JP2011208129A - Gelling agent for aqueous liquid, aqueous liquid gel, and method for producing aqueous liquid gel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem that a conventional gelling agent for aqueous liquids is not suitable for air fresheners because it causes quality deterioration with the lapse of time, shows poor solubility to water of a raw material in the preparation of a water-based gel, produces a low transparency water-based gel, and causes deterioration of perfumes being raw materials due to the generation of ammonia in the preparation of the water-based gel.SOLUTION: A gelling agent for an aqueous liquid (D) contains: a reaction product (C) obtained by the reaction of a polymer (X) including, as an essential unit, at least one of monomer (A) selected from the group comprising a 5-10C ethylenic unsaturated polycarboxylic acid, its acid anhydride, fumaric acid and an ethylenic unsaturated monocarboxylic acid with an onium cation and/or ammonium; and at least one crosslinking agent, selected from the group comprising following crosslinking agents: a polyvalent epoxy group-containing compound (B1), a polyvalent oxazoline group-containing compound (B2), a polyvalent carbodiimide group-containing compound (B3), and a polyvalent aziridine group-containing compound (B4).

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-based fragrance (Patent Documents 1 to 4) formed using water as a solvent, 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 a water-based fragrance has a drawback that the organic solution, for example, an alcohol-water mixed solution has a very low absorption capacity or has a low gel strength after absorption.
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) 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) It has been known.

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 disadvantages such as deformation of the gel or spillage of the gel when the container is moved or tilted. Inconvenient to cause liquid separation phenomenon.

As a result of intensive studies aimed at obtaining an aqueous liquid gelling agent and an aqueous liquid gel production method that have improved the above problems, the present inventors have reached the present invention.
That is, the present invention provides at least one monomer (A) selected from the group consisting of ethylenically unsaturated polycarboxylic acids having 5 to 10 carbon atoms and acid anhydrides thereof, fumaric acid and ethylenically unsaturated monocarboxylic acids. At least one crosslinking selected from the group consisting of a reaction product (C) by the reaction of a polymer (X) having an essential structural unit with an onium cation and / or ammonium, and the following crosslinking agents (B1) to (B4). A gelling agent for an aqueous liquid (D) comprising an agent; an aqueous liquid gel obtained by gelling (D) with this gelling agent; and the group consisting of (X) and (B1) to (B4) It is a method for producing an aqueous liquid gel, characterized in that at least one crosslinking agent selected from the above and a composition comprising (D) are subjected to a crosslinking reaction.
Crosslinking agent (B1): Multivalent epoxy group-containing compound Crosslinking agent (B2): Multivalent oxazoline group-containing compound Crosslinking agent (B3): Multivalent carbodiimide group-containing compound Crosslinking agent (B4): Multivalent aziridine group-containing compound

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) Since the gel obtained by gelling an aqueous liquid with the gelling agent for aqueous liquid of the present invention and the gel obtained by the production method of the present invention have good shape retaining properties, It is easy to handle without deforming or spilling gel.
(2) Since the gel obtained by gelling the aqueous liquid with the gelling agent for aqueous liquid of the present invention and the gel obtained by the production method of the present invention are transparent, they are excellent in aesthetics.
(3) The gel obtained by gelling the aqueous liquid with the gelling agent for aqueous liquid of the present invention and the gel obtained by the production method of the present invention are free from the phenomenon of liquid separation from the gel or cracking of the gel. Excellent stability.
(4) Since a fragrance can be mixed and gelled with an aqueous liquid containing a high concentration of alcohol, it has excellent volatility such as a fragrance even when the temperature in winter is low.
Moreover, the manufacturing method of the aqueous liquid gel of this invention has the following effects.
(5) Since the production method of the present invention can produce the gel at a low temperature, the fragrance volatilization and the fragrance alteration during the production hardly occur.

  In the present invention, the reaction product (C) is at least one selected from the group consisting of an ethylenically unsaturated polycarboxylic acid having 5 to 10 carbon atoms and its acid anhydride, fumaric acid and ethylenically unsaturated monocarboxylic acid. The polymer (X) having the monomer (A) as an essential constituent unit may be prepared and then reacted with an onium cation and / or ammonia, or the radical polymerizable monomer (A) and the onium cation and It may also be a polymerized reaction product with ammonia. The former is obtained, for example, by reacting a polymer (X) obtained by polymerizing a polymer (X) having the monomer (A) as an essential constituent unit in a solvent with an onium cation and / or ammonia. It is what The latter is obtained, for example, by polymerizing a reaction product of the monomer (A) with an onium cation and / or ammonia in the presence or absence of a solvent. From the viewpoint of the ease of reaction of the monomer, the former is preferred.

In this invention, itaconic acid, citraconic acid, etc. are mentioned as C5-C10 ethylenically unsaturated polycarboxylic acid which is a structural unit of polymer (X), and its acid anhydride.
Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, monoalkyl maleate (alkyl group having 1 to 9 carbon atoms) ester, fumaric acid monoalkyl (1 to 9 carbon atoms) ester, crotonic acid, sorbic acid , Itaconic acid monoalkyl (carbon number 1 to 9) ester, itaconic acid glycol monoether, cinnamic acid, citraconic acid monoalkyl (carbon number 1 to 9) ester, and the like.
In addition, (meth) acrylic acid means methacrylic acid and / or acrylic acid, and (meth) acrylic ... means methacryl ... and / or acrylic .... The same applies hereinafter.
Among the monomers (A), (meth) acrylic acid, fumaric acid and itaconic acid are preferable from the viewpoint of polymerizability, and (meth) acrylic acid is more preferable.

  In the present invention, as the structural unit of the polymer (X), a radical reactive monomer (E) other than the monomer (A) may be used and copolymerized with (A).

  Examples of the radical reactive monomer (E) include a hydroxyl group-containing radical polymerizable monomer (E-1), an amide group-containing radical polymerizable monomer (E-2), and a tertiary amino group-containing radical polymerizable monomer. Monomer (E-3), epoxy group-containing radical polymerizable monomer (E-4), sulfonic acid group-containing radical polymerizable monomer (E-5), phosphoric acid 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). Examples include acrylate, polypropylene glycol (Mw: 100 to 4,000) mono (meth) acrylate, and methoxypolyethylene glycol (Mw: 100 to 4000) mono (meth) acrylate.
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].
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.
Examples of (E-7) include 4-vinylpyridine, vinylimidazole, N-vinylpyrrolidone and N-vinylacetamide.

  Among the above radical-reactive 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: 100-4000) mono (meth) acrylate, methoxypolyethylene glycol (Mw: 100-4000) 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) acrylic acid. The number of carbon atoms of the amide and the alkyl group is a hydroxyalkyl mono (meth) acrylate 2-3. These monomers (E) may be used alone or in combination of two or more if necessary. Here, (meth) acrylamide means acrylamide and / or methacrylamide,... Acid (salt) means... Acid and / or.

In the present invention, the onium cation is one selected from the group consisting of a quaternary ammonium cation (I), a tertiary sulfonium cation (II), a quaternary phosphonium cation (III), and a tertiary oxonium cation (IV). Or 2 or more types of cations are mentioned.
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 and / or alkenyl group having 4 to 30 or more carbon atoms;
Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethylpropylammonium, dimethylpropylammonium, ethylmethyldipropylammonium, tetrapropylammonium, butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium and the like;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

For the polymer (X), the monomer (A) and, if necessary, the radical reactive monomer (E) are known in the presence or absence of a solvent, such as thermal radical polymerization, photo radical polymerization, anion polymerization, etc. It can obtain by superposing | polymerizing by the method of. 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. Preferably, the solvent is removed.

  The weight average molecular weight (measured by gel permeation chromatography (hereinafter referred to as GPC)) of the produced polymer (X) is preferably from the viewpoint of shape retention and gel strength of the gel after gelation. It is 2,000 to 5,000,000, more preferably 3,000 to 3,000,000.

  A reaction product (C) obtained by reacting the polymer (X) with an onium cation and / or ammonium is obtained by reacting the polymer (X) with an onium cation and / or ammonium.

  Various methods can be employed for the reaction between the polymer (X) and the onium cation, but the solid powder of the polymer (X) is dispersed in a slurry and the onium cation-containing compound is added to the solvent. For example, a method of bringing the polymer (X) into contact with a solvent solution of an onium cation-containing compound is preferably employed. The onium cation-containing compound used in the reaction may be an onium cation hydroxide or an onium cation carbonate.

  Various methods can be employed for the reaction between the polymer (X) and ammonia, but the solid powder of the polymer (X) is dispersed in a slurry and contacted while bubbling ammonia gas into the solvent. Or a method of dissolving the polymer (X) powder in aqueous ammonia is preferably employed.

  The reaction of the polymer (X) with the onium cation and / or ammonia may be any of onium cation alone, combined use of onium cation and ammonia, and ammonia alone.

The reaction product (C) can also be obtained by polymerizing a reaction product obtained by reacting the monomer (A) with an onium cation and / or ammonium.
The reaction of the monomer (A) with the onium cation and / or ammonium can be carried out by the same method as described above, and the obtained reactant can be polymerized by the same method as described above.

  In the case of the reaction product (C) obtained by the reaction of the onium cation alone or a combination of the onium cation and ammonia with the polymer (X), the total amount of the onium cation and ammonia reacted in the reaction product (C). Is gel transparency after gelation, gel shape retention and gel strength with respect to 1 mol of all carboxyl groups (including carboxyl groups derived from carboxylic acid anhydride groups) contained in polymer (X). In view of the above, 0.3 to 1 mol is preferable, more preferably 0.3 to 0.75 mol, and particularly preferably 0.3 to 0.65 mol.

  In the case of the reaction product (C) resulting from the reaction between ammonia alone and the polymer (X), the amount of ammonia reacted in the reaction product (C) is the total carboxyl content in the polymer (X). From 1 to 1 mol of a group (including a carboxyl group derived from a carboxylic acid anhydride group), 0.3 to 1 mol is preferable from the viewpoint of gel transparency after gelation, gel shape retention and gel strength. , More preferably 0.3 to 0.75, particularly preferably 0.3 to 0.65 mol.

  The viscosity at 25 ° C. of the aqueous solution (5 wt% concentration) of the reaction product (C) is 5 to 100,000 mPa · s from the viewpoint of gel transparency after gelation, gel shape retention and gel strength. Is preferable, more preferably 10 to 10,000 mPa · s, and particularly preferably 15 to 5,000 mPa · s.

In the present invention, the crosslinking agent (B1) is a polyvalent epoxy group-containing compound, and there is no limitation as long as it is a polyvalent epoxy group-containing compound having two or more epoxy groups in the molecule. From the viewpoint of strength, the number of epoxy groups contained in the molecule is preferably 3 or more, more preferably 3 to 8, and particularly preferably 3 to 6. The epoxy equivalent (molecular weight per epoxy group) of (B1) is preferably 85 to 400 g / eq, more preferably 85 to 300 g / eq. When the epoxy equivalent is 400 g / eq or less, the crosslinked structure does not become loose and the shape retention of the gel is good. On the other hand, when the epoxy equivalent is 85 g / eq or more, the gel has a better shape retention. Since it becomes a structure, it is preferable.
Examples of (B1) include the following (B11) to (B15).

(B11) Glycidyl ether type epoxy compound (i) Diglycidyl ether of dihydric phenol C6-C30 diglycidyl ether of dihydric phenol, for example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol C diglycidyl Ether, bisphenol AE diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl di Glycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethyl Phenyl diglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furo diglycidyl ether and diglycidyl ether obtained from bisphenol A2 moles and 3 moles of epichlorohydrin in the reaction;

(Ii) Polyglycidyl ethers of polyhydric phenols having 3 to 6 or more valences, polyglycidyl ethers of 3 to 6 or more polyhydric phenols having 6 to 50 or more carbon atoms, such as pyrogallol triglycidyl Ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tert-butyl-butylhydroxymethane triglycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 4'-oxybis (1,4-phenylethyl) phenyl glycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol resin or cresol novolac resin, glycidyl ether of limonene phenol novolac resin, phenol and glyoxal, glutaraldehyde Or polyglycidyl ether of polyphenol obtained by condensation reaction with formaldehyde and polyglycidyl ether of polyphenol obtained by condensation reaction of resorcin and acetone;

(Iii) Diglycidyl ether of aliphatic dihydric alcohol Diglycidyl ether of diol having 2 to 60 carbon atoms, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and alkylene oxide of bisphenol A [ethylene oxide and / or propylene oxide (1 to 20 mol) ] Diglycidyl ether of adducts;
(Vi) Polyglycidyl ethers of 3 to 6 or more aliphatic alcohols Glycidyl ethers of 3 to 6 or more polyhydric alcohols having 3 to 50 or more carbon atoms, such as trimethylolpropane tri Glycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether and poly (n = 2-5) glycerol polyglycidyl ether;

(B12) Glycidyl ester type epoxy compound (i) A glycidyl ester of an aromatic polycarboxylic acid having 6 to 20 or more carbon atoms and 2 to 6 or more carbon atoms (note that carbon of the carboxylic acid is not included in the carbon number) )
Aromatic polycarboxylic acids such as glycidyl esters such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester and trimellitic acid triglycidyl ester;
(Ii) Glycidyl ester of aliphatic or alicyclic polycarboxylic acid having 6 to 20 or more carbon atoms and 2 to 6 or more carbon atoms (note that carbon of carboxylic acid is not included in the carbon number)
Glycidyl esters of aliphatic or alicyclic polycarboxylic acids, for example, aromatic nucleus hydrogenated products of the above-mentioned aromatic polycarboxylic acids, diglycidyl esters of dimer acid, diglycidyl oxalate, diglycidyl malate, diglycidyls Succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, (co) polymer of glycidyl (meth) acrylate (degree of polymerization 2-10 for example), tricarbyl acid triglycidyl ester;

(B13) Glycidylamine type epoxy compound (i) Glycidylamine of aromatic amine having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms Glycidylamine of aromatic amine, for example, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyldiaminodiphenylsulfone and N, N, O -Triglycidylaminophenol;
(Ii) Glycidyl amines of aliphatic amines having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms Glycidyl amines of aliphatic amines such as N, N, N ′, N′— Tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidylhexamethylenediamine;
(Iii) Glycidylamines of alicyclic amines having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms. Glycidylamines of alicyclic amines such as N, N, N ′, N ′ -Hydrogenated compound of tetraglycidylxylylenediamine;
(Iv) a glycidylamine of a heterocyclic amine having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms, a glycidylamine of a heterocyclic amine, such as trisglycidylmelamine;

(B14) Chain aliphatic epoxides Chain aliphatic epoxides having 6 to 50 or more carbon atoms and 2 to 6 or more valences, such as epoxidized polybutadiene and epoxidized soybean oil having an epoxy equivalent of 85 to 400 g / eq;

(B15) Cycloaliphatic epoxides Cycloaliphatic epoxides having 6 to 50 or more carbon atoms and 2 to 4 or more epoxy groups, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, Bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3 , 4-Epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, aromatic nucleus hydrogenated product of the above epoxy compounds of phenol

  In addition, compounds other than (B11) to (B15) can be used as long as they are epoxy compounds having an epoxy group capable of reacting with active hydrogen. These epoxy compounds can be used in combination of two or more.

  Among these (B1), glycidyl ether type epoxy compound (B11) and glycidyl ester type epoxy compound (B12) are preferable, and (B11) is particularly preferable from the viewpoint of shape retention and strength of the aqueous gel.

  From the viewpoint of excellent transparency of the aqueous liquid gel, the crosslinking agent (B1) is a water-soluble epoxy compound (ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl). Ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, poly (n = 2 to 5) glycerol polyglycidyl ether, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate and the like are preferable. . The water-soluble (B1) means that 10 g of an epoxy compound is mixed with 90 g of water at 25 ° C. with stirring, and the water solubility is 50% by weight or more.

  In the gelling agent of the present invention, when the crosslinking agent (B1) is water-soluble or water-dispersible, it can be mixed with the reaction product (C) as it is.

  On the other hand, as a mixing method when the crosslinking agent (B1) is water-insoluble or non-dispersible in water, water is gradually added with stirring while adding or adding an emulsifier to the crosslinking agent (B1) in advance. A method of charging: a method of adding an emulsifier to the cross-linking agent (B1) in advance or mixing it with the reaction product (C) while adding it. In this case, a part or all of the emulsifier may be added to the reaction product (C) in advance.

  Emulsifiers that can be used include anionic, cationic, nonionic and amphoteric surfactants, polymeric emulsifying dispersants, and combinations of two or more thereof, such as U.S. Pat. No. 3,929,678 and U.S. Pat. The thing as described in 4331447 specification is mentioned.

  Anionic surfactants include ether carboxylic acids having C8-24 hydrocarbon groups and salts thereof, sulfonates having C8-24 hydrocarbon groups, and one or two C8-24 hydrocarbon groups. Sulfosuccinates, phosphate esters or ether phosphates having C8-24 hydrocarbon groups and salts thereof, fatty acid salts having C8-24 hydrocarbon groups, and acylation having C8-24 hydrocarbon groups Amino acid salts, etc .; nonionic surfactants include aliphatic alcohol (C8-24) AO (C2-8) adducts (degree of polymerization 1-100), polyvalent (divalent-10 valent or higher) alcohol fatty acids (C8-24) ester, fatty acid (C8-24) alkanolamide, (poly) oxyalkylene (C2-8, degree of polymerization 1-100) alkyl (C1-22) Ether, (poly) oxyalkylene (C2-8, degree of polymerization 1-100) alkyl (C8-24) amine and alkyl (C8-24) dialkyl (C1-6) amine oxide, etc .; Quaternary ammonium salt type, amine salt type, etc .; amphoteric surfactants include betaine type amphoteric surfactants, amino acid type amphoteric surfactants and the like.

  The polymer type emulsifying dispersant includes polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, and carboxyl group-containing (co) polymers such as polyacrylic acid soda, and the number average molecular weight is 1, Polymeric dispersants having urethane bonds or ester bonds described in US Pat. No. 5,906,704, etc. [for example, polycaprolactone polyol and polyether diol linked with polyisocyanate] Can be used.

Among these emulsifiers, nonionic surfactants and polymer-type emulsifying dispersants are preferred from the viewpoint of excellent transparency of the aqueous gel, and particularly preferably a polymer having a urethane bond or an ester bond described in the above publication. Type emulsifying dispersant.
The addition amount of the emulsifier is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the weight of the crosslinking agent (B1), from the viewpoint of excellent transparency of the aqueous gel.

In the present invention, the crosslinking agent (B2) is a polyvalent oxazoline group-containing compound and is not particularly limited as long as it is a compound having two or more oxazoline groups in the molecule. Specifically, 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2, 2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2'- Octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4′-dimethyl-2-oxazoline), 2,2′-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline), bis- (2-oxazolinylcyclohexane) sulfide and bis- (2-oxazolinyl norbornane) sulfide, -Vinyl-2- Examples thereof include aqueous resins obtained by polymerization of unsaturated oxazolines such as xazoline and 2-isopropenyl-2-oxazoline and other unsaturated compounds, and are compatible with the reaction product (C) and / or aqueous liquid (D). From this point of view, an aqueous resin is preferable. The aqueous resin means a resin that can be dissolved in water or dispersed in water.
The water-based resin preferably has an acrylic main chain. Specifically, 4,5-dihydro-2- (isopropenyl) -1,3-oxazole ethyl acrylate methyl methacrylate And the like.

In (B2), it is preferable from the viewpoint of excellent compatibility with the reaction product (C) and / or the aqueous liquid (D) that an aqueous resin is used as a solution or an aqueous resin is used as an emulsion.
The aqueous resin can be dissolved in a suitable solvent in advance and used as a solution. Specific examples of the solvent include water and water-soluble solvents such as 1-methoxy-2-propanol. At this time, the solid content of the solution is preferably 5 to 30% by weight.
When the aqueous resin is used as an emulsion, the solid content of the emulsion is preferably 10 to 60% by weight.

The aqueous resin, the aqueous resin solution, and the aqueous resin emulsion can be produced by a known method, and commercially available products may be used.
Examples of commercially available water-based resins include Epocros WS-300, Epocros WS-500, and Epocros WS-700 (all manufactured by Nippon Shokubai Co., Ltd.). Examples of the aqueous resin emulsion include Epocross K-1010E, Epocross K-1020E, Epocross K-1030E, Epocross K-2010E, Epocross K-2020E, and Epocross K-2030E (all manufactured by Nippon Shokubai Co., Ltd.).

  In the present invention, the crosslinking agent (B3) is a polyvalent carbodiimide group-containing compound and is not particularly limited as long as it is a compound having two or more carbodiimide groups in the molecule. Specific examples include water-based resins in which triisopropylbenzene polycarbodiimide having two or more carbodiimide groups in the molecule is dispersed in water, and is compatible with the reaction product (C) and / or the aqueous liquid (D). From the viewpoint, an aqueous resin is preferable. The aqueous resin means a resin that can be dissolved in water or dispersed in water.

In (B3), it is preferable from the viewpoint of excellent compatibility with the reaction product (C) and / or the aqueous liquid (D) that an aqueous resin is used as a solution or an aqueous resin is used as an emulsion.
The aqueous resin can be dissolved in a suitable solvent in advance and used as a solution. Specific examples of the solvent include water and water-soluble solvents such as 1-methoxy-2-propanol. At this time, the solid content of the solution is preferably 5 to 30% by weight.
When the aqueous resin is used as an emulsion, the solid content of the emulsion is preferably 10 to 60% by weight.

The aqueous resin, the aqueous resin solution, and the aqueous resin emulsion can be produced by a known method, and commercially available products may be used.
Examples of commercially available water-based resins include Carbodilite SV-02, Carbodilite V-02, Carbodilite V-02-L2, and Carbodilite V-04 (all manufactured by Nisshinbo Industries, Inc.).
Examples of the water-based resin emulsion include UCARLNK Croslinker XL-29SE (manufactured by Union Carbide), Carbodilite E-01, Carbodilite E-02, Carbodilite E-03, and Carbodilite E-04 (all manufactured by Nisshinbo Co., Ltd.). .

  In the present invention, the crosslinking agent (B4) is a polyvalent aziridine group-containing compound and is not particularly limited as long as it is a compound having two or more aziridine groups in the molecule. Specifically, 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] and 2,4,6-tris (1 ′ -Aziridinyl) -1,3,5-triazine and the like.

  The cross-linking agent used in the gelling agent for the aqueous liquid (D) of the present invention is not particularly limited as long as it contains at least one cross-linking agent selected from the group consisting of (B1) to (B4). Or two or more of them may be used in combination. Among these, the polyvalent oxazoline group-containing compound (B2) is preferable because it reacts with a carboxyl group at a relatively low temperature.

  The total content of the crosslinking agents (B1) to (B4) is 0.5 to 25.9% by weight, based on the weight of the gelling agent, from the viewpoint of shape retention and gel strength of the gel after gelation. More preferably, it is 0.83 to 25.0% by weight, and particularly preferably 1.48 to 23.1% by weight. Moreover, the total content of the crosslinking agents (B1) to (B4) in the aqueous liquid gel is the gel strength, the aesthetics of the aqueous liquid gel (the amount of the residual crosslinking agent after the water and volatile components are scattered from the gel increases). From the viewpoint of the aesthetics of the remaining gel and the odor of the remaining cross-linking agent, 0.1 to 7.0% by weight is preferable, more preferably 0.15 to 5.0% by weight, and particularly preferably 0.3. -3.0 wt%.

  The content of the reaction product (C) is not particularly limited because it can be changed in various ways depending on the conditions for crosslinking, the target performance, etc., but the gel retention after gelation is based on the weight of the gelling agent. From the viewpoint of formability and gel strength, the content is preferably 74.1 to 99.5% by weight, more preferably 75.0 to 99.17% by weight, and particularly preferably 76.9 to 98.52% by weight. The content of the reaction product (C) in the aqueous liquid gel is 2.0 to 20 from the viewpoint of gel transparency after gelation, gel shape retention and gel strength, and gel odor suppression. 0.0 weight% is preferable, More preferably, it is 4.0-15.0 weight%, Most preferably, it is 5.0-12.0 weight%.

  Ratio of the total content of (B1) to (B4) based on the weight of the gelling agent in the gelling agent of the present invention and the content of (C) based on the weight of the gelling agent {(B1) to The total content of (B4) / content of (C)} is preferably 0.005 to 0.35, more preferably 0.0375 to 0.30, from the viewpoint of excellent shape retention of the aqueous liquid gel. Especially preferably, it is 0.04-0.25.

  As the aqueous liquid (D), 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. The reaction product (C) and the crosslinking agent to be used are preferably soluble. 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. Preferred examples of the water-soluble alcohol include aliphatic alcohols having 1 to 6 carbon atoms and 1 to 5 valences. Specifically, methanol, ethanol, n-propanol, i-propanol, n-butanol, i- Preferred examples include butanol, s-butanol, t-butanol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and 3-methoxy-3-methyl-1-butanol. Specific examples of the water-soluble ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether and dipropylene glycol monomethyl ether. From the viewpoint of solubilizing hydrophobic compounds (such as deodorants and / or fragrances), methanol, ethanol, i-propanol, propylene glycol, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol monomethyl ether and N-methyl-2-pyrrolidone are preferred.

  In the aqueous liquid (D), the weight ratio of the water-soluble compound to water (the weight of the water-soluble compound / the weight of water) is such that the reaction product (C) and the cross-linking agent used are both soluble in the aqueous liquid. The ratio is preferable, from the viewpoint that the hydrophobic compound (deodorant and / or fragrance etc.) is easily dissolved and the fragrance of the hydrophobic compound (deodorant and / or fragrance etc.) after gelation is not inhibited. 0/100 to 100/0, more preferably 10/90 to 99/1, next preferably 30/70 to 98.5 / 1.5, particularly preferably 50/50 to 95/5. .

  As a method for using the gelling agent of the present invention, a method similar to a known method (Japanese Patent Laid-Open No. 2000-192011) using a gelling agent and an aqueous liquid (D) is used. (I) a method in which at least one cross-linking agent selected from the group consisting of (C) and (B1) to (B4) and (D) are directly mixed and then reacted; (ii) an aqueous liquid of (C) (D) A method in which at least one cross-linking agent selected from the group consisting of (B1) to (B4) is mixed in the solution and then reacted, (iii) (C) is converted from the group consisting of (B1) to (B4) A method in which an aqueous liquid (D) solution of at least one selected crosslinking agent is mixed and then reacted, (iv) an aqueous liquid (D) solution of (C), and (B1) to (B4) Each of the aqueous liquid (D) solutions of at least one crosslinking agent After mixing the two, it is possible to create an aqueous solution gel at a method of reacting the like. From the viewpoint of easily obtaining a uniform gel, the preferred method for using a gelling agent is (iv).

  As an aqueous liquid gel, in addition to at least one cross-linking agent selected from the group consisting of reaction products (C) and (B1) to (B4) and an aqueous liquid (D), deodorizing properties and / or fragrances are provided. The substance (F), other additives, etc. which have can be mixed and gelatinized. Other additives are not particularly limited as long as they are water-soluble or water-insoluble, but solvents (alcohols, acetone, etc.), pigments, dyes, anti-aging agents, UV absorbers, UV screening agents, surfactants and preservatives, etc. Is mentioned. Depending on the purpose, these compounds having any concentration can be used. If an insoluble additive is added to the aqueous liquid, the transmittance is lowered. Therefore, from the viewpoint of the transparency of the aqueous liquid gel, the water-insoluble one is added so that the aqueous liquid gel has a transmittance of 70% or more. It is preferable.

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 Phosphorus, carvone, menthone, camphor, acetophenone, P-methylacetophenone and ketones such as ionone, amyl Lactones or oxides such as tyrolactone, 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 acetate, ethyl myristate, ethyl benzoate, benzyl benzoate, methyl phenylacetate, butyl phenylacetate, methyl cinnamate, cinnamyl cinnamate, sartinic acid Le, 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 a mixed substance prepared by mixing two or more types.

  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 perfume industries may be added.

  The amount of the deodorant and / or fragrance substance (F) used varies slightly depending on the type, but from the viewpoint of deodorization performance and / or scent persistence, it is preferably 0. 1 to 15% by weight is preferred.

  In the present invention, the additive (F) alone or the aqueous liquid (F) having a deodorizing property and / or fragrance may contain other additives as required. Examples of such additives include pigments (including fluorescent pigments and phosphorescent pigments), dyes, anti-aging agents, UV absorbers, UV screening agents, antiseptics, fungicides, antifoaming agents, oxygen scavengers, and antioxidants. Agents, surfactants, alcohols, fillers, extenders and the like.

  The method for producing the aqueous liquid gel of the present invention is, for example, a method in which (i) (C) and at least one crosslinking agent selected from the group consisting of (B1) to (B4) and (D) are directly mixed and then reacted. (Ii) A method in which at least one cross-linking agent selected from the group consisting of (B1) to (B4) is mixed in the aqueous liquid (D) solution of (C) and then reacted, (iii) A method in which an aqueous liquid (D) solution of at least one crosslinking agent selected from the group consisting of B1) to (B4) is mixed and then reacted; (iv) an aqueous liquid (D) solution of (C); (B1) After preparing each aqueous liquid (D) solution of at least one cross-linking agent selected from the group consisting of (B4) in advance, there is a method of reacting them after mixing them, but it is easy to obtain a uniform gel, A preferred method is (iv).

When the reaction with (C) and at least one cross-linking agent selected from the group consisting of (B1) to (B4) proceeds, the viscosity of the reaction system increases. When it further proceeds, it gels. The temperature and reaction time when reacting (C) with at least one crosslinking agent selected from the group consisting of (B1) to (B4) are not particularly limited, but the aqueous liquid does not evaporate and the crosslinking reaction From the viewpoint of easiness, the reaction temperature is preferably 5 to 60 ° C, more preferably 15 to 58 ° C, further more preferably 20 to 55 ° C, and particularly preferably 30 to 50 ° C.
Regarding the reaction time, when the reaction is carried out at 5 to 39 ° C., the reaction is completed within 10 days from half a day, and when the reaction is carried out at 40 to 60 ° C., several hours to 1 day are required.

  A highly transparent aqueous liquid gel can be 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 is charged in a 10 mm thick glass cell with a sealed stopper to make it sealed, and a cross-linking reaction is performed at 50 ° C. for 24 hours to prepare an aqueous liquid gel. Furthermore, after temperature-controlling at 25 degreeC for 6 hours, the transmittance | permeability of visible light (700 nm) is measured with a spectrophotometer (the Shimadzu Corporation make, UV-1200).

  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 Reaction Product (C1) Polyacrylic acid 250,000 (7.4 parts) to ethanol (71.1 parts), 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate ( When a 48% methanol solution (21.5 parts) having a molecular weight of 204) was added and stirred at 50 to 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 80 ° C. and a vacuum degree of −100 kPa for 3 hours, and then pulverized with a cooking mixer to have a volume average particle size of 350 μm (trade name, manufactured by Nikkiso Co., Ltd.). : Measured with a Microtrac FRA particle size analyzer), and a reaction product (C1) having an onium cation neutralization rate of 49.2 mol% was obtained. The neutralization rate is a ratio with respect to all carboxyl groups including carboxyl groups derived from carboxylic acids and acid anhydrides, and the same applies to the following production examples, examples and comparative examples.
In addition, the following were used for polyacrylic acid 250,000.
Polyacrylic acid 250,000: Polyacrylic acid, average molecular weight of about 250,000, manufactured by Wako Pure Chemical Industries, Ltd.

Production Example 2 Preparation of polymer (X1) and reaction product (C2) To 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. . This solution was put into an adiabatic polymerization layer, and the dissolved oxygen amount of the solution was adjusted to 0.1 ppm through nitrogen. Then, 0.0005 g of 35% hydrogen peroxide, 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, polymer (X1) instead of polyacrylic acid 250,000, 77.5 parts instead of ethanol (71.1 parts), 1,2,3,4-tetramethyleneimidazolinium monomethyl A reaction product (C2) having an onium cation neutralization rate of 49.2 mol% was obtained in the same manner except that 15.1 parts were used instead of a 48% methanol solution (21.5 parts) of carbonate (molecular weight: 204). )

Production Example 3 Preparation of Reaction Product (C3) In Production Example 1, polymer (X1) instead of polyacrylic acid 250,000, 83.4 parts instead of ethanol (71.1 parts), 1, 2, Onium cation neutralization rate in the same manner except that 9.2 parts were used instead of 48% methanol solution (21.5 parts) of 3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight: 204) 30.0 mol% of a reaction product (C3) was obtained.

Production Example 4 Preparation of Reaction Product (C4) In Production Example 1, polymer (X1) instead of polyacrylic acid 250,000, 61.9 parts instead of ethanol (71.1 parts), 1, 2, Onium cation neutralization rate in the same manner except that 30.7 parts were used instead of 48% methanol solution (21.5 parts) of 3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight: 204). 100.0 mol% of the reaction product (C4) was obtained.

Production Example 5 Preparation of Reaction Product (C5) In Production Example 1, 81.1 parts, 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight) instead of ethanol (71.1 parts) 204) The reaction product having an onium cation neutralization rate of 30.4 mol% by the same method except that TEAH-40W (11.5 parts) was used instead of the 48% methanol solution (21.5 parts). (C5) was obtained.
The TEAH-40W used the following.
TEAH-40W: 40% aqueous solution of tetraethylammonium hydroxide (molecular weight: 147), manufactured by Lion Akzo.

Production Example 6 Preparation of Reaction Product (C6) Polyacrylic acid 250,000 (7.4 parts) to ethanol (80.0 parts), 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate ( When a 48% methanol solution (11.0 parts) having a molecular weight of 204) and an aqueous ammonia solution (1.56 parts) having an ammonia content of 28% were added and stirred at 50 to 60 ° C., they were uniformly dissolved in 4 hours. The aqueous solution thus obtained was dried using a vacuum dryer at a drying temperature of 80 ° C. and a vacuum degree of −100 kPa for 3 hours, and then pulverized with a cooking mixer to have a volume average particle size of 350 μm (trade name, manufactured by Nikkiso Co., Ltd.). : Measured with Microtrac FRA particle size analyzer), reaction product (C6) having an onium cation neutralization rate of 25.2 mol% and an ammonia neutralization rate of 25.0 mol% was obtained.

Production Example 7 Preparation of Reaction Product (C7) In Production Example 6, instead of polyacrylic acid 250,000 (7.4 parts), polymer (X1) and ethanol (80.0 parts) were used instead of 83.8. Instead of a 48% methanol solution (11.0 parts) of 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight: 204), ammonia having an ammonia content of 28% A reaction product (C7) having an onium cation neutralization rate of 25.1 mol% and an ammonia neutralization rate of 25.1 mol% by the same method except that 1.10 parts was used instead of the aqueous solution (1.56 parts). Got.

Production Example 8 Preparation of Reaction Product (C8) In Production Example 6, instead of ethanol (80.0 parts), 63.9 parts 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight) : 204), except that 26.2 parts were used instead of 48% methanol solution (11.0 parts), and 2.50 parts were used instead of ammonia aqueous solution (1.56 parts) having an ammonia content of 28%. By the method, a reaction product (C8) having an onium cation neutralization rate of 60.0 mol% and an ammonia neutralization rate of 40.0 mol% was obtained.

Production Example 9 Preparation of Reaction Product (C9) In Production Example 6, instead of ethanol (80.0 parts), 52.7 parts, 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight) : 204) in place of 48% methanol solution (11.0 parts), except that 39.3 parts and 0.63 parts in place of ammonia aqueous solution (1.56 parts) with 28% ammonia content were used. By the method, a reaction product (C9) having an onium cation neutralization rate of 90.0 mol% and an ammonia neutralization rate of 10.0 mol% was obtained.

Production Example 10 Preparation of Reaction Product (C10) In Production Example 6, instead of ethanol (80.0 parts), 80.3 parts 1,2,3,4-tetramethyleneimidazolinium monomethyl carbonate (molecular weight) :) except that a 45% methanol solution (10.7 parts) of 1-ethyl-3-methylimidazolium monomethyl carbonate (molecular weight: 187) was used instead of the 48% methanol solution (11.0 parts) In the same manner, a reaction product (C10) having an onium cation neutralization rate of 25.1 mol% and an ammonia neutralization rate of 25.0 mol% was obtained.

Production Example 11 Preparation of Reaction Product (C11) To polyacrylic acid 250,000 (7.4 parts), ion-exchanged water (90.7 parts) and an aqueous ammonia solution (1.9 parts) having an ammonia content of 28% were added. When 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 80 ° C. and a vacuum degree of −100 kPa for 3 hours, and then pulverized with a cooking mixer to have a volume average particle size of 350 μm (trade name, manufactured by Nikkiso Co., Ltd.). : Measured with a Microtrac FRA particle size analyzer), and a reaction product (C11) having an ammonia neutralization rate of 30.4 mol% was obtained.

Production Example 12 Preparation of Reaction Product (C12) In Production Example 11, polymer (X1) instead of polyacrylic acid 250,000, 90.4 parts instead of ion-exchanged water (90.7 parts), ammonia content A reaction product (C12) having an ammonia neutralization rate of 50.2 mol% was obtained in the same manner except that 2.2 parts were used instead of the 28% aqueous ammonia solution (1.9 parts).

Production Example 13 Preparation of aqueous liquid solution (C13) of reaction product Polymer (X1) (10.0 parts) was added to TEAH-40W (9.0 parts), an aqueous ammonia solution having an ammonia content of 28% (0.6 parts) ), Ion-exchanged water (124.2 parts) and ethanol (14.5 parts) were added and stirred at 50 to 60 ° C. to uniformly dissolve in 4 hours, onium cation neutralization rate of 25.0 mol%, ammonia neutralization An aqueous liquid solution (C13) of the reaction product having a rate of 10.0 mol% was obtained.

Production Example 14 Preparation of aqueous liquid (D1) Ethanol (40 parts) was added to ion-exchanged water (60 parts) to prepare a uniform and transparent aqueous liquid (D1).

Production Example 15 Preparation of aqueous liquid (D2) Propylene glycol monomethyl ether (10 parts) was added to ion-exchanged water (90 parts) to prepare a uniform and transparent aqueous liquid (D2).

Production Example 16 Preparation of Aqueous Liquid (D3) As a substance having deodorizing properties, ion-exchanged water (85.2 parts) and ethanol (9.8 parts) were added to Epolion SK-500 (5 parts) and dissolved 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 17 Preparation of aqueous liquid (D4) Nonipol 120 (0.5 parts), ethanol (9.9 parts) and ion-exchanged water (89.1 parts) were uniformly added to a floral fragrance (0.5 parts). It melt | dissolved and the aqueous liquid (D4) was adjusted.
In addition, the floral fragrance | flavor and nonipol 120 used the following.
Floral fragrance: Product name “Lavender”, product number “OFR-2321”, manufactured by Hasegawa Fragrance Co., Ltd. Nonipol 120: Polyoxyethylene nonylphenyl ether-based nonionic surfactant, manufactured by Sanyo Chemical Industries, Ltd.

Example 1 Preparation of aqueous liquid gel (G1) D1 (94.7 parts) prepared in Production Example 14 was added to C1 (5.0 parts) prepared in Production Example 1, and stirred at 25 ° C. for 30 minutes to be uniform. After dissolution, ethylene glycol diglycidyl ether (0.3 parts) was further added as the polyvalent epoxy group-containing compound (B1-1), and the mixture was stirred at 25 ° C. for 30 minutes to prepare a uniform and transparent aqueous liquid. The aqueous liquid 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). This aqueous liquid gel (G1) has a reaction product (C) amount of 5.0%, a polyvalent epoxy-containing compound (B1-1) amount of 0.3%, a polyvalent epoxy-containing compound (B1-1) / The reaction product (C) ratio was 0.06, and the ethanol / water ratio was 40/60.

Example 2 Preparation of Aqueous Liquid Gel (G2) Ethanol (92.0 parts) was added to C5 (5.0 parts) prepared in Production Example 5 and stirred at 25 ° C. for 30 minutes to dissolve uniformly. Epocros WS-300 (3.0 parts) was added as a divalent oxazoline group-containing compound (B2-1), and stirred at 25 ° C. for 30 minutes to prepare a uniform and transparent aqueous liquid. The aqueous liquid thus obtained was reacted in a 50 ° C. constant temperature bath for 24 hours to obtain a uniform and transparent aqueous liquid gel (E2). This aqueous liquid gel (G2) comprises 5.0% of the reaction product (C), 0.3% of the polyvalent oxazoline group-containing compound (B2-1), and the polyvalent oxazoline group-containing compound (B2-1). ) / Reaction product (C) ratio 0.06 and ethanol / water ratio 97.1 / 2.9.
In addition, the following was used for Epocross WS-300.
Epocros WS-300: Oxazoline group-containing polymer (trifunctional) aqueous solution, solid content 10%, manufactured by Nippon Shokubai Co., Ltd.

Example 3 Preparation of aqueous liquid gel (G3) After adding ion-exchanged water (94.37 parts) to C2 (5.0 parts) prepared in Production Example 2 and stirring uniformly at 25 ° C. for 30 minutes, the mixture was uniformly dissolved. Furthermore, carbodilite SV-02 (0.63 parts) was added as a polyvalent carbodiimide group-containing compound (B3-1), and the mixture was stirred at 25 ° C. for 30 minutes to prepare a uniform and transparent aqueous liquid. The aqueous liquid thus obtained was reacted for 24 hours in a 50 ° C. constant temperature bath to obtain a uniform and transparent aqueous liquid gel (G2). This aqueous liquid gel (G2) is composed of 5.0% of the reaction product (C), 0.25% of the polyvalent carbodiimide group-containing compound (B3-1), polyvalent carbodiimide group-containing compound (B3) / The reaction product (C) ratio was 0.05, and the ethanol / water ratio was 0/100.
Carbodilite SV-02 used the following.
Carbodilite SV-02: aqueous solution of polyvalent carbodiimide group-containing compound, solid content 40%, manufactured by Nisshinbo Industries, Ltd.

Example 4 Preparation of Aqueous Liquid Gel (G4) Ethanol (94.9 parts) was added to C5 (5.0 parts) prepared in Production Example 5 and stirred at 25 ° C. for 30 minutes to dissolve uniformly. 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] (0.1 part) was added as a divalent aziridine group-containing compound (B4-1) and stirred at 25 ° C. for 30 minutes to obtain a uniform A clear aqueous liquid was prepared. The aqueous liquid thus obtained was reacted for 24 hours in a 50 ° C. constant temperature bath to obtain a uniform and transparent aqueous liquid gel (G4). This aqueous liquid gel (G4) comprises a reaction product (C) of 5.0%, a polyvalent aziridine-containing compound (B4-1) of 0.1%, a polyvalent aziridine-containing compound (B4-1) / The reaction product (C) ratio was 0.02, and the ethanol / water ratio was 100/0.

Example 5 and Examples 11-14
In Example 2, aqueous gels (G6) and (G11) to (G14) were obtained in the same manner as in Example 2 except that the amounts charged were those shown in Tables 1 and 2. (1) Amount of reaction product (C) in aqueous liquid gel of aqueous gel (G6) and (G11) to (G14), (2) Sum of crosslinking agents (B1) to (B4) in aqueous liquid gel Tables 1 and 2 show the amounts, (3) [(B1) to (B4)] / (C) ratios, and (4) alcohol / water ratios.

Examples 6-10 and Examples 15-17
In Example 1, aqueous gels (G6) to (G10) and (G15) to (G17) were obtained in the same manner as in Example 1 except that the amount charged was changed to the values shown in Tables 1 and 2. Aqueous gels (G6) to (G10) and (E15) to (E17) (1) Amount of reaction product (C) in aqueous liquid gel, (2) Crosslinkers (B1) to (B) in aqueous liquid gel Tables 1 and 2 show the total amount of B4), the ratio of (3) [(B1) to (B4)] / (C), and the ratio of (4) alcohol / water.

Comparative Example 1
In accordance with Patent Document 9 (Japanese Patent Laid-Open No. 1-119258), a gel was prepared as follows. D1 (94.5 parts) prepared in Production Example 14 was added to Carbopol 980 (1.5 parts), heated to boiling while stirring to dissolve Carbopol 980, and then cooled to 25 ° C ( a) A liquid was obtained. Nonipol 120 (0.5 part) used in Production Example 17 was added to the floral fragrance (0.5 part) used in Production Example 17, 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 (G18).
In addition, the following was used for the carbopol 980.
Carbopol 980: carboxy vinyl polymer, manufactured by BF Goodrich

Comparative Example 2
In accordance with Example 1 of Patent Document 12 (Japanese Patent Laid-Open No. 2003-3029), a diacetacrylamide copolymer-modified polyvinyl alcohol was prepared 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. Subsequently, after cooling the obtained solution to 50 ° C. or lower, as a surfactant, Nonipol 120 (0.6 parts) used in Production Example 17, ethanol (9.4 parts), and Floral used in Production Example 17 were used. An aqueous gel fragrance composition was prepared by mixing 10% by weight of an adipic acid dihydrazide aqueous solution (8 parts) as a system fragrance (0.6 parts) and a crosslinking agent. Subsequently, the obtained composition 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 (G19).

  Table 3 shows the evaluation results of Examples 1 to 17 and Comparative Examples 1 and 2.

The evaluation method is as follows.
(1) Appearance of gel (1)
The appearance of the gel prepared according to the transmittance evaluation method described above was evaluated by transmittance as follows.
○: Transmittance of 70 or more and 100 or less Δ ... Transmittance of 30 or more and less than 70 x: Transmittance of 0 or more and less than 30 (2) Appearance of gel (2)
The gel used in gel appearance (1) cooled at −20 ° C. for 16 hours is allowed to stand at 25 ° C. for 8 hours, and the gel appearance is determined according to the transmittance according to the transmittance evaluation method described above. It was evaluated as follows.
○ ... Transmittance of 70 or more and 100 or less Δ ... Transmittance of 30 or more and less than 70 x ... Transmittance of 0 or more and less than 30

(3) Transmittance The transmittance was measured according to the evaluation method described above.
(4) Low-temperature stability A 50 g sample was placed in a cylindrical container with a tight seal with a diameter of 4 cm, and the gel prepared by reacting at 50 ° C. for 24 hours was left in a 4 ° C. constant temperature bath for 1 week, and then left at 25 ° C. for 8 hours. After that, the separated material on the surface of the gel was wiped off with Kimwipe Wiper S-200, and the weight increase of Kimwipe was evaluated as follows.
○: Weight increase of 0.10 g or less Δ: Weight increase of over 0.10 g and 0.20 g or less x: Weight increase of water separation of over 0.20 g Kimwipe Wiper S-200: Pulp sheet , 100% pulp, sheet size (120 mm x 215 mm), manufactured by Nippon Paper Crecia.

(5) Gel shape retention A half amount (6 cm from the bottom) of the gel is sealed in a glass container with a cylindrical seal with a diameter of 3.5 cm and a height of 12 cm, and the gel is prepared by reacting at 50 ° C. for 24 hours. And left at 25 ° C. for 6 hours. After marking the position (A) in contact with the upper surface of the gel, the container was laid down beside it, and the position (B) was lowered vertically from the tip of the gel one hour after laying down to the glass surface. The distance from the position (A) to the position (B) was defined as the gel moving distance, and the shape retention of the gel was evaluated.
○: Gel movement distance of 2 cm or less Δ: Gel movement distance of more than 2 cm, 4 cm or less x: Gel movement distance of more than 4 cm, fluidized (6) High temperature stability The sample prepared by the “gel shape retention” evaluation method described above was allowed to stand in a constant temperature bath at 50 ° C. for 72 hours, and the container was laid down beside it in an atmosphere of 50 ° C. The gel movement distance was measured in accordance with the “gel shape retention” evaluation method, and the high-temperature stability was evaluated as follows.
○: The movement distance of the gel is 2 cm or less. Δ: The movement distance of the gel is more than 2 cm, and the movement distance is 4 cm or less.

(7) Presence or absence of ammonia odor Adjust the gel by sealing a half amount (6 cm from the bottom) of a gel in a glass container with a cylindrical seal with a diameter of 3.5 cm and a height of 12 cm and reacting at 50 ° C. for 24 hours. The mixture was further left at 25 ° C. for 6 hours. Ten general men and women each opened a glass container and evaluated the presence or absence of ammonia odor.
○… No more than 2 people who felt the odor of ammonia △… Three people who felt the odor of ammonia 3 to 5 people ×… No more than 6 people who felt the odor of ammonia

  From the results of Table 3, it can be seen that the examples of Examples 1 to 17 are excellent in gel appearance, transmittance, low temperature stability, shape retention, high temperature stability, and presence of ammonia odor. In Comparative Examples 1 and 2, water separation from the gel occurred at low temperatures, and the low-temperature stability was poor. Further, Comparative Example 1 had poor shape retention and high temperature stability because no crosslinked structure was formed.

  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 (7)

At least one monomer (A) selected from the group consisting of an ethylenically unsaturated polycarboxylic acid having 5 to 10 carbon atoms and its acid anhydride, fumaric acid and ethylenically unsaturated monocarboxylic acid is an essential constituent unit. A reaction product (C) obtained by the reaction of the polymer (X) with the onium cation and / or ammonium, and at least one crosslinking agent selected from the group consisting of the following crosslinking agents (B1) to (B4). A gelling agent for an aqueous liquid (D).
Crosslinking agent (B1): Multivalent epoxy group-containing compound Crosslinking agent (B2): Multivalent oxazoline group-containing compound Crosslinking agent (B3): Multivalent carbodiimide group-containing compound Crosslinking agent (B4): Multivalent aziridine group-containing compound Based on the weight of the gelling agent, the content of the reaction product (C) is 74.1 to 99.5% by weight, and the total content of the crosslinking agents (B1) to (B4) is 0.5 to 25. The ratio of the total content of (B1) to (B4) to the content of (C) {the total content of (B1) to (B4) / the content of (C)} is 0.9% by weight. It is 005-0.35, The gelatinizer for aqueous liquids of Claim 1. In the reaction product (C), the total amount of reacted onium cation and ammonium is 1 mol of all carboxyl groups (including carboxyl groups derived from carboxylic anhydride groups) contained in the polymer (X). The aqueous liquid gelling agent according to claim 1 or 2, wherein the amount is 0.3 to 1 mol. The aqueous liquid gel formed by gelatinizing an aqueous liquid (D) with the gelatinizer for aqueous liquids in any one of Claims 1-3. The aqueous liquid gel according to claim 4, 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 1-3, the substance (F) which has deodorizing property, and / or fragrance, and aqueous solution (D). At least one monomer (A) selected from the group consisting of an ethylenically unsaturated polycarboxylic acid having 5 to 10 carbon atoms and its acid anhydride, fumaric acid and ethylenically unsaturated monocarboxylic acid is an essential constituent unit. Reaction product (C) by the reaction of polymer (X) with onium cation and / or ammonium, at least one crosslinking agent selected from the group consisting of the following crosslinking agents (B1) to (B4), and an aqueous liquid ( A method for producing an aqueous liquid gel, comprising a step of crosslinking reaction of the composition comprising D).
Crosslinking agent (B1): Multivalent epoxy group-containing compound Crosslinking agent (B2): Multivalent oxazoline group-containing compound Crosslinking agent (B3): Multivalent carbodiimide group-containing compound Crosslinking agent (B4): Multivalent aziridine group-containing compound