JP2005095357A - Alcohol supply material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alcohol supply material that can supply alcohol emitted and accordingly stabilize the concentration of alcohol inside the container, in case wet tissues contained in a container are reduced in concentration of alcohol inside the container by the emission of internal alcohol from the opening when opening and closing the container, and are not able to effectively sterilize. <P>SOLUTION: In a polymer (1) with a unit (a) that carries a carboxyl group and/or sulfonic acid group as an essential unit, an alcohol supply material is made of an alcoholic solvent (B) and a crosslinking body (A) of the polymer (1) in which the percentage of the unit is 20 to 100% by weight based on the polymer (1), and 30 to 100 mol % of proton of the group is substituted for quaternary ammonium cation (I), tertiary sulfonium cation (II), etc. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

    The present invention relates to an alcohol supply material.

It has been known for a long time that alcohol, especially ethanol, has a disinfecting and bactericidal action, and what is called a “wet tissue” in which alcohol or the like is impregnated into a nonwoven fabric or paper using this, It is used as tissue paper for wiping towels and toilet seats (for example, Patent Document 1).
JP 63-40555 A

  However, even when wet tissue is stored in the container, when opening and closing the container during use, the alcohol inside the opening volatilizes and the alcohol concentration in the container decreases, so that the sterilization effect etc. can not be fully exhibited was there.

As a result of intensive studies in view of the above situation, the present inventors have found that the crosslinked product of a specific composition has an extremely high absorption amount of the alcohol solvent, and even if alcohol is volatilized when the container is opened and closed by installing it in the container. As a result, it was found that the amount of alcohol could be supplied, and as a result, the alcohol concentration in the container was stabilized, and the present invention was achieved.
That is, the present invention provides the polymer (1) having the structural unit (a) having a carboxyl group and / or a sulfonic acid group as an essential structural unit, wherein the proportion of the structural unit is 20 to 100 weight based on the (1). And 30 to 100 mol% of protons of the acid group are quaternary ammonium cation (I), tertiary sulfonium cation (II), quaternary phosphonium cation (III), and tertiary oxonium cation. (IV), comprising a cross-linked product (A) of a polymer (1) substituted with one or more onium cations selected from the group consisting of alkylpyridinium cations (V) and an alcohol solvent (B) An alcohol supply; and articles comprising the same.

  The cross-linked product in the alcohol supply material of the present invention has a remarkably high liquid absorption amount with respect to various alcohol-based solvents as compared with conventional cross-linked products. The alcohol vapor can be supplied for a long time. It can be useful for a long period of time without significantly reducing the alcohol concentration in the article by storing it in an alcohol-permeable packaging material and using it in an article containing alcohol as an active ingredient. Therefore, it is useful as a wet tissue for miscellaneous goods or medical use or as an alcohol absorbent cotton.

In the present invention, the cross-linked product (A) of the polymer (1) is used to absorb and / or gel the target alcohol solvent.
Here, the alcohol solvent is a water-soluble alcohol that can be mixed with water at an arbitrary ratio or a mixture of this with water, and there is no particular limitation as long as it is such a solvent. The water-soluble alcohol is preferably an aliphatic alcohol having 1 to 6 carbon atoms and having a valence of 1 to 5. Specifically, methanol, ethanol, n-propanol, i-propanol, n-butanol, i- Examples include butanol, s-butanol, t-butanol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like. Preferred are methanol, ethanol, and i-propanol. When water is mixed, the weight ratio of alcohol to water is preferably 0.1 to 99 / 99.9 to 1, more preferably 1 to 90/99 to 10.
The polymer (1) is not particularly limited as long as the polymer (1) satisfies the above conditions, and is preferably a vinyl resin from the viewpoint of production.

In the polymer (1) having the structural unit (a) having a carboxyl group and / or a sulfonic acid group as an essential structural unit, the proportion of the structural unit is 20 to 100% by weight based on the (1), and 30 to 100 mol% of protons of the acid group are quaternary ammonium cation (I), tertiary sulfonium cation (II), quaternary phosphonium cation (III), tertiary oxonium cation (IV), alkyl A crosslinked product (A) of the polymer (1) substituted with one or more onium cations selected from the group consisting of pyridinium cations (V) is described in JP-A No. 2003-251178. The same thing can be used.
As a monomer which comprises the structural unit (a) which has a carboxyl group and / or a sulfonic acid group, what is described in Unexamined-Japanese-Patent No. 2003-251178 can be used. Specifically, for example, a monomer having a carboxyl group [for example, a monocarboxylic acid having 3 to 10 carbon atoms such as (meth) acrylic acid or ethacrylic acid]; a monomer having a sulfonic acid group [for example, aliphatic vinyl sulfonic acid [ Vinyl sulfonic acid, styrene sulfonic acid and the like], and the like, and one or more of these can be used as the structural unit in the polymer (1). Preferably, it is a structural unit having a C 3-30 carboxyl group and / or a sulfonic acid group.

Further, (a) is the same as that described in JP-A-2003-251178. Preferably, the carboxyl group- and sulfonic acid group-containing monomer is subjected to vinyl polymerization to form a structural unit.
The structural unit (b) other than (a) is not particularly limited, regardless of whether it is water-soluble or water-insoluble, but is preferably vinyl polymerized into other structural units. The content of the structural unit having a carboxyl group and / or a sulfonic acid group in the polymer (1) is usually 20 to 100% by weight, preferably 40 to 99.9% by weight, more preferably 60 to 99.8% by weight. %. If the content is less than 20%, even if the proton of a carboxyl group or a sulfonic acid group is replaced with an onium cation described later, the liquid absorption amount with respect to the target alcohol solvent decreases, or the target alcohol solvent with a small amount. May not be gelled.

  As the other structural unit (b), when a structural unit other than the structural unit having a carboxyl group and / or a sulfonic acid group is formed by vinyl polymerization, the other copolymerizable monomer (b) includes a polymerizable non-polymerizable monomer. Examples thereof include monomers having one saturated group, and those described in JP-A No. 2003-251178 can be used. Specifically, for example, (meth) acrylic acid alkyl or cycloalkyl (1 to 30 carbon atoms) esters [methyl (meth) acrylate, etc.]; (meth) acrylic acid oxyalkyl (1 to 4 carbon atoms) [( (Meth) hydroxyethyl acrylate, (meth) acrylic acid mono (polyethylene glycol) ester [number average molecular weight of polyethylene glycol (hereinafter referred to as PEG): 106-4,000, (meth) acrylamides having 3-30 carbon atoms [( Meth) acrylamide etc.], C3-C30 allyl ethers [methyl allyl ether etc.] etc. can be mentioned. What is necessary is just to copolymerize 1 type (s) or 2 or more types of the monomer which forms these other structural units with the monomer which comprises said (a) within the range of predetermined amount.

Among the monomers forming the other structural units, (meth) acrylic acid alkyl esters, oxyalkyl (meth) acrylates, and allyl ethers are from the viewpoint of the polymerizability of the monomers and the stability of the produced polymer. preferable.
In the present invention, since absorption and / or gelation of alcohol solvents is targeted, the SP values of the solvent and the monomer (b) are adjusted in accordance with the SP values (solubility parameters) of the target solvents. It is preferable to select a monomer (b) having a difference of 5 or less because the liquid absorption amount and gelling power are likely to increase, and the SP value of the target solvent and the SP value of the monomer (b) are 3 or less. Is more preferable.

In the present invention, the carboxyl group and / or sulfonic acid group protons are converted to quaternary ammonium cations (I), tertiary phosphonium cations (II), quaternary phosphonium cations (III), tertiary oxonium cations ( It is essential to substitute 30 to 100 mol% with one or more onium cations selected from the group of cations consisting of IV) and alkylpyridinium cations (V).
As the quaternary ammonium cation (I), those described in JP-A No. 2003-251178 can be used except for the alkylpyridinium cation (V). For example, the following (I-1) to (I-11) Is mentioned.
(I-1) an aliphatic quaternary ammonium having 4 to 30 or more carbon atoms having an alkyl and / or alkenyl group;
Tetramethylammonium, tetraethylammonium, trimethylpropylammonium, dimethylpropylammonium, etc .;

(I-2) Aromatic quaternary ammonium having 6 to 30 or more carbon atoms;
Trimethylphenylammonium, triethylphenylammonium, benzyltrimethylammonium, etc .;
(I-3) an alicyclic quaternary ammonium having 3 to 30 or more carbon atoms;
N, N-dimethylpyrrolidinium, N, N-diethylpyrrolidinium, N, N dimethylmorpholinium, etc .;
(I-4) an imidazolinium having 3 to 30 or more carbon atoms;
1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, etc .;
(I-5) an imidazolium having 3 to 30 or more carbon atoms;
1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, etc .;
(I-6) Tetrahydropyrimidinium having 4 to 30 or more carbon atoms (a substituent may be bonded to form a bicyclo ring);
1,3-dimethyltetrahydropyridinium, 1,2,3-trimethyltetrahydropyridinium, 1,2,3,4-tetramethyltetrahydropyridinium, etc .;

(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 and the like;
(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, 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 and the like;
(I-10) Guanidium having a tetrahydropyrimidinium skeleton having 4 to 30 or more carbon atoms;
2-dimethylamino-1,3,4-trimethyltetrahydropyrimidinium 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 and the like;

Examples of the tertiary phosphonium cation (II) include the following (II-1) to (II-3).
(II-1) an aliphatic tertiary phosphonium having 1 to 30 or more carbon atoms having an alkyl and / or alkenyl group;
Trimethylsulfonium, triethylsulfonium, etc .;
(II-2) an aromatic tertiary phosphonium having 6 to 30 or more carbon atoms;
Phenyldimethylsulfonium, phenylethylmethylsulfonium, phenylmethylbenzylsulfonium, etc .;
(II-3) an alicyclic tertiary phosphonium having 3 to 30 or more carbon atoms;
Methylthiolanium, phenylthiolanium, methylthianium, 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, 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;
1,1-dimethylphosphonium, 1,1-diethylphosphoranium, 1,1-dimethylphosphorinanium, etc .;

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, etc .;
(IV-2) Aromatic tertiary oxonium having 6 to 30 or more carbon atoms;
Phenyldimethyloxonium, phenylethylmethyloxonium, phenylmethylbenzyloxonium, etc .;
(IV-3) an alicyclic tertiary oxonium having 3 to 30 or more carbon atoms;
Methyl oxolanium, phenyl oxolanium, methyl oxonium, etc .;

Examples of the alkylpyridinium cation (V) include the following (V-1) to (V-2).
(V-1) an alkylpyridinium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms;
Methylpyridinium, ethylpyridinium, cetylpyridinium, etc .;
(V-2) aromatic pyridinium having 6 to 30 or more carbon atoms;
Phenylpyridinium, benzylpyridinium, etc .;
Among these, a preferred onium cation is (I), more preferred are (I-1), (I-4) and (I-5), and particularly preferred are (I-4) and (I I-5). These onium cations may be used alone or in combination of two or more.

In the present invention, examples of the method for introducing the onium cation into the polymer include a method in which the proton of the carboxyl group and / or the sulfonic acid group of the polymer is substituted with the onium cation. Any method can be used as a method for substituting a proton with an onium cation as long as it is a method capable of substituting a predetermined amount of onium cation. For example, a hydroxide of the onium cation (for example, tetraethylammonium hydroxide) Or monomethyl carbonate (for example, 1,2,3,4-tetramethylimidazolinium monomethyl carbonate) is added to a polymer containing a carboxyl group and / or a sulfonic acid group, and if necessary, dehydration or decarboxylation, It can be easily replaced by demethanol. Moreover, you may substitute similarly in the step of monomer.
Regarding the stage of substitution with an onium cation, for example, a method of polymerizing after the monomer containing a carboxyl group and / or sulfonic acid group is substituted with an onium cation, or a polymer having a carboxyl group and / or a sulfonic acid group is prepared. After that, the method can be exemplified by a method of substituting the proton of the acid with an onium cation, but at any stage as long as the proton of the carboxyl group and / or the sulfonic acid group of the final polymer is substituted. Also good.

  The degree of substitution of the proton of the carboxyl group and / or sulfonic acid group with the onium cation (substitution degree) is 30 to 100 mol%, preferably 50 to 100 mol%, more preferably 70 to 100 mol%. Other protons may be left as they are, or may be substituted with a substance other than the above onium cation, such as a sodium salt or a potassium salt. Preferably, it remains unsubstituted. If the degree of substitution by the onium cation is less than 30 mol%, the dissociation of the carboxyl group, sulfonic acid group and onium cation of the polymer (1) may be too low, and the swelling power and gelling power may be low.

In the present invention, the polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group, and having the carboxyl group and / or the sulfonic acid group substituted with a predetermined amount of an onium cation, Specifically, it is crosslinked at any stage to obtain a crosslinked product.
Examples of the crosslinking method include the methods described in JP-A No. 2003-251178, and examples thereof include the following methods (i) to (v).
(i) crosslinking with a copolymerizable crosslinking agent;
Copolymerizable crosslinkers that can be copolymerized or have 2 to 4 or more double bonds in the molecule [polyvinyl crosslinkers such as divinylbenzene, (meth) such as N, N'-methylenebisacrylamide Acrylamide type crosslinking agents, polyvalent allyl ether type crosslinking agents such as pentaerythritol triallyl ether, and polyvalent (meth) acrylic acid ester type crosslinking agents such as trimethylolpropane triacrylate].
(ii) cross-linking with a reactive cross-linking agent;
Polyhydric isocyanate type crosslinking agents such as 4,4'-diphenylmethane diisocyanate, polyvalent epoxy type crosslinking agents such as poly (2 to 10) glycerol poly (2 to 12) glycidyl ether, polyhydric alcohol type crosslinking such as glycerin Agents, polyvalent amines such as hexamethylenetetramine and poly (2-6) ethyleneimine, imine type crosslinkers, haloepoxy type crosslinkers such as epichlorohydrin, polyvalent metal salt type crosslinkers such as aluminum sulfate, and the like are used.

(iii) crosslinking with a polymerization reactive crosslinking agent;
A glycidyl (meth) acrylate type crosslinking agent such as glycidyl methacrylate, an allyl epoxy type crosslinking agent such as allyl glycidyl ether, or the like is used.
(iv) cross-linking by irradiation;
A method of crosslinking the polymer (1) by irradiating the polymer (1) with radiation such as ultraviolet rays, electron beams, γ rays, or the like, and simultaneously polymerizing and crosslinking by irradiating the monomers with ultraviolet rays, electron beams, γ rays, etc. How to do etc.
(v) crosslinking by heating;
A method in which the polymer (1) is heated to 100 ° C. or more and thermally crosslinked between the molecules of the polymer (1) [crosslinking between carbons due to generation of radicals by heating or crosslinking between functional groups].
The preferred cross-linking methods vary depending on the use and form of the final product, but when considered comprehensively, (i) cross-linking with a copolymer cross-linking agent, (ii) cross-linking with a reactive cross-linking agent, and (iv) radiation. Cross-linking by irradiation.

Among the copolymerizable crosslinking agents, preferred are polyvalent (meth) acrylamide type crosslinking agents, allyl ether type crosslinking agents, and polyvalent (meth) acrylic acid ester type crosslinking agents, and more preferred are allyl ethers. It is a mold cross-linking agent.
Among the reactive crosslinking agents, preferred are a polyvalent isocyanate type crosslinking agent and a polyvalent epoxy type crosslinking agent, and more preferred are a polyvalent isocyanate type crosslinking agent having three or more functional groups in the molecule or It is a polyvalent epoxy type cross-linking agent.
The degree of crosslinking can be appropriately selected depending on the purpose of use, but when a copolymerizable crosslinking agent is used, it is preferably 0.001 to 10% by weight, and 0.01 to 5% by weight based on the total monomer weight. More preferred.
The amount of addition in the case of using a reactive crosslinking agent is preferably 0.001 to 10% by weight, although the preferred amount of addition varies depending on the form of the alcohol supply agent used as the crosslinked product (A). In the case where an integrated gel containing an alcohol solvent is prepared, 0.01 to 50% by weight is preferable.

In the present invention, a method for polymerizing the carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, and another monomer (b) copolymerized as necessary is also described in JP-A No. 2003-251178. The method may be the same, and a solution polymerization method is preferable.
Examples of the organic solvent by solution polymerization are the same as those described in JP-A No. 2003-251178. For example, alcohol, carbonate, lactone, ketone, carboxylic acid ester, ether, aromatic hydrocarbons, water and the like can be mentioned. These solvents may be used alone or in combination of two or more.
The polymerization concentration in the solution polymerization is not particularly limited and varies depending on the intended use, but is preferably 1 to 80% by weight, more preferably 5 to 60% by weight.
The polymerization initiator may be a normal one, such as an azo initiator [azobisisobutyronitrile, azobiscyanovaleric acid, azobis (2,4-dimethylvaleronitrile), azobis (2-amidinopropane) dihydrochloride, etc.], Peroxide initiators [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, hydrogen peroxide, etc.], redox initiators [peroxide initiators and reducing agents (ascorbic acid and persulfate) Salt) and the like].

Examples of other polymerization methods include a method of adding a photosensitizing initiator [benzophenone or the like] and irradiating with ultraviolet rays or the like, a method of irradiating with radiation such as γ rays or electron beams, and the like.
The amount of initiator added when a polymerization initiator is used is not particularly limited, but is preferably 0.0001 to 5%, more preferably 0.001 to 2%, based on the total weight of monomers used.
The polymerization temperature varies depending on the intended molecular weight, the decomposition temperature of the initiator, the boiling point of the solvent used, and the like, but is preferably -20 to 200 ° C, more preferably 0 to 100 ° C.

When making a crosslinked body into a particulate form, the particle diameter is 0.1-5,000 micrometers in a volume average particle diameter, More preferably, it is 50-2,000 micrometers. Moreover, less than 0.1 μm is preferably 10% by weight or less of the whole, and more than 5,000 μm is preferably 10% by weight or less, more preferably 5% or less.
The particle size was measured in the Perry's Chemical Engineers Handbook 6th Edition (McGlow-Hill Book Company, 1984, page 21) using a low-tap test sieve shaker and a JIS Z8801-2000 standard sieve. (Hereinafter, the particle diameter is measured by this method.)

The method for obtaining the particulate form may be the same as the method described in JP-A No. 2003-251178, and examples include the following methods (i) to (iv).
(i): A method in which the copolymerizable crosslinking agent is copolymerized to prepare a crosslinked body (A) of the polymer (1) and pulverized into particles.
(ii): A method in which polymer (1) is polymerized to form polymer (1), and then polymer (1) is crosslinked by means of the reactive crosslinking agent or irradiation, and then pulverized to form particles.
(iii): A method in which a polymer is obtained by copolymerization and crosslinking, and then an onium cation compound is added to replace a proton in an acid group with a predetermined amount of onium cation, followed by pulverization to form particles. (iv); after copolymerization to form an uncrosslinked polymer, the onium cation compound and the reactive crosslinking agent or by irradiation with radiation to crosslink the polymer at the same time as replacing the proton of the acid group, A method of grinding into particles.
The method and conditions for drying and grinding may be the same as those described in JP-A No. 2003-251178.
In this way, a particulate crosslinked body (A) is obtained.

The alcohol supply material of the present invention is composed of the crosslinked product (A) and the alcohol solvent (B), and can be processed into various forms depending on the purpose, but the preferred form is particulate, The form of a sheet form and integral gelation can be mentioned. These forms may be the same as those described in JP-A No. 2003-251178.
The absorption amount of the alcohol supply material is preferably designed so that the absorption amount with respect to ethanol is 10 to 1,000 g / g, and more preferably 50 to 900 g / g. If the amount of absorption is 10 g / g or more, the amount of liquid to be retained is significantly larger than that of the conventional one, and the alcohol supply capacity is prolonged, and if it is 1,000 g / g or less, the alcohol supply material that has retained liquid (B). There is no problem that the gel strength is too weak.

The method of making the shape of the alcohol supply material into a sheet shape (stage before absorbing the alcohol solvent) may be the same as that described in JP-A No. 2003-251178. Examples of the method for forming a sheet include the following methods (v) to (vii).
(v) A method in which the particulate cross-linked product (A) is sandwiched between nonwoven fabrics or papers to form a sandwich sheet.
(vi) After impregnating and / or applying a non-crosslinked body of the polymer (1) to a substrate composed of one or more of nonwoven fabric, woven fabric, paper, and film, (i) to (v ) Is used to crosslink the polymer (1), and if necessary, the solvent is distilled off to form a sheet.
(vii) 20 to 100% by weight of a carboxyl group and / or sulfonic acid group-containing monomer in which 30 to 100% by mole of protons are substituted with the onium cation, and 0 to 80% by weight of another copolymerizable monomer, After impregnating and / or applying the mixed solution comprising the crosslinking agent of i) and / or (iii) to a substrate composed of one or more of nonwoven fabric, woven fabric, paper, and film, A method in which a material is polymerized using a polymerization initiator and / or the means (iv) and / or (v), and if necessary, the solvent is distilled off to form a sheet.
Among these methods, (vi) or (vii) is preferable from the viewpoint of easy adjustment of the thickness of the prepared sheet (s) and the absorption rate of the prepared sheet.

When the shape is a sheet, the thickness of the sheet (s) is preferably 1 to 5,000 μm, more preferably 5 to 2,000, and particularly preferably 10 to 1.000 μm. Regarding the sheet length and width, the preferred length is 0.01 to 10,000 m, and the preferred width is 0.1 to 300 cm.
For the basis weight of the crosslinked polymer of the present invention in the sheet (s), the unit weight, preferably ^{10~3,000g / m 2, 20~1,000g / m} 2 is more preferable.

In the present invention, a base material such as a nonwoven fabric, a woven fabric, paper, or a film, which is used as necessary in order to form the sheet, may be a known substrate, for example, a synthetic fiber having a basis weight of about 10 to 500 g and / or Examples thereof include non-woven fabrics or woven fabrics made of natural fibers, paper (quality paper, thin paper, Japanese paper, etc.), films made of synthetic resin, and two or more base materials thereof and composites thereof.
Among these substrates, preferred are non-woven fabrics and composites of non-woven fabrics with plastic films and metal films, and particularly preferred are plastic films and metal films with one side non-woven and one side non-liquid permeable. It is a complex.
Although there is no limitation in particular regarding the thickness of these base materials, Preferably it is 1-5,000 micrometers, More preferably, it is 10-2,000 micrometers. If the thickness is less than 1 μm, it is difficult to impregnate or apply a predetermined amount of the polymer (1). On the other hand, if the thickness exceeds 5000 μm, the sheet is too thick and the entire body becomes large when placed in a container. It becomes difficult to use.
The coating method or impregnation method of the polymer (1) to the substrate may be a known method, for example, a normal coating or padding method may be applied. After coating or padding treatment, polymerization is performed. The solvent used for dilution and viscosity adjustment may be distilled off by a method such as drying if necessary.

Thus, since the sheet | seat containing the produced crosslinked body (A) absorbs an alcoholic solvent (B) efficiently, it is used as a sheet-type alcohol supply material.
The absorption amount to the alcohol-based solvent of the sheet-type alcohol feed material is preferably 0.1 to 100 g / cm ² sheets, and more preferably from 1 to 100 g / cm ^2.

  The ratio of (A) / (B) in the integral gelled alcohol supply material comprising (A) and (B) is preferably 0.1 to 99/1 to 99.9% by weight, more preferably 0. 0.5 to 50/50 to 99.5% by weight, particularly preferably 1 to 30/70 to 99% by weight, and most preferably 1 to 20/80 to 99% by weight. When the ratio of (A) is 0.1% by weight or more, the generated alcohol-containing gel has sufficient gel strength and can be gelled as a whole, while the content is 99% by weight or less. Since the amount is too large, it can be used as an alcohol supply material.

The production method of the integrated gelled alcohol supply material may be the same as that described in JP-A No. 2003-251178, and an integrated gel is produced by the methods listed in (viii) and (ix) below. What can be done is preferred.
(viii): A method of forming an integrated gel by dissolving the polymer (1) in (B) and crosslinking the (1) with any of the crosslinking means (i) to (v).
(ix) A method in which, in (B), the onium cation group monomer and the acid group monomer are polymerized in the presence of the copolymerizable crosslinking agent to form an integrated gel.

The form of the gel composed of the crosslinked polymer of the present invention and the alcohol solvent may be the same as that described in JP-A No. 2003-251178, and a preferred shape is a sheet. The thickness of the sheet gel is preferably 1 to 10,000 μm, and more preferably 10 to 1,000 μm.
There are no particular limitations on the method for producing gels of these shapes, for example, the polymer (1) on a release paper, a film, a nonwoven fabric, or the like, which is gelled in a container or cell in accordance with the shape to be produced. And a method of preparing a sheet-like gel by a method such as laminating or coating a mixture of (B) with a monomer and the like.

As the alcohol supply material in the present invention, the material impregnated with (B) may be used as it is. However, at least a part of the base material that can transmit the vapor of the alcohol solvent (B), preferably the vapor of ethanol ( It is preferably housed in a packaging material made of a vapor-permeable base material).
Here, the base material capable of transmitting the vapor (B) is a base material having an alcohol solvent vapor permeability, preferably an ethanol vapor permeability of 1 g / m ² · 24 hr (50% RH / 40 ° C.) or more. ^{preferably, 3g / m 2 · 24hr (} 50% RH / 40 ℃) or more substrates are more ^{preferably, 5g / m 2 · 24hr (} 50% RH / 40 ℃) or more substrates are most preferred. Here, the alcohol solvent vapor permeability is indicated by the amount (g) of alcohol solvent vapor passing through 1 m ^{2 of the} substrate in 24 hours in an environment of a temperature of 40 ° C. and a relative humidity of 50%. The value is measured according to JISZ-0208, which is generally used for measuring the water vapor transmission rate of a resin film. Such a material may be the same as that described in JP-A No. 2003-251178, such as paper, non-woven fabric, perforated plastic film, microporous membrane, sheet material having pores or gaps, polyethylene, Nonporous films such as polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVAL), polyvinyl alcohol, ionomer, nylon, cellulose triacetate, or laminates of these are used. As long as the contents do not leak through, water resistance, oil resistance treatment, printing, etc. may be applied as necessary.

In the alcohol supply material of the present invention, substances other than (A) and (B) may coexist in the packaging material. As this substance, the same substance as described in JP-A No. 2003-251178 can be used. For example, resin that absorbs (B), ethanol carrier such as silicon dioxide and vermiculite, other fungicide components and antibacterial components (anionic surfactants, cationic surfactants, chitosan, benzalkonium chloride, etc.) Quaternary ammonium salts, paraoxybenzoic acid, chlorhexidine gluconate, iodine component, etc.), anti-nulling agents, fragrances, deodorants, moisturizers, fragrances and the like, but are not limited thereto. The method for allowing the above substances to coexist is not particularly limited as long as the ability of supplying alcohol and the effects of other coexisting substances are not hindered. For example, these substances are mixed with an alcohol supply material in advance and then stored in the packaging material. Thus, a laminated sheet having a structure of (packaging material / (A) + coexisting substance / packaging material) may be used, or these coexisting substances may be stored in a separate layer from the above (A). In this case, a sheet or the like is interposed between the layer (A) and the coexisting substance layer, so that a laminated sheet having a structure of (packaging material / (A) layer / intervening sheet / coexisting substance layer / packaging material) can be used. good.
The alcohol supply material of the present invention is useful for wet tissues and alcohol absorbent cotton.

An article including an alcohol supply material according to the present invention is an openable / closable container comprising a base material (hereinafter referred to as a vapor-impermeable base material) that does not transmit alcohol-based solvent vapor and ethanol vapor. It is an article that is installed inside.
Here, the base material that does not transmit the alcohol solvent vapor is a base material having an alcohol solvent vapor permeability, preferably an ethanol vapor permeability of 1 g / m ² · 24 hr (50% RH / 40 ° C.) or less. More preferably, a substrate of 0.8 g / m ² · 24 hr (50% RH / 40 ° C.) or less is more preferable, and a substrate of 0.5 g / m ² · 24 hr (50% RH / 40 ° C.) or less is most preferable. . Here, the alcohol-based solvent vapor permeability is measured according to JISZ-0208 as in the previous period under the same measurement conditions as described above. Such base materials include plastic films such as low density polyethylene, biaxially stretched polypropylene, polyester, nylon, polyvinyl chloride, and polyvinylidene chloride, and laminates thereof, metal films such as aluminum foil and aluminum vapor deposition films, and the like. A laminate of the plastic film and the metal film, and a laminate of them with paper, non-woven fabric, woven fabric, etc., which are alcohol vapor impervious and do not leak through. There is no particular limitation as long as it is a material.

  The size and shape of the article of the present invention is not particularly limited as long as it contains an alcohol supply material in an openable / closable container. For example, a cylindrical article such as a household wet tissue or a pack such as a portable towel. Can be illustrated. As a method of use, a wet tissue or absorbent cotton containing alcohol or other components is allowed to coexist in the article of the present invention, and a necessary amount of tissue or absorbent cotton is taken out from the opening / closing part, or the above tissue or absorbent cotton is separately used. Although the method of attaching the opening-and-closing part of the article of the present invention to the container put inside and supplying alcohol vapor from the opening can be illustrated, it is not limited to these.

The ratio of the alcohol supply material in the article is not particularly limited as long as a necessary amount of alcohol vapor can be supplied. However, when the wet tissue or absorbent cotton coexists in the article, the alcohol supply material in the article has a weight ratio of 0. 0.01 to 50% is preferable, and 0.1 to 30% is more preferable. Moreover, 0.01 to 50% is preferable by volume ratio, and 0.1 to 30% is more preferable.
Since the article of the present invention can highly prevent a decrease in alcohol concentration at the time of opening and closing the container, in addition to conventional miscellaneous goods applications (for example, hand towels, etc.), it has not been used so far. It can also be suitably used for tissue.
Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these.
Hereinafter, unless otherwise specified,% indicates% by weight.

360 g (5 mol) of acrylic acid, 1.08 g of pentaerythritol triallyl ether and 1140 g of water were placed in a 2 liter adiabatic polymerization tank.
After cooling the temperature of the monomer solution to 0 ° C. and reducing the dissolved oxygen through nitrogen to the solution, 0.36 g of 2,2′-azobis (2-amidinopropane) hydrochloride and 35% peroxidation were used as a polymerization initiator. Hydrogen water 3.1g and L-ascorbic acid 0.38g were added, and superposition | polymerization was started.
After polymerization, the resulting hydrogel was subdivided using a meat chopper, and this gel was then subjected to 60 mg of 1,2,3,4-tetramethylimidazolinium cation methyl carbonate (molecular weight: 203). When 1353 g (4 mol) of a% methanol solution was added, decarboxylation and demethanol occurred.
The gel to which the imidazolinium cation was added was subjected to 100 ° C. hot air through the gel using a band-type dryer (air-permeable dryer, manufactured by Inoue Metal Co., Ltd.), and water and by-products used as a solvent. The methanol was distilled off and dried.
The dried product was pulverized using a cutter mill to prepare a particulate crosslinked product having an average particle size of 400 μm, and the alcohol-based solvent described in Table 1 was absorbed therein to obtain the supply material (L1) of the present invention. .

  Instead of the methyl carbonate of 1,2,3,4-tetramethylimidazolinium cation used in Example 1, 3307 g (4.5 mol) of a 20% aqueous solution of tetraethylammonium hydroxide (molecular weight: 147) was used. Except having used, operation similar to Example 1 was performed and the alcohol solvent of Table 1 was absorbed, and the alcohol supply material (L2) of this invention was obtained.

184 g (1 mol) of p-styrene sulfonic acid, 104 g (1 mol) of styrene and 1.8 g of divinylbenzene were dissolved in 500 g of ethyl acetate.
To this monomer solution, 332 g (0.8 mol) of 45% ethanol solution of monomethyl carbonate (molecular weight: 187) of 1-ethyl-3-methylimidazolium cation was added, and part of the proton of sulfonic acid was imidazolium. Substitution with cation.
After reducing dissolved oxygen through nitrogen in this monomer solution, using a water bath, the monomer solution was heated to 60 ° C., and 0.6 g of azobis (2,4-dimethylvaleronitrile) was diluted with 12 g of ethanol. The agent solution was dropped and polymerized. The generated gel containing toluene was subdivided, and the solvent dried at 50 ° C. under a reduced pressure of 100 hectopascals was distilled off using a vacuum dryer.
The dried product was pulverized using a cutter mill to prepare a crosslinked product having an average particle size of 400 μm, and the alcohol-based solvent described in Table 1 was absorbed therein to obtain an alcohol supply material (L3) of the present invention.

Comparative Example 1
The method described in Example 3 of JP-A-58-154709, that is, 100 g of an 80% aqueous solution of methacryloxyethyltrimethylammonium chloride, which is a monomer having a quaternary amino group, and 0.06 g of NN methylenebisacrylamide Then, 0.8 g of 2,2′-azobis (2-amidinopropane) hydrochloride was added and mixed as an initiator.
This solution was placed in a box-shaped container heated in a constant temperature water bath at 85 ° C. and polymerized. The polymer is taken out and pulverized using a cutter mill to prepare a crosslinked product having an average particle diameter of 400 μm, and the alcohol-based solvent shown in Table 1 is absorbed therein to obtain a comparative supply material (L′-1). It was.

Comparative Example 2
In a method described in Example 1 of JP-A-60-179410, that is, in a 500 ml round bottom flask equipped with a stirrer, a cooler and a dropping funnel, 230 ml of cyclohexane and 1.0 g of ethyl cellulose were charged and heated to 75 ° C. Separately, 12 g of acrylic acid, 26.2 g of dimethylaminoethyl methacrylate, which is a tertiary amino group-containing monomer, and 70 g of distilled water are mixed in an Erlenmeyer flask, and further 5 g of 35% hydrochloric acid and 0.5 g of N, N-methylenebisacrylamide are mixed. In addition, it was uniformly dissolved.
To this monomer solution, 0.02 g of ammonium persulfate was added as an initiator, and this solution was dropped into the round bottom flask over 1.5 hours for polymerization.
After polymerization, cyclohexane is removed by decantation, and the resulting bead-like particles are dried at 90 ° C. using a vacuum dryer to prepare a crosslinked product having an average particle size of about 200 microns. The system solvent was absorbed and the comparative alcohol supply material (L'-2) was obtained.

The liquid absorption amount and liquid retention amount of the particulate alcohol supply materials in the alcohol supply materials (L1) to (L3) and (L′-1) and (L′-2) with respect to various alcohol solvents are measured by the following methods. did. The results are shown in Table 1.
[Measurement of liquid absorption and liquid retention]
Measurement of liquid absorption amount: 1.00 g of a particulate crosslinked body was added to a nylon mesh bag (opening: 75 μm) having a width of 10 cm and a length of 20 cm, and the mixed solvent of ethanol / water (mixing weight ratio = 50/50) for 3 hours, and then the excess mixed solvent was drained for 30 minutes. The same operation was performed using an empty bag, and the liquid absorption (g / g) was measured by the following formula.
Liquid absorption amount (g / g) = weight of sample bag after swelling−measurement of weight retention amount of empty bag after immersion: Nylon mesh bag whose absorption amount was measured was subjected to centrifugal dehydration device (manufactured by Kokusan Co., Ltd.) The solution was put into a centrifugal diameter of 15 cm and centrifuged for 5 minutes at a rotational speed of 1500 rpm, and the same operation was performed on the empty bag after immersion, and the amount of liquid retained was measured by the following equation.
Retentive volume (g / g) = weight of sample bag after dehydration−weight of empty bag after dehydration Ethanol / water weight ratio is 75/25, and ethanol, methanol, and IPA are similarly operated. The liquid absorption amount and the liquid retention amount with respect to each solvent were measured.

In a 1 liter round bottom flask equipped with a stirrer, nitrogen inlet tube, condenser, dropping funnel, thermometer, 72 g of acrylic acid and monomethoxypolyethylene glycol acrylate (Blemmer AME-400, manufactured by NOF Corporation, PEG number average molecular weight) : About 400) 28 g of methanol and 100 g of methanol were added, and the contents of the flask were replaced with dissolved oxygen through nitrogen, and the temperature of the contents was raised to 50 ° C. using a water bath.
Separately, a solution prepared by dissolving 0.1 g of azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 9.9 g of methanol was dropped over about 2 hours using a dropping funnel while stirring under a nitrogen stream. The polymerization was continued for 2 hours at 50 ° C. after the completion of the dropping, and then the temperature was raised to 70 ° C. for 2 hours to complete the polymerization.
The resulting polymer solution was cooled to room temperature, and then 271 g of a 60% methanol solution of monomethyl carbonate (molecular weight 203) of 1,2,3,4-tetramethylimidazolinium cation used in Example 1 ( About 0.8 mol) was dropped to the polymer solution in the round bottom flask using a dropping funnel, and decarboxylation was observed along with the dropping. After the entire amount of the imidazolinium cation solution was dropped, stirring was continued for about 2 hours to obtain a polymer solution substituted with the imidazolinium cation (polymer concentration: about 47%).
After adding and mixing 0.047 g of polyglycerol polyglycidyl ether (Denacol 521, manufactured by Nagase ChemteX Corporation, number of epoxies: about 5) as a reactive crosslinking agent to 100 g of the polymer solution substituted with this imidazolinium cation. After coating the release paper with a thickness of 200 μm using a knife coater, the polymer was cross-linked by heating and drying for 10 minutes using a circulating air dryer at 100 ° C. Was distilled off.
After drying, the release paper was removed from the polymer to obtain a sheet (M1) having a thickness of about 80 μm. The basis weight of (M1) was about 100 g / m2. The alcohol solvent of the present invention was obtained by absorbing (M1) the alcohol solvent shown in Table 2.

  A polymer solution obtained by immersing a polyester / polyethylene non-woven fabric (Alcima A0404WTO, manufactured by Unitika Co., Ltd.) having a thickness of 47 μm in a mixed solution of the polymer solution substituted with the imidazolinium cation obtained in Example 4 and polyglycerol polyglycidyl ether was used. The nonwoven fabric impregnated with mangle is squeezed so that the amount of impregnation of about 100 g / m 2 is about 100 g / m 2, then heated and dried for 15 minutes in a circulating dryer at 90 ° C., and the basis weight of the alcohol supply material of the present invention is about A 47 g / m @ 2 sheet (M2) was obtained. The thickness of this sheet was about 65 μm. The alcohol solvent of the present invention was obtained by absorbing (M2) the alcohol-based solvent described in Table 2.

Comparative Example 3
The nonwoven fabric (Alcima A0404WTO) used in Example 5 was used as a comparative sheet (M′-1) as it was.

With respect to the sheets (M1), (M2), and (M′-1), the liquid absorption amount and the liquid retention amount with respect to various alcohol solvents were measured by the following methods. The results are shown in Table 2.
[Measurement of sheet liquid absorption and liquid retention]
Measurement of liquid absorption amount of absorbent sheet: After the sheet cut to 5 × 5 cm was immersed in a mixed solvent of ethanol / water (mixed weight ratio = 50/50) for 3 hours, the sheet was fixed with a clip, 30 The mixed solvent in excess was drained for 1 minute, and the liquid absorption (g / cm ² ) was measured by the following formula.
Sheet liquid absorption (g / cm ² ) = weight of subsequent sheet / 25 (cm ² )
Measurement of liquid retention amount of sheet: The sheet whose absorption amount was measured was placed in a nylon mesh bag, placed in a centrifugal dewatering device (manufactured by Kokusan Co., Ltd., centrifugal diameter: 15 cm), and centrifuged for 5 minutes at a rotational speed of 1500 rpm. The liquid retention amount was measured by the following formula.
Liquid retention amount (g / cm ² ) = weight of sample bag after dehydration (g) −weight of empty bag (g)
/ 25 (cm ² )
The same operation was performed with respect to the ethanol / water ratio of 75/25 and ethanol, methanol, and IPA, and the amount of liquid absorbed and the amount of liquid retained for each solvent were measured.

In a 1 liter round bottom flask equipped with a stirrer, nitrogen inlet tube, condenser, dropping funnel, thermometer, 72 g of acrylic acid and monomethoxypolyethylene glycol acrylate (Blemmer AME-400, manufactured by NOF Corporation, PEG number molecular weight: About 400) 28 g and 100 g of methanol were added, and the contents of the flask were replaced with dissolved oxygen through nitrogen, and the temperature of the contents was raised to 50 ° C. using a water bath.
Separately, a solution obtained by dissolving 0.1 g of azobis-2,4-dimethylvaleronitrile, which is a polymerization initiator, in 9.9 g of methanol was dropped over about 2 hours using a dropping funnel while stirring in a nitrogen stream. The polymerization was continued for 2 hours at 50 ° C. after the completion of the dropping, and then the temperature was raised to 70 ° C. for 2 hours to complete the polymerization.
After cooling the polymer solution formed to room temperature, 322 g of a 60% methanol solution of monomethyl carbonate (molecular weight 203) of 1,2,3,4-tetramethylimidazolinium used in Example 1 (approximately 0.95 mol) was added dropwise to the polymer solution in the round bottom flask using a dropping funnel, and it was observed that decarboxylation occurred along with the dropping. After the entire amount of the imidazolinium cation solution was dropped, stirring was continued for about 2 hours to obtain a polymer solution substituted with the imidazolinium cation (polymer concentration: about 42%).
To 100 g of this polymer solution, 950 g of a mixed solvent of ethanol / water = 60/40 was added to dissolve the polymer to obtain a solution having a polymer concentration of 5%.
0.5 g of polyglycerol polyglycidyl ether used in Example 4 was added to 100 g of this mixed solution, placed in a 100 ml sample bottle, the sample bottle was sealed, and heated in a thermostat at 70 ° C. for 1 hour to gel. Thus, an integral gelled alcohol supply material (N1) comprising the alcohol supply material of the present invention and an alcohol solvent was obtained.

Comparative Example 4
In order to prepare a polyethylene oxide (PEO) alcohol-based solvent-containing gel, 3 g of polyethylene glycol (molecular weight: 400) monoacrylate, which is a monomer and a crosslinking agent described in Examples of JP-A-6-68906, and polyethylene glycol -2 g of ludiacrylate and 95 g of a mixed solvent of ethanol / water = 60/40 were mixed as a solvent.
After 0.05 g of azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to this 5% monomer solution and dissolved, it was placed in a 100 ml sample bottle and kept at 60 ° C. for 5 hours under a nitrogen stream. Polymerization was performed to obtain a comparative integrated gelled alcohol supply material (N′-1) composed of a crosslinked product and an alcohol solvent.

Regarding the integrated gelled alcohol supply material (N1) (N′-1), the gelled state immediately after the production and after the transformation was measured by the following method. The results are shown in Table 3.
[Measurement of gelation state immediately after creation and after transformation]
The prepared gel was observed and evaluated according to the following criteria to obtain a gelled state immediately after the preparation.
(Double-circle): The whole is gelatinized completely and the intensity | strength of a gel is also strong.
○: The whole is completely gelled, but the strength of the gel is weak.
Δ: The gel is in a semi-dissolved state, and the gel flows when the sample bottle is tilted down.
X: The whole is liquid and is not gelled.
The prepared sample bottle containing the gel was completely sealed and heated in a constant temperature bath at 80 ° C. for 30 days, and the state of the gel after heating was changed to a gelled state after transformation.

A biaxially oriented polypropylene film (20 μm) / polyethylene film (20 μm) laminated film (ethanol vapor permeability 5 g / m ² · 24 hr (50% RH / 40 ° C.)) in L1 obtained in Example 1 The crosslinked product was uniformly dispersed at a rate of 25 g / m 2, and a nylon (20 μm) / aluminum foil (7 μm) / polyethylene (20 μm) laminate film (alcohol vapor permeability 0.5 g / m ² · 24 hr (50% RH / 40 ° C.)) is cut into 60 mm × 60 mm square, the end is heat-sealed with a width of 10 mm, immersed in a 60% aqueous ethanol solution, and then the same operation as that for measuring the liquid retention amount is performed. Thus, an alcohol supply material (P1) was obtained.

  In Example 7, the alcohol supply material (P2) of the present invention was used in the same manner as in Example 7 except that the absorbent sheet (M2) obtained in Example 5 was cut into 50 mm × 50 mm instead of the crosslinked product. Got.

  In Example 7, the alcohol supply material of the present invention (N1) was used in the same manner as in Example 7 except that the integral gelled alcohol supply material (N1) obtained in Example 6 was used instead of the crosslinked product. P3) was obtained.

Comparative Example 5
In Example 7, a comparative alcohol supply material (P′-1) was obtained in the same manner as in Example 7 except that the crosslinked body in the comparative (L′-1) was used instead of the crosslinked body.

Comparative Example 6
In Example 7, the alcohol supply material (P′-2) of the present invention was obtained in the same manner as in Example 7 except that the comparative absorbent sheet (M′-1) was used instead of the crosslinked product.

Comparative Example 7
In Example 7, the alcohol supply material (P′-3) of the present invention was obtained in the same manner as in Example 7 except that the comparative integral gel (N′-1) was used instead of the crosslinked product. .

Regarding the alcohol supply materials (P1) to (P3) and (P′-1) to (P′-3), an ethanol vapor emission test was performed by the following method.
[Ethanol vapor dissipation test]
A packaging bag with an inner size of 155 mm × 210 mm made of a film in which a KOP film (polypropylene coated with polyvinylidene chloride) and an LLDPE film (linear low-density polyethylene) is laminated is prepared. Any one of the obtained alcohol supply materials (P1) to (P3) and (P′-1) to (P′-3) was accommodated and heat-sealed. The six packaging bags thus obtained were left in a constant temperature bath at 25 ° C., and the ethanol vapor concentration in the packaging bags was measured by the following method on the first, fifth, tenth, fifteenth, and twenty days after the standing. The results are shown in Table 4.

The measurement of ethanol vapor was performed using gas chromatography. The measurement conditions were as follows.
Measuring device model: GC-14A (FID) (manufactured by Shimadzu Corporation)
Filler: PEG-20M 10%
Carrier: Chromosorb WAW DMCS
Column: SUS 2m x 3mm
Carrier gas: N2 1.4kg / cm2
H2 1.0kg / cm2
Air 1.0kg / cm2
Temperature of sample injection section and detection section: 150 ° C
Column temperature: 80 ° C
In Table 4, the ethanol vapor concentration is shown in%.

  Place the above (P1) on the bottom of a cylindrical container (with a diameter of 12 cm and a height of 17 cm) that can be opened and closed at the top center of polypropylene, and above it is below the grid-shaped disk with a diameter of 9 cm A polypropylene cocoon child with four legs 3 mm in diameter and 1.5 cm in height was placed there. On this cocoon cake, 100 non-woven fabric made of pulp for wet tissue (14 cm × 20 cm) wound in a roll shape was put so that 60% ethanol aqueous solution was absorbed to saturation to obtain the article (Q1) of the present invention. . Further, a product without (P1) was used as a comparative article (Q′-1).

The obtained article (Q1) (Q′-1) was subjected to an alcohol vapor supply test by the following method.
[Ethanol vapor supply test]
The wet tissue in the article (Q1) (Q′-1) can be taken out one by one from the roll core toward the upper center part of the container, and the nonwoven fabric is taken out one by one per day. The measurement was performed using gas chromatography in the same manner as the ethanol vapor emission test. The results are shown in Table 5. In Table 5, the ethanol concentration is shown in%.

Since the alcohol supply material of the present invention can supply ethanol over a long period of time, the vapor concentration in the container can be kept stable. By installing it in a wet tissue container or an alcohol absorbent cotton container, conventional miscellaneous goods use Besides, it can be suitably used for medical applications that could not be used conventionally.

Claims (9)

In the polymer (1) having the structural unit (a) having a carboxyl group and / or a sulfonic acid group as an essential structural unit, the proportion of the structural unit is 20 to 100% by weight based on the (1), and 30 to 100 mol% of protons of the acid group are quaternary ammonium cation (I), tertiary sulfonium cation (II), quaternary phosphonium cation (III), tertiary oxonium cation (IV), alkyl An alcohol supply material comprising a crosslinked product (A) of the polymer (1) substituted with one or more onium cations selected from the group consisting of pyridinium cations (V) and an alcohol solvent (B). The alcohol supply material according to claim 1, wherein the onium cation is a quaternary ammonium cation. The alcohol supply material according to claim 1 or 2, wherein the quaternary ammonium cation is one or more selected from the group consisting of an aliphatic ammonium cation, an imidazolinium cation and an imidazolium cation. The alcohol supply material according to any one of claims 1 to 3, wherein the (B) is a water-soluble alcohol or a mixed solution thereof with water. The alcohol supply material according to any one of claims 1 to 4, wherein the cross-linked product (A) has a liquid absorption amount of 10 to 1,000 g / g with respect to ethanol. An alcohol supply material comprising the alcohol supply material according to claim 1 housed in one or more alcohol-permeable packaging materials selected from the group consisting of nonwoven fabric, paper, woven fabric, plastic film and metal film. . The alcohol supply material according to any one of claims 1 to 6, which is used for a wet tissue or an alcohol absorbent cotton. An article in which the alcohol supply material according to any one of claims 1 to 7 is installed in an openable and closable container comprising an alcohol vapor impermeable base material. 9. The article according to claim 8, wherein the article is for general use or medical use.