JP6101131B2 - Gelling agent for aqueous liquid, aqueous liquid gel, and method for producing aqueous liquid gel - Google Patents

Description

  The present invention relates to an aqueous liquid gelling agent, an aqueous liquid gel, 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) A 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 relates to an aqueous liquid gelling agent, an aqueous liquid gel, and an aqueous liquid gel, which are capable of obtaining an aqueous liquid gel having high shape retention at room temperature and high temperature, excellent transparency, and excellent storage stability at low temperature. It aims at providing the manufacturing method of.

As a result of intensive studies to obtain a gelling agent for an aqueous liquid, an aqueous liquid gel, and a method for producing an aqueous liquid gel, the present inventor has 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, 3-dioxo-2-radically polymerizable monomer having an oxa propylene group (a1) and the following radical polymerizable monomer (a2) Ri polymer der as essential constituent units, a water-soluble transition metal compound (B ) is a gelling agent for organic titanium compound and / or an organic zirconium compound der Ru aqueous solution (D).
(B): A compound in which a ligand is bonded to one transition metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
(A2): A carboxylate (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation and a carboxylate (a22) in which the proton is substituted with an alkali metal cation.
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). Ri polymer der in units, water-soluble transition metal compound (B) is a method for producing an organic titanium compound and / or an organic zirconium compound der Ru aqueous liquid gels.
(B): A compound in which a ligand is bonded to one transition metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
(A2): carboxylate (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation, and carboxylate in which the proton of the carboxyl group in (a1) is substituted with an alkali metal cation (A22).

The gelling agent for aqueous liquid, the aqueous liquid gel, and the method for producing the aqueous liquid gel of the present invention have the following effects.
(1) An aqueous liquid gel obtained by gelling an aqueous liquid with the gelling agent for aqueous liquid of the present invention and an aqueous liquid gel obtained by the production method of the present invention have good shape retention at room temperature and high temperature. When moved or knocked down, the gel does not deform or spills 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 and the aqueous liquid gel obtained by the production method of the present invention have high transparency and excellent aesthetics.
(3) The aqueous liquid gel obtained by gelling the aqueous liquid with the gelling agent for aqueous liquid of the present invention and the aqueous liquid gel obtained by the production method of the present invention are separated from the gel even under a low temperature environment. Since no cracks occur, it has 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 (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation and a carboxylate (a22) in which the proton is substituted with an alkali metal 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 with an alkali metal hydroxide or the like. From the viewpoint of ease of reaction of the monomer, ammonia or an onium cation hydroxide, an onium salt and an alkali metal hydroxide are reacted with the polymerized (a1) and (a1) and A polymer having (a2) as an essential constituent unit is preferable.

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, phthalic acid, itaconic acid and citracone Acid] and polycarboxylic acid anhydrides [maleic anhydride, phthalic anhydride, itaconic anhydride, citraconic anhydride, etc.] .
(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, maleic anhydride and phthalic anhydride are preferable, and (meth) acrylic acid is more preferable. ) Acrylic acid, maleic acid and maleic anhydride.

  In the present invention, (a2) is a carboxylate (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation, and the proton of the carboxyl group in (a1) is substituted with an alkali metal cation. The carboxylate (a22). In (a2), the carboxyl group includes a group in which a 1,3-dioxo-2-oxapropylene group is substituted with two carboxyl groups.

The onium cation includes 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) an aliphatic 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'-dimethylbenzimidazolazom, 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, gel shape retention and gel strength, and (I-1), (I-4) and (I-) are more preferable. 5), particularly preferably (I-4) and (I-5).
These onium cations may be used alone or in combination of two or more.

The onium salt is a salt of the onium cation and a counter anion. Examples of the counter anion include hydroxide ions (OH ⁻ ), halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like), Carboxylate anion {carbonic acid or ion of C1-10 carboxyl group-containing compound (—COO ⁻ )}, phosphate ion {phosphoric acid or ion of C1-10 phosphate group-containing compound (—OPO ₃ ²⁻ )} and Examples thereof include sulfonate ions {sulfonic acid or ions of a C1-10 sulfo group-containing compound (—SO ₃ ⁻ )}.
Of at least one selected from the group consisting of ammonia, onium hydroxide and onium salt, from the viewpoint of gel transparency after gelation, low temperature stability of gel, shape retention of gel and gel strength Cationic hydroxides and onium cation carbonates are preferred.

Examples of the alkali metal cation include lithium ion, sodium ion and potassium ion. Among these alkali metal cations, sodium ions and potassium ions are preferable from the viewpoint of absorption characteristics, and sodium ions are more preferable. These alkali metal cations may be used alone or in combination of two or more.
Examples of the method of reacting an alkali metal hydroxide and the like include a method of adding an alkali metal hydroxide and / or a salt and neutralizing or exchanging the salt.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
For alkali metal salts, examples of counter anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ^−, etc.), carboxylate anions {ion of C 1-10 carboxyl group-containing compounds (—COO ^−). )}, Phosphate ion {phosphoric acid or C1-10 phosphate group-containing compound ion (-OPO ₃ ^2- )} and sulfonate ion {sulfonic acid or C1-10 sulfo group-containing compound ion (-SO ₃ ^-)} and the like.
Of these, alkali metal hydroxides are preferred from the viewpoints of absorption characteristics and reactivity.

In the polymer (A), the substitution molar ratio (Q) by the onium cation and the alkali metal cation in (A) obtained by the following mathematical formula (1) is the gel transparency after gelation, the shape retention of the gel and From the viewpoint of gel strength, 0.1 to 1.0 is preferable, more preferably 0.1 to 0.9, particularly preferably 0.2 to 0.9, and most preferably 0.2 to 0.7. It is.
Substitution 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 and the alkali metal cation in (A)]
Here, the carboxylate represents an onium salt of a carboxylic acid, an alkali metal salt of a carboxylic acid, and a polyvalent metal salt belonging to Group 2 or Group 13 of the periodic table of the carboxylic acid carboxylic acid.

In the polymer (A), the onium cation substitution rate determined by the following formula (2) is preferably 70 to 99%, more preferably 80 to 99%, particularly preferably from the viewpoint of solubility in a high-concentration alcohol solution. Is 90-99%.
Onium cation substitution rate (%) = (L) / (L + M) × 100 (2)
[In Formula (2), L represents the total number of moles of the onium cation in (A), and M represents the total number of moles of the alkali metal cation in (A). ]

In the present invention, in addition to the carboxylate obtained by substituting the proton of the carboxyl group in (a1) with an onium cation and the carboxylate substituted by an alkali metal cation, the proton of the carboxyl group in (a1) A carboxylate formed by substitution with a polyvalent metal ion belonging to Group 2 or Group 13 of the Table can be included in the structural unit.
The polyvalent metal ions belonging to Group 2 or Group 13 of the Periodic Table include alkaline earth metal ions such as calcium ions and magnesium ions, and metal ions of metals belonging to Group 13 such as aluminum ions.
As a method of substituting polyvalent metal ions belonging to Group 2 or 13 of the periodic table, a hydroxide and / or salt of polyvalent metal ions belonging to Group 2 or 13 of the periodic table is added, and The method of summing or salt exchange is mentioned.
Examples of the hydroxide of polyvalent metal belonging to Group 2 or Group 13 of the periodic table include calcium hydroxide, magnesium hydroxide, aluminum hydroxide and the like.
In addition, regarding the polyvalent metal salt belonging to Group 2 or Group 13 of the periodic table, examples of the counter anion include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like), carboxylate anions {C1 to Ions of 10 carboxyl group-containing compounds (—COO ⁻ )}, phosphate ions {phosphoric acid or ions of C 1-10 phosphate group-containing compounds (—OPO ₃ ²⁻ )} and sulfonate ions {sulfonic acid or C1 To 10 sulfo group-containing compounds (—SO ₃ ⁻ )} and the like.
Among these, from the viewpoint of reactivity, a hydroxide of a polyvalent metal belonging to Group 2 or Group 13 of the periodic table is preferable.

In the present invention, the molar ratio of the alkali metal cation in the polymer (A) to the polyvalent metal ion belonging to Group 2 or 13 of the periodic table (total number of moles of alkali metal cation / Group 2 or 13 of the periodic table). The total number of polyvalent metal ions belonging to the group is preferably 2.3 or more, more preferably 4.0 or more, from the viewpoint of solubility in (D).
In addition, the substitution rate with a polyvalent metal belonging to Group 2 or Group 13 of the periodic table determined by the following mathematical formula (3) is preferably 0 to 0.3, more preferably from the viewpoint of solubility in (D). Is 0-0.2.
Substitution rate by polyvalent metal belonging to Group 2 or Group 13 of the Periodic Table = U / (S + T × 2) (3)
[In Formula (3), 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), U represents the total number of moles of polyvalent metal ions belonging to Group 2 or Group 13 of the Periodic Table in (A)]

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 and an alkali metal hydroxide and the like, followed by neutralization reaction and / or salt exchange. Specifically, a solid powder of the polymer (X) having (a1) as an essential constituent unit is dispersed in a slurry form in a solvent (water and / or organic solvent, etc.) to give ammonia, onium hydroxide and onium. A method of obtaining a polymer (A) by contacting at least one selected from the group consisting of a salt and an alkali metal hydroxide while adding them to a solvent, or a polymer having (a1) as an essential constituent unit A solution in which at least one selected from the group consisting of ammonia, onium hydroxides and onium salts and an alkali metal hydroxide are dissolved in the powder of (X) (as a solvent, water and / or an organic solvent) Etc.) is preferably employed to obtain the polymer (A).
In addition, ammonia and / or an onium salt and an alkali metal hydroxide are added to the monomer solution containing (a1), and neutralization reaction and / or salt exchange are performed, thereby including (a1) and (a2). A monomer solution is prepared, and the polymer solution (A) can be prepared by polymerizing the monomer solution.

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-1 ′), and an acrylamide group-containing radical polymerizable monomer. (E-2), tertiary amino group-containing radical polymerizable monomer (E-3), epoxy group-containing radical polymerizable monomer (E-4), sulfo group-containing radical polymerizable monomer (E -5), a phosphate group-containing radical polymerizable monomer (E-6) and other radical polymerizable monomers (E-7).

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.
(E-1 ′) includes a compound in which the hydroxyl group of (E-1) is substituted with an alkoxy group having 1 to 10 carbon atoms. Specifically, methoxypolyethylene glycol (Mw: 100 to 4000) mono (Meth) acrylate etc. are mentioned.
Examples of (E-2) include (meth) acrylamide and N-alkyl (C1 to C3) substituted (meth) acrylamide (N-methylacrylamide and N, N-dimethylacrylamide, etc.).
Examples of (E-3) include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylamide.
Examples of (E-4) include glycidyl (meth) acrylate.
(E-5) 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 , (Meth) acrylic alkyl sulfonic acid [sulfoethyl (meth) acrylate and sulfopropyl meth) acrylate and the like] and (meth) acrylamide alkyl sulfonic acid [2-acrylamido-2-methylpropane sulfonic acid and the like]. In addition, the sulfo group in (E-5) is neutralized and / or salt-exchanged with a metal (an alkali metal and / or a polyvalent metal belonging to Group 2 or 13 of the periodic table) hydroxide or the like. Also good. Specifically, acrylamide-2-methylpropanesulfonic acid (salt) may be used. Here, "... acid (salt)" means "... acid" and / or "... acid salt".
Examples of (E-6) include (meth) acrylic acid hydroxyalkyl phosphoric acid monoesters [2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate and the like] and the like. Further, the phosphate group in (E-6) is neutralized and / or salt-exchanged with a metal (alkali metal and / or polyvalent metal belonging to Group 2 or 13 of the periodic table) hydroxide or the like. It's okay.
Examples of (E-7) 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, methoxypolyethylene glycol (Mw: 100 to 4000) mono (meth) acrylate, (meth) acrylamide, N-alkyl substituted (meth) acrylamide (N -Methylacrylamide and N, N-dimethylacrylamide), N-vinylacetamide, acrylamide-2-methylpropanesulfonic acid (salt), sulfoalkyl (meth) acrylate and styrenesulfonic acid, more preferably (meth) acrylamido. And hydroxyalkyl mono (meth) acrylates having 2 to 3 carbon atoms in the alkyl group.
A monomer (E) may be used independently and may be used together 2 or more types.

When the polymer (A) contains the radical polymerizable monomer (a) {(a1) and (a2) by reacting with ammonia and / or the onium salt and alkali metal hydroxide after the polymerization. When (a1) and the monomer containing (a1) and (a2) are polymerized, the radically polymerizable monomer (E) is added to the solvent (a1) and (a2) if necessary, and the solvent In the presence or absence of the polymer, it can be obtained by polymerization by a known method such as thermal radical polymerization, photoradical polymerization 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 of allowing any aqueous liquid to be gelled, it is preferably a solvent 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.
The weight average molecular weight was determined by gel permeation chromatography (GPC) method using three columns of columns: Guardcolumn PW _XL , TSKgel G6000PW _XL and TSKgel G3000PW _XL , column temperature: 40 ° C., mobile phase: 30% aqueous methanol (v / V) (containing 0.5% (w / v) sodium acetate), flow rate: 1.0 mL / min, sample concentration: 0.25 wt%, injection amount: 200 μL.

  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 organometallic compound that reacts with the polymer (A) to form a crosslinked structure in the polymer (A), such as 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), an organic titanium compound and an organic zirconium compound are preferable from the viewpoint of easy gelation and coloring, 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 transition metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond. is there. (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 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.
The above (B) is preferably a water-soluble transition metal compound having the chelate ligand from the viewpoint of gelation speed, more preferably hydroxycarboxylic acid, aminocarboxylic acid and A water-soluble transition metal compound having at least one selected from the group consisting of amino alcohols.

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 gelation speed, titanium lactate, dihydroxy titanium bis (lactate), titanium lactate ammonium salt, titanium diammonium, dihydroxy bis (slate), di-n-butoxy titanium bis (triethanolaminate), di Isopropoxy titanium bis (triethanolamate) and titanium tetrakis (acetylacetonate) are preferred, and titanium lactate and (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 the organic zirconium compound, zirconylaminocarboxylic acid chloride, monohydroxytris (lactate), zirconium ammonium and tetrakis (lactate) zirconium ammonium are preferable from the viewpoint of the shape retention and strength of the aqueous gel.

The organic titanium compound comprises the above-described chelate ligand (dicarboxylic acid or salt thereof, aminocarboxylic acid or salt thereof, hydroxycarboxylic acid or salt thereof, diol, diamine, aminoalcohol and β-diketone) and titanium tetraalkoxide. It can be obtained by reacting. 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.
The organic zirconium compound can be obtained by reacting the above-mentioned chelate ligand (hydroxycarboxylic acid, aminoalcohol and β-diketone) with zirconium tetraalkoxide, zirconium carbonate, zirconium carbonate 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 1 to 45% from the viewpoint of the shape retention and gel strength of the gel after gelation, based on the weight of the gelling agent. %, More preferably 3 to 40% by weight, next more 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 shape retention and gel strength, it is preferably 55 to 99% by weight, more preferably 60 to 97% by weight, next more preferably 60 to 96% by weight, and particularly preferably 75 to 95% by weight.

  The ratio of the weight of (B) and the weight of (A) in the gelling agent of the present invention {weight of (B) / weight of (A)} is from the viewpoint that the shape retention of the aqueous liquid gel is excellent. 0.01-0.82 is preferable, More preferably, it is 0.03-0.70, Next 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, i-, from the viewpoint of ease of water dissolution in water. Propanol, 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) as water-soluble alcohols and water-soluble ethers, methanol, ethanol, i-propanol, propylene glycol, 3-methoxy-3-methyl-1 -At least one selected from the group consisting of butanol, propylene glycol monomethyl ether, propylene 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, the shape retention of the gel, the ease of dissolution of the hydrophobic compound (deodorant and / or fragrance, etc.) and the hydrophobic compound (deodorant and / or after gelation) From the viewpoint of not inhibiting the fragrance of the fragrance and the like, 0/100 to 95/5 is preferable, more preferably 0/100 to 90/10, next preferably 0/100 to 85/15, particularly preferably 0/100. 100-80 / 20.

  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 from a viewpoint of shape retention.

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.
In the above (i) to (iv), the substance (F) and the additive (G) may be contained in (D) as necessary.

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 a polymer (A), a water-soluble transition metal compound (B) and an aqueous liquid (D).
The content of the polymer (A) in the aqueous liquid gel is based on the weight of the aqueous liquid gel from the viewpoints of gel transparency after gelling, gel shape retention and gel strength, and gel odor suppression. It is preferably 2.3 to 19.8% by weight, more preferably 3.5 to 19.4% by weight, and particularly preferably 4.4 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 the odor of the residual crosslinking agent) and 0.05 to 9.0% by weight, preferably 0.15 to 6.0% by weight, particularly preferably 0.15 to 6.0% by weight, based on the weight of the aqueous liquid gel. Preferably it is 0.19-5.0 weight%, Most preferably, it is 0.6 to 4.3 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 weight of the aqueous liquid gel, it is preferably 71.2 to 97.65% by weight, more preferably 74.6 to 96.35% by weight, particularly preferably 75.8 to 95.41% by weight, most preferably 76.5-95% 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 fragrance substance (F) mentioned above, solubilization of volatile retention agents such as batch oil, modulators such as eugenol, ethylene glycol alkyl ether, propylene glycol alkyl ether and propylene glycol alkyl ether Various components used in the solvent or volatilization regulator and other fragrance industries 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, preservatives, 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 the deodorant and / or from the viewpoint of gel transparency, gel shape retention and 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 4.4 to 19.2% by weight, based on the weight of the fragrance.
The content of the water-soluble transition metal compound (B) in the deodorant and / or fragrance of the present invention is the deodorant and / or fragrance from the viewpoint of gel strength, aesthetics of the aqueous liquid gel and odor of the remaining cross-linking agent. 0.05 to 9.0% by weight, preferably 0.15 to 6.0% by weight, particularly preferably 0.19 to 5.0% by weight, and most preferably 0, based on the weight of .6 to 4.3% by weight.
The content of the aqueous liquid (D) in the deodorant and / or fragrance of the present invention is 56.2 based on the weight of the deodorant and / or fragrance from the viewpoint of gel strength and aesthetics of the aqueous liquid gel. To 97.55% by weight, more preferably 59.6 to 96.25% by weight, particularly preferably 60.8 to 95.31% by weight, and most preferably 61.5 to 94.9% by weight. %.
The content of the substance (F) in the deodorant and / or fragrance of the present invention is slightly different depending on the type, but from the viewpoint of deodorization performance and / or fragrance persistence, 0.1 to 15% by weight is preferred based on weight.

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 (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation and a carboxylate (a22) in which the proton is substituted with an alkali metal cation.

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 (A) is dissolved in an aqueous liquid (D) and (B) are mixed and reacted ( iii) A method in which (A) is mixed and reacted with a solution in which (B) is dissolved in the aqueous liquid (D) (iv) A solution in which (A) is dissolved in the aqueous liquid (D), and (B) is an aqueous liquid ( A method in which the solutions dissolved in D) are respectively prepared in advance, and both are mixed and reacted. Of these, (iv) is preferred from the viewpoint of obtaining a uniform gel.
Moreover, in the gelatinizer of this invention, it is preferable to use (B) as an internal crosslinking agent from a viewpoint of 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, when the reaction is carried out at 5 to 39 ° C. from the viewpoint of easy evaporation of the aqueous liquid and crosslinking reaction, the reaction is preferably completed within 1 minute to 10 days, and 40 to 60 When the reaction is carried out at 0 ° C., it is preferably completed in 1 minute to 1 day.

  A highly transparent aqueous liquid gel is obtained by the production method of the present invention. 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 cell into a cell with an optical path length of 10 mm with a sealed stopper and sealed, and the aqueous liquid gel is prepared by cross-linking reaction at 50 ° C. for 24 hours. To do. 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 1,000,000 (43.9 parts) with ion-exchanged water (213.0 parts) and 48% of sodium hydroxide (molecular weight: 40.0) When an aqueous solution (6.34 parts) was added and stirred at 50 to 60 ° C., it was uniformly dissolved in 1 hour. Furthermore, when 48% methanol solution (32.35 parts) of 1,2,3,4-tetramethylimidazolinium monomethyl carbonate (molecular weight: 204) was added and stirred at 50-60 ° C., it was uniformly dissolved in 4 hours. . The aqueous solution thus obtained was dried using a vacuum dryer at a drying temperature of 105 ° C. and a vacuum degree of 5 kPa for 3 hours, and then pulverized by 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 substitution molar ratio (Q) of 0.25 was obtained.
The polyacrylic acid 1,000,000 used the following.
Polyacrylic acid 1,000,000: Polyacrylic acid, Mw about 1,000,000, manufactured by Wako Pure Chemical Industries, Ltd. The substitution molar ratio (Q) in Production Example 1 is T = 0 in the above formula (1). The following formula was used.
Substitution molar ratio (Q) = (V1 + V2) / S
S: Number of moles of acrylic acid in polyacrylic acid used for production of polymer (A1) (polyacrylic acid usage / 72.06)
V1: Number of moles of sodium hydroxide used for production of polymer (A1) V2: Number of moles of 1,2,3,4-tetramethylimidazolinium monomethyl carbonate used for production of 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, instead of “polyacrylic acid 1,000,000 (43.9 parts)”, “polymer (X1) 37.1 parts” and ion-exchanged water “213.0 parts” “235.0 parts”, “10.80 parts” instead of “6.34 parts” of a 48% aqueous solution of sodium hydroxide, “1,2,3,4-tetramethylimidazolinium monomethyl carbonate ( The substitution molar ratio (Q) was 0.90 in the same manner except that “TEAH-40W (71.50 parts)” was used instead of “48% methanol solution (molecular weight: 204) (32.35 parts)”. A polymer (A2) was obtained. The substitution molar ratio (Q) was calculated by the same method as in Production Example 1.
TEAH-40W: 40% aqueous solution of tetraethylammonium hydroxide (molecular weight: 147), manufactured by Lion Akzo

<Production Example 3> Preparation of polymer (A3) Isovan-18 (39.5 parts) in 48% aqueous solution (4.25) of ion-exchanged water (95.0 parts) and sodium hydroxide (molecular weight: 40.0) Part) was added and stirred at 90 to 100 ° C. to dissolve uniformly in 5 hours. After cooling to 50-60 ° C., ethanol (386.0 parts), 1-ethyl-3-methylimidazolium monomethyl carbonate (molecular weight: 187) in 45% methanol (191.60 parts) were added, and 50-60 When stirred at 0 ° C., it was uniformly dissolved in 4 hours. The aqueous solution thus obtained was dried using a vacuum dryer at a drying temperature of 105 ° C. and a vacuum degree of 5 kPa for 3 hours, and then pulverized by a cooking mixer to have a volume average particle size of 350 μm (trade name: manufactured by Nikkiso Co., Ltd.). A polymer (A3) having a substitution molar ratio (Q) of 1.00.
ISOBAM -18: isobutylene / maleic anhydride copolymer, substitution of a molar ratio (isobutylene / maleic anhydride) = 1/1, Mw3.0 × 10 5 ~3.5 × 10 5, manufactured by Kuraray Co., Ltd. Production Example 3 The molar ratio (Q) was calculated by the following mathematical formula where S = 0 in the mathematical formula (1).
Substitution molar ratio (Q) = (V1 + V2) / (T × 2)
T: Number of moles of maleic anhydride in isoban-18 used for production of polymer (A3) (amount of isoban-18 used / 154.17)
V1: Number of moles of sodium hydroxide used for the production of the polymer (A3) V2: Number of moles of the polymer (1-ethyl-3-methylimidazolium monomethyl carbonate used for the production of A3)

<Production Example 4> Preparation of polymer (A4) In Production Example 3, the isoban 18 was replaced with "39.5 parts" and "28.9 parts", and the ion-exchanged water was replaced with "95.0 parts". 143.0 parts "," 48% aqueous solution of sodium hydroxide (4.25 parts) "instead of" 48% aqueous solution of potassium hydroxide (molecular weight: 56.10) (19.70 parts) "," ethanol ( Instead of “386.0 parts)” and “TEAH” instead of “45% methanol solution (191.60 parts) of 1-ethyl-3-methylimidazolium monomethyl carbonate (molecular weight: 187)”. A polymer (A4) having a substitution molar ratio (Q) of 0.50 was obtained in the same manner except that "-40W (6.90 parts)" was used. The substitution molar ratio (Q) of Production Example 4 was calculated by the following mathematical formula where S = 0 in the mathematical formula (1).
Substitution molar ratio (Q) = (V1 + V2) / (T × 2)
T: Number of moles of maleic anhydride in isoban-18 used for production of polymer (A4) (amount of isoban-18 used / 154.17)
V1: Number of moles of potassium hydroxide used for the production of the polymer (A4) V2: Number of moles of TEAH-40W used for the production of the polymer (A5)

<Production Example 5> Preparation of polymer (A5) In Production Example 3, "GANTREZ AN139 (37.0 parts)" instead of "Isoban 18 (39.5 parts)" and ion-exchanged water "95.0 parts""91.5parts", 48% aqueous solution of sodium hydroxide in place of "4.25 parts""8.30parts", ethanol in place of "386.0 parts""285.0 parts Instead of “45% methanol solution (191.60 parts) of 1-ethyl-3-methylimidazolium monomethyl carbonate (molecular weight: 187)”, “1,2,3,4-tetramethylimidazolinium” A polymer (A5) having a substitution molar ratio (Q) of 0.70 was obtained by the same method except that a 48% methanol solution (98.60 parts) of monomethyl carbonate (molecular weight: 204) was used.
GANTREZ AN139: Methyl vinyl ether / maleic anhydride copolymer, molar ratio (methyl vinyl ether / maleic anhydride) = 1/1, Mw 6.90 × 10 ⁵ , substitution molar ratio in Production Example 5 manufactured by ISP Japan Q) was calculated by the following mathematical formula where S = 0 in the mathematical formula (1).
Substitution molar ratio (Q) = (V1 + V2) / (T × 2)
T: Number of moles of maleic anhydride in GANTREZ AN139 used for production of polymer (A5) (Amount of GANTREZ AN139 used / 156.14)
V1: Number of moles of sodium hydroxide used for production of polymer (A5) V2: Number of moles of 1,2,3,4-tetramethylimidazolinium monomethyl carbonate used for production of polymer (A5)

<Production Example 6> Preparation of aqueous liquid (D1) Ethanol (90 parts) was added to ion-exchanged water (10 parts) to prepare a uniform and transparent aqueous liquid (D1).

<Production Example 7> Preparation of aqueous liquid (D2) Propylene glycol monomethyl ether (60 parts) was added to ion-exchanged water (40 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 perfume: product name “lavender”, product number “OFR-2321”, Hasegawa Inc. Nonipol 120: polyoxyethylene nonylphenyl ether nonionic surfactant, manufactured by Sanyo Chemical Industries

<Production Example 10> Preparation of aqueous polymer solution (A6) of polymer A 48% aqueous solution of ion-exchanged water (106.0 parts) and sodium hydroxide (molecular weight: 40.0) in isoban-18 (42.5 parts). When (11.50 parts) was added and stirred at 90 to 100 ° C., it was uniformly dissolved in 5 hours. After cooling to 50-60 ° C., ethanol (190.0 parts), 1-ethyl-3-methylimidazolium monomethyl carbonate (molecular weight: 187) in 45% methanol (23.00 parts) was added, and 50-60 When stirred at 0 ° C., it was uniformly dissolved in 4 hours to obtain an aqueous liquid solution (A6) of a polymer having a substitution molar ratio (Q) of 0.35.

<Example 1> Preparation of aqueous liquid gel (G1) After adding 96.8 parts of ion-exchanged water to 2.3 parts of (A1) prepared in Production Example 1, the mixture was stirred at 25 ° C for 5 minutes to uniformly dissolve. Furthermore, ORGATICS TC-400 (0.9 parts) 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 (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 4 hours. The gelation time was determined by placing the pre-reaction solution (1) in a container (a glass container with a cylindrical seal plug with a diameter of 3.5 cm and a height of 12 cm) into a thermostatic bath at 50 ° C., and then removing the container every 30 minutes. It was defined as the time during which the solution did not flow after 5 seconds after taking it out and lying down beside (90 degrees) (hereinafter the same). The aqueous liquid gel (G1) has a polymer (A1) content of 2.3%, a water-soluble transition metal compound (B1) content of 0.72%, and a water-soluble transition metal compound (B1) / polymer. The weight ratio of (A1) was 0.31, and the weight ratio of alcohol / water was 0.2 / 99.8.
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) Add 94.2 parts of (D3) prepared in Production Example 8 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 (2). Prepared. 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 6 hours. The aqueous liquid gel (G2) has a polymer (A2) content of 4.4%, a water-soluble transition metal compound (B2) content of 0.62%, and a water-soluble transition metal compound (B2) / polymer. The weight ratio of (A2) was 0.14, and the weight ratio of alcohol / water was 11/89.
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 3> Preparation of aqueous liquid gel (G3) 70.7 parts of (D4) prepared in Production Example 9 was added to 15.0 parts of (A1) prepared in Production Example 1 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 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 7 hours. This aqueous liquid gel (G3) 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) / heavy The weight ratio of the union (A1) was 0.29, and the weight ratio of alcohol / water was 8.8 / 91.2.
In addition, the following were used for ORGATICS ZB-126.
ORGATIXX ZB-126: Zirconyl chloride aqueous solution, solid content 30%, manufactured by Matsumoto Fine Chemical Co., Ltd.

<Example 4> Preparation of aqueous liquid gel (G4) 63.6 parts of ethanol and 7.1 parts of ion-exchanged water were 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 (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 (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 79/21.

<Example 5> Preparation of aqueous liquid gel (G5) After adding 92.2 parts of ion-exchanged water to 6.3 parts of (A4) prepared in Production Example 4, the mixture was stirred at 25 ° C for 5 minutes and dissolved uniformly. Furthermore, ORGATICS TC-400 (1.5 parts) 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 (5). 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 2.5 hours. In this aqueous liquid gel (G5), the amount of the polymer (A4) is 6.3%, the amount of the water-soluble transition metal compound (B1) is 1.2%, the water-soluble transition metal compound (B1) / polymer ( The weight ratio of A4) was 0.19, and the weight ratio of alcohol / water was 0.3 / 99.7.

<Example 6> Preparation of aqueous liquid gel (G6) After 91.0 parts of ion-exchanged water was added to 6.3 parts of (A4) prepared in Production Example 4, the mixture was stirred at 25 ° C for 5 minutes and dissolved uniformly. Further, ORGATICS 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 (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 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 (B2) / polymer ( A4) The ratio was 0.19, and the alcohol / water ratio was 1.2 / 98.8.

<Example 7> Preparation of aqueous liquid gel (G7) After adding 89.7 parts of ion-exchanged water to 6.3 parts of (A4) prepared in Production Example 4, the mixture was stirred at 25 ° C for 5 minutes and dissolved uniformly. Further, ORGATIZ ZB-126 (4.0 parts) was added as a water-soluble transition metal compound (B3), and the mixture was 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 8 hours. This aqueous liquid gel (G7) is composed of 6.3% polymer (A4), 1.2% 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 0/100.

<Example 8> Preparation of aqueous liquid gel (G8) (A4) prepared in Production Example 4 was added to 6.3 parts with 44.2 parts of ethanol and 44.2 parts of ion-exchanged water and stirred at 25 ° C for 5 minutes. After uniformly dissolving, 5.3 parts of Orgatics TC-400 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 (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 1.5 hours. This aqueous liquid gel (G8) 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 51/49.

<Example 9> Preparation of aqueous liquid gel (G9) 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 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 (9). . 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 1.5 hours. This aqueous liquid gel (G9) 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 90/10.

<Example 10> Preparation of aqueous liquid gel (G10) 96.8 parts of (D1) prepared in Production Example 6 was added to 19.2 parts of (A3) prepared in Production Example 3 and stirred at 25 ° C for 5 minutes. And then uniformly dissolved in water, the organic transition TC-400 (1.0 part) is 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 (10). 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 (A3) content of 19.2%, a water-soluble transition metal compound (B1) content of 0.80%, a water-soluble transition metal compound (B1) / polymer The weight ratio of (A3) was 0.042, and the weight ratio of alcohol / water was 90/10.

<Example 11> Preparation of aqueous liquid gel (G11) Add 79.5 parts of (D2) prepared in Production Example 7 to 19.2 parts of (A3) prepared in Production Example 3 and stir at 25 ° C for 5 minutes. Then, ORGATICS TC-400 (1.32 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 (11). Prepared. 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 hours. The aqueous liquid gel (G11) 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 60/40.

<Example 12> Preparation of aqueous liquid gel (G12) To 19.2 parts of (A3) prepared in Production Example 3, 64.4 parts of ethanol and 16.1 parts of ion-exchanged water were added and stirred at 25 ° C for 5 minutes. And uniformly dissolved, and further added ORGATICS TC-400 (0.24 parts) as a water-soluble transition metal compound (B1), stirred at 25 ° C. for 5 minutes to obtain a uniform and transparent pre-reaction solution (12). Prepared. 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 5 hours. The aqueous liquid gel (G12) 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 (A1). ) Ratio 0.01 and alcohol / water ratio 80/20.

<Example 13> Preparation of aqueous liquid gel (G13) Add 89.6 parts of (D2) prepared in Production Example 7 to 8.4 parts of (A5) prepared in Production Example 5 and stir 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 ( 13) was prepared. 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 2 hours. This aqueous liquid gel (G13) 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) / heavy weight The weight ratio of the union (A5) was 0.19, and the weight ratio of alcohol / water was 60/40.

<Example 14> Preparation of aqueous liquid gel (G14) 46.5 parts of aqueous liquid (A6) prepared in Production Example 10 was added to 56.5 parts of ion-exchanged water, and the mixture was stirred and uniformly dissolved at 25 ° C for 5 minutes. Then, 1.5 parts of ORGATICS TC-400 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 (14). 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 (A6) content of 6.3%, a water-soluble transition metal compound (B1) content of 1.2%, a water-soluble transition metal compound (B1) / heavy weight The weight ratio of the union (A6) was 0.19, and the weight ratio of alcohol / water was 25/75.

<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>
According to Example 1 of patent document 12 (Unexamined-Japanese-Patent No. 2003-3029), the dicent acrylamide copolymer modified polyvinyl alcohol was produced as follows.
Into a flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, vinyl acetate (672 parts), diacetone acrylamide (10 parts), and methanol (178 parts) were charged to replace the atmosphere in the system. After that, 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 for complete dissolution. 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 left to stand at 25 ° C. for 2 days to cause a gelation reaction, thereby obtaining a transparent aqueous gel-like 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 results of evaluating the aqueous liquid gels obtained in Examples 1 to 14 and Comparative Examples 1 and 2 by the following evaluation method.

The evaluation method is as follows.
(1) Appearance of gel (1)
The transmittances of the aqueous liquid gels (G1) to (G16) prepared according to the transmittance evaluation method described above were measured. The results are shown in Table 2.

(2) Appearance of gel (2)
The aqueous liquid gels (G1) to (G16) used in gel appearance (1) were cooled at −20 ° C. for 16 hours and allowed to stand 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 pre-reaction solutions (1) to (14) and (16) and the aqueous liquid gel (G15) obtained in 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. Wipe off with 200 and measure the weight gain of Kimwipe. 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 with a diameter of 3.5 cm and a height of 12 cm The aqueous liquid 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 according to 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, it can be seen that the aqueous liquid gels of the present invention of Examples 1 to 14 have a transmittance equal to or higher than that of Comparative Examples 1 and 2 in the appearance (transparency) of the gel and have high transparency. Moreover, the external appearance (1) of the gel which measured the transmittance | permeability of the created gel, and the external appearance (2) of the gel which measured the transmittance | permeability of the gel which left the thing cooled at -20 degreeC for 16 hours for 8 hours, As compared with Comparative Examples 1 and 2, it is found that the change in transmittance is small and the storage stability at low temperature is high. In addition, (3) it can be seen from the evaluation of storage stability at low temperature that the storage stability at low temperature is high. Further, it can be seen that the shape retention at room temperature and the shape retention at high temperature are excellent.

  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 (8)

A gelling agent containing a polymer (A) and the following water-soluble transition metal compound (B), wherein the polymer (A) has a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group It is a polymer having the polymerizable monomer (a1) and the following radical polymerizable monomer (a2) as essential constituent units, and the water-soluble transition metal compound (B) is an organic titanium compound and / or an organic zirconium compound. Gelling agent for aqueous liquid (D).
(B): A compound in which a ligand is bonded to one transition metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
(A2): A carboxylate (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation and a carboxylate (a22) in which the proton is substituted with an alkali metal cation. Based on the weight of the gelling agent, the content of the polymer (A) is 55 to 99% by weight, the content of the water-soluble transition metal compound (B) is 1 to 45% by weight, 2. The gelling agent for an aqueous liquid (D) according to claim 1, wherein the ratio of the weight to the weight of (A) {weight of (B) / weight of (A)} is 0.01 to 0.82. The polymer (A) has a substitution molar ratio (Q) by an onium cation and an alkali metal cation in (A) determined by the following mathematical formula (1) of 0.1 to 1.0. A gelling agent for aqueous liquid (D).
Substitution 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 and the alkali metal cation in (A). ] The gelling agent for aqueous liquid (D) according to any one of claims 1 to 3 , wherein in the polymer (A), the onium cation substitution rate determined by the following formula (2) is 70 to 99%.
Onium cation substitution rate (%) = (L) / (L + M) × 100 (2)
[In Formula (2), L represents the total number of moles of the onium cation in (A), and M represents the total number of moles of the alkali metal cation in (A). ] The aqueous liquid gel formed by gelatinizing an aqueous liquid (D) with the gelatinizer for aqueous liquids in any one of Claims 1-4. The aqueous liquid gel according to claim 5, which has a transmittance of 70 to 100%. The deodorizing and / or fragrance | flavor which comprises the gelatinizer for aqueous liquids in any one of Claims 1-4, the substance (F) which has deodorizing property, and / or fragrance, and an aqueous liquid (D). 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) has 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 and the water-soluble transition metal compound (B) is an organic titanium compound and / or an organic zirconium compound.
(B): A compound in which a ligand is bonded to one transition metal atom by at least one selected from the group consisting of a covalent bond, a hydrogen bond and a coordination bond.
(A2): A carboxylate (a21) in which the proton of the carboxyl group in (a1) is substituted with an onium cation and a carboxylate (a22) in which the proton is substituted with an alkali metal cation.