8 hours. This aqueous liquid gel (G8) is composed of 6.3% of polymer (A4), 1.2% of water-soluble transition metal compound (B-1), water-soluble transition metal compound (B3) / polymer ( A4) The ratio was 0.19, and the alcohol / water ratio was 97.0 / 3.0.

<Example 9> Preparation of aqueous liquid gel (G9) Add 96.8 parts of (D3) prepared in Production Example 8 to 2.3 parts of (A3) prepared in Production Example 3 and stir at 25 ° C for 5 minutes. And then uniformly dissolved in the mixture, and ORGATICS TC-400 (0.9 parts) is further added as a water-soluble transition metal compound (B1) and stirred at 25 ° C. for 5 minutes to obtain a uniform and transparent pre-reaction solution (9). Prepared. The pre-reaction solution (9) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G9). The gel time of the aqueous liquid gel (G9) was 4 hours. This aqueous liquid gel (G9) has a polymer (A3) content of 2.3%, a water-soluble transition metal compound (B1) content of 0.72%, a water-soluble transition metal compound (B1) / polymer ( A3) The ratio was 0.31, and the alcohol / water ratio was 10.2 / 89.8.

<Example 10> Preparation of aqueous liquid gel (G10) 89.6 parts of (D4) prepared in Production Example 9 was added to 8.4 parts of (A5) prepared in Production Example 5 and stirred at 25 ° C for 5 minutes. And then uniformly dissolved, and ORGATICS TC-400 (2.0 parts) is further added as a water-soluble transition metal compound (B-1), and stirred at 25 ° C. for 5 minutes to obtain a uniform and transparent pre-reaction solution ( 10) was prepared. The pre-reaction solution (10) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G10). The gel time of the aqueous liquid gel (G10) was 2 hours. This aqueous liquid gel (G10) has a polymer (A5) content of 8.4%, a water-soluble transition metal compound (B1) content of 1.6%, a water-soluble transition metal compound (B1) / polymer ( A5) The ratio was 0.19, and the alcohol / water ratio was 11.4 / 88.6.

<Example 11> Preparation of aqueous liquid gel (G11) After adding 56.5 parts of ethanol to 42.0 parts of aqueous liquid (A6) prepared in Production Example 10, the mixture was stirred at 25 ° C for 5 minutes to uniformly dissolve it. Furthermore, 1.5 parts of ORGATICS TC-400 was added as a water-soluble transition metal compound (B1), and the mixture was stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (11). The pre-reaction solution (11) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G11). The gel time of the aqueous liquid gel (G11) was 2.5 hours. This aqueous liquid gel (G11) has a polymer (A6) content of 6.3%, a water-soluble transition metal compound (B1) content of 1.2%, a water-soluble transition metal compound (B1) / polymer ( A6) The ratio was 0.19, and the alcohol / water ratio was 100/0.

<Example 12> Preparation of aqueous liquid gel (G12) Add 88.4 parts of (D1) prepared in Production Example 6 to 6.3 parts of (A4) prepared in Production Example 4 and stir at 25 ° C for 5 minutes. Then, 5.3 parts of Orgatics TC-400 is further added as a water-soluble transition metal compound (B1) and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (12). did. The pre-reaction solution (12) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G12). The gel time of the aqueous liquid gel (G12) was 1.5 hours. This aqueous liquid gel (G12) has a polymer (A4) content of 6.3%, a water-soluble transition metal compound (B1) content of 4.2%, a water-soluble transition metal compound (B1) / polymer ( A4) The ratio was 0.67, and the alcohol / water ratio was 40.7 / 59.3.

<Example 13> Preparation of aqueous liquid gel (G13) Add 87.4 parts of (D1) prepared in Production Example 6 to 6.3 parts of (A4) prepared in Production Example 4 and stir at 25 ° C for 5 minutes. Then, 6.3 parts of Orgatics TC-400 is further added as a water-soluble transition metal compound (B1) and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (13). did. The pre-reaction solution (13) thus obtained was reacted for 24 hours in a 50 ° C. constant temperature bath to obtain a uniform and transparent aqueous liquid gel (G13). The gel time of the aqueous liquid gel (G13) was 1.5 hours. This aqueous liquid gel (G13) has a polymer (A4) content of 6.3%, a water-soluble transition metal compound (B1) content of 5.0%, a water-soluble transition metal compound (B1) / polymer ( A4) The ratio was 0.80, and the alcohol / water ratio was 40.8 / 59.2.

<Example 14> Preparation of aqueous liquid gel (G14) 80.6 parts of (D1) prepared in Production Example 6 was added to 19.2 parts of (A1) prepared in Production Example 1 and stirred at 25 ° C for 5 minutes. Then, 0.24 parts of Orgatics TC-400 is further added as a water-soluble transition metal compound (B1) and stirred at 25 ° C. for 5 minutes to prepare a uniform and transparent pre-reaction solution (14). did. The pre-reaction solution (14) thus obtained was reacted in a constant temperature bath at 50 ° C. for 24 hours to obtain a uniform and transparent aqueous liquid gel (G14). The gel time of the aqueous liquid gel (G14) was 5 hours. This aqueous liquid gel (G14) has a polymer (A1) content of 19.2%, a water-soluble transition metal compound (B1) content of 0.19%, a water-soluble transition metal compound (B1) / polymer ( A4) The ratio was 0.010, and the alcohol / water ratio was 40/60.

<Comparative Example 1>
Add 94.5 parts of (D1) prepared in Production Example 6 to 1.5 parts of Carbopol 980 described in Patent Document 9 (Japanese Patent Application Laid-Open No. 1-119258), and heat to boiling while stirring. After the pole 980 was dissolved, it was cooled to 25 ° C. to obtain a liquid (a). Nonipol 120 (0.5 part) used in Production Example 9 was added to the floral flavor (0.5 part) used in Production Example 9, and the mixture was stirred and dissolved to obtain a liquid (b). Triethanolamine (3.0 parts) was used as the liquid (c). Next, when the liquid (b) and the liquid (c) were mixed and mixed while adding the liquid (a), a transparent gel was instantaneously formed. This gel was designated as an aqueous gel (G15). The gel time of the aqueous liquid gel (G15) was 0 hour.
In addition, the following was used for the carbopol 980.
Carbopol 980: carboxy vinyl polymer, manufactured by BF Goodrich

<Comparative example 2>
In accordance with Example 1 of Patent Document 12 (Japanese Patent Laid-Open No. 2003-3029), a diacetone acrylamide copolymer-modified polyvinyl alcohol was prepared as follows.
A flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with vinyl acetate (672 parts), diacetone acrylamide (10 parts), and methanol (178 parts), and the system was purged with nitrogen. Thereafter, the internal temperature was raised to 60 ° C. To this system, a solution of 2,2′-azobisisobutyronitrile (1 part) dissolved in methanol (50 parts) was added to initiate polymerization. Over 5 hours after the initiation of polymerization, a solution of diacetone acrylamide (55 parts) dissolved in methanol (35 parts) was added dropwise at a constant rate, and after 6 hours, the polymerization was stopped. The polymerization yield was 78%. The remaining vinyl acetate was distilled while adding methanol vapor to the resulting reaction mixture to obtain a 50% methanol solution of a vinyl acetate polymer containing a diacetone acrylamide copolymer component. To this mixture (500 parts), methanol (50 parts) and a 4% methanol solution of sodium hydroxide (10 parts) were added and mixed well, and a saponification reaction was carried out at 40 ° C. The obtained gel-like material was pulverized, washed thoroughly with methanol and then dried to obtain diacetone acrylamide copolymer-modified polyvinyl alcohol. The obtained diacetacrylamide copolymer-modified vinyl alcohol (4 parts) was dispersed in ion-exchanged water (77.4 parts), heated to 90 ° C. and stirred for 30 minutes to be completely dissolved. Next, after cooling the obtained solution to 50 ° C. or lower, as a surfactant, Nonipol 120 (0.6 parts) used in Production Example 9, ethanol (9.4 parts), and Floral used in Production Example 9 were used. A pre-reaction solution (16) was prepared by mixing 10% by weight aqueous solution (8 parts) of adipic acid dihydrazide as a crosslinking agent (0.6 parts) and a crosslinking agent. Subsequently, the obtained pre-reaction solution (16) was allowed to stand for 24 hours in a constant temperature bath at 50 ° C. to cause a gelation reaction, thereby obtaining a transparent aqueous gel fragrance. This gel was designated as an aqueous gel (G16). The gel time of the aqueous liquid gel (G16) was 6 hours.

  Table 2 shows the evaluation results of Examples 1 to 14 and Comparative Examples 1 and 2.

The evaluation method is as follows.
(1) Appearance of gel (1)
The transmittance of the gel prepared according to the transmittance evaluation method described above was measured. The results are shown in Table 2.

(2) Appearance of gel (2)
The gel used in gel appearance (1) was cooled at -20 ° C. for 16 hours, left at 25 ° C. for 8 hours, and the transmittance was measured. The results are shown in Table 2.

(3) Storage stability at low temperature 50 g of each of the aqueous gels (G15) obtained in the pre-reaction solutions (1) to (14), (16) and Comparative Example 1 was taken in a cylindrical container with a sealed cap having a diameter of 4 cm. The gel prepared by reacting (heating) at 50 ° C. for 24 hours was left in a thermostatic bath at −25 ° C. for 1 week, and further left at 25 ° C. for 8 hours, and then the gel surface separation was removed from the Kimwipe Wiper S-200. And the weight increase of Kimwipe was measured. The results are shown in Table 2. The smaller the increase in weight, the higher the storage stability at low temperatures.
Weight increase = (Weight of wipe after wiping) − (Weight of wipe before wiping)
Kimwipe Wiper S-200: Pulp sheet, 100% pulp, sheet size (120 mm × 215 mm), manufactured by Nippon Paper Crecia Co., Ltd.

(4) Shape retention of gel at room temperature Half amount (6 cm from the bottom) of pre-reaction solutions (1) to (14), (16) in a glass container with a cylindrical seal plug having a diameter of 3.5 cm and a height of 12 cm The aqueous gel (G15) obtained in Comparative Example 1 was sealed and reacted (heated) at 50 ° C. for 24 hours to prepare a sample. Further, it was left at 25 ° C. for 6 hours. Mark the position (X) in contact with the upper surface of the gel, then lay the container on the side with the mark (X) directly below, and mark the position (Y) at the tip of the gel one hour after laying down. It was. The distance from the position (X) to the position (Y) was defined as the moving distance of the gel, and the shape retention of the gel was evaluated. The results are shown in Table 2. In addition, it shows that the shape retention property of the gel at room temperature is so high that the movement distance of a gel is short.

(5) Shape retention of gel at high temperature The sample prepared by the “gel shape retention” evaluation method described above is left in a 50 ° C. constant temperature bath for 72 hours, and the container is placed beside it in an atmosphere of 50 ° C. One hour after laying down, the distance moved by the gel was measured in accordance with the “gel shape retention” evaluation method described above. The results are shown in Table 2. In addition, it shows that the shape retention property of the gel at high temperature is so high that the movement distance of a gel is short.

From the results in Table 2, it can be seen that in Comparative Examples 1 and 2, liquid separation from the gel occurred at low temperatures, and the storage stability at low temperatures was poor. Further, in Comparative Example 1, since the crosslinked structure was not formed, the shape retention at room temperature and high temperature was poor.
On the other hand, the aqueous liquid gels of the present invention of Examples 1 to 13 have the gel appearance (transparency) equivalent to or higher than those of Comparative Examples 1 and 2, and the storage stability at low temperatures is Comparative Examples 1 and 2. Compared to Comparative Example 2, the shape retention at room temperature is comparable to that of Comparative Example 2, the shape retention at high temperature is superior to that of Comparative Example 2, and all effects are achieved simultaneously. I understand.

  The aqueous liquid gel obtained with the aqueous liquid gelling agent of the present invention and the gel obtained by the method for producing an aqueous liquid gel are useful as a deodorant and / or fragrance.

Claims (9)

A gelling agent containing the polymer (A) and the following water-soluble transition metal compound (B),
The polymer (A) includes a radical polymerizable monomer (a1) having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group and the following radical polymerizable monomer (a2) as essential constituent units. Gelling agent for aqueous liquid (D) which is a polymer.
(A2): A carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation.
(B): A compound in which a ligand is bonded to one metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond. The content of the polymer (A) is 55 to 99% by weight and the content of the water-soluble transition metal compound (B) is 1 to 45% by weight based on the weight of the gelling agent. An aqueous liquid gelling agent. The weight ratio {content of (B) / content of (A)} of the content of the water-soluble transition metal compound (B) and the content of the polymer (A) in the gelling agent is 0.01-0. The gelling agent for aqueous liquid according to claim 1 or 2, which is .82. The aqueous liquid according to any one of claims 1 to 3, wherein in the polymer (A), the neutralization molar ratio (Q) in (A) determined by the following mathematical formula (1) is 0.05 to 1.0. Gelling agent.
Neutralization molar ratio (Q) = (V) / (S + T × 2) (1)
[In formula (1), S is the total number of moles of carboxyl groups and carboxylates in (A), T is the total number of moles of 1,3-dioxo-2-oxapropylene groups in (A), V represents the total number of moles of the onium cation in (A)] The water-soluble transition metal compound (B) is an organotitanium compound and / or an organozirconium compound, The gelling agent for an aqueous liquid according to any one of claims 1 to 4. The aqueous liquid gel formed by gelatinizing an aqueous liquid (D) with the gelatinizer for aqueous liquids in any one of Claims 1-5. The aqueous liquid gel according to claim 6, which has a transmittance of 70 to 100%. An aqueous liquid gelling agent according to any one of claims 1 to 5, a deodorant and / or aromatic substance (F), and an aqueous liquid (D) deodorant and / or fragrance. A method for producing an aqueous liquid gel comprising a step of crosslinking a polymer (A) and the following water-soluble transition metal compound (B) in an aqueous liquid (D),
The polymer (A) includes a radical polymerizable monomer (a1) having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group and the following radical polymerizable monomer (a2) as essential constituent units. A method for producing an aqueous liquid gel which is a polymer.
(A2): A carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation.
(B): A compound in which a ligand is bonded to one metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.