JP2001245913A - Nonaqueous thermo-gel composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous thermo-gel composition having a shape retaining property and generating heat by contact with water in use, and a thermo-sheet having the nonaqueous thermo-gel composition. SOLUTION: This nonaqueous thermo-gel composition is characterized by containing polyhydric alcohols and polymer dissolved in the polyhydric alcohols or swollen by the polyhydric alcohols. This thermo-sheet is provided with a support and the nonaqueous thermo-gel composition provided on the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous thermal gel composition characterized in that it generates heat by contact with water during use, and a thermal sheet having the non-aqueous thermal gel composition.

[0002]

2. Description of the Related Art Heretofore, there have been known so-called disposable warmers utilizing air oxidation of iron, compositions using a heating wire, and compositions utilizing heat of hydration as compositions that generate heat by themselves and give a warm feeling to the skin and the like. (Japanese Unexamined Patent Application Publication No. 10-152432,
JP-A-8-231386, JP-A-8-133966, JP-A-8-127532, JP-A-7-284507, JP-A-7-284506, and JP-A-5-170644. Here, there are those utilizing the heat of hydration of polyhydric alcohols as those utilizing the heat of hydration, and include gel-like compositions obtained by mixing a water-soluble anionic polymer with polyhydric alcohols. Are known (JP-A-5-22926, JP-A-2-22).
311408). However, since the anionic polymer used as the gelling agent is essentially incompatible with the polyhydric alcohol, only a small amount of the polymer can be blended and a desirable gel or sheet composition cannot be formed. On the other hand, there is a water-containing composition in which a water-soluble polymer and a saccharide are blended with a polyhydric alcohol (JP-A-6-92820). But this is
It gives a warm feeling by adding water in advance, generates less heat at the time of application, and is not preferable in terms of storage stability because it contains saccharides. Furthermore, since the water-soluble polymer is essentially incompatible with the polyhydric alcohol, a sufficient amount cannot be blended as a gel base. Further, the water-soluble polymer and saccharide compounded here are added for the purpose of improving detergency, feeling of use, and texture, and do not form a gel-like composition and stay for a certain period of time. It is not possible to give the required heating effect or to apply it on a support and form it into a sheet. JP-A-11-310797 discloses a detergent composition containing a polyhydric alcohol-soluble polymer compound. However, the polyhydric alcohol dissolving ability of the polymer described herein is as low as, for example, 0.01% by mass, and the compounding amount in the product is 10% by mass or less, which gives a gel composition. is not. On the other hand, those utilizing the heat of hydration include those utilizing activated zeolite and the heat of hydration of inorganic salts (JP-A-54-126741,
JP-A-6-100411, JP-A-6-336413, JP-A-5-9109, JP-A-63-54308, JP-A-1
1-228332). However, although these calorific values are large, it is difficult to maintain an appropriate warm feeling for a long period of time.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a non-aqueous thermal gel composition which has shape retention properties and can generate heat upon contact with water.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has determined that polyhydric alcohols that generate heat upon hydration are used as exothermic agents and dissolved or dissolved in the polyhydric alcohols. By using a polymer that swells as a base and impregnating the polymer base material with a heating agent, a composition having the required form retention and capable of generating heat upon contact with water has been found. Accordingly, the present invention provides a non-aqueous thermal gel composition comprising a polyhydric alcohol and a polymer that dissolves in the polyhydric alcohol or swells with the polyhydric alcohol. I do. The present invention also provides a thermal sheet comprising a support and the non-aqueous thermal gel composition of the present invention provided on the support.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The polyhydric alcohol used in the present invention is preferably a liquid (for example, at 36.degree. C.) which generates heat of hydration upon hydration upon contact with water. It is preferable that the temperature rises by 2 ° C. or more when mixed with water. In addition, since volatile polyhydric alcohols have a problem in that the temperature decreases due to heat of vaporization, the polyhydric alcohols used in the present invention are preferably non-volatile. Those having 2 to 4 hydroxyl groups in the molecule are preferred. Specifically, polyhydric alcohols that can be used include, for example, 1,
3-butanediol, ethylene glycol, propylene glycol, glycerin, diglycerin, triglycerin, polyglycerin, diethylene glycol, dipropylene glycol, diethylene glycol monoalkyl ether, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol, hydrogenated castor oil (30E .O.) And sorbitol. Of these, nonvolatile polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol, diethylene glycol monoalkyl ether, glycerin, diglycerin, triglycerin, and polyglycerin are preferred, and particularly preferred. Are diethylene glycol monoalkyl ether, glycerin, polyethylene glycol (Mw = 300, 400, 600), polyethylene glycol / polypropylene glycol, and polypropylene glycol. The blending amount of the polyhydric alcohol with respect to the thermal gel composition of the present invention is, for example, 10 to 95% by mass, preferably 20 to 90% by mass, and more preferably 3% by mass.
0 to 80% by mass. The blending amount of the polyhydric alcohol is preferably high enough to obtain sufficient heat generation and low enough not to ooze out of the thermal gel composition of the present invention.

[0006] The polymer used in the present invention is not particularly limited as long as it dissolves or swells in polyhydric alcohols which are exothermic agents. Here, dissolving means that a 1% by mass polyhydric alcohol solution of the polymer becomes uniform. Swelling, when mixed with a constant mass of polyhydric alcohol,
The state in which the polymer absorbs the polyhydric alcohol and increases the volume, and the mass of the polymer-polyhydric alcohol mixture is
It means that the mass is twice or more the mass of the polymer before mixing. The polymer is preferably one that dissolves or swells in polyhydric alcohols to form a gel, and among them, a nonionic polymer can be suitably used.

Examples of the polymer used in the present invention include:
Hydroxypropylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, (meth) acrylic acid /
(Meth) acrylic ester copolymer, N-methacryloylethyl-N, N-dimethylammonium-α-N
-Methyl carboxy betaine polymer, polyacrylic acid,
Polyvinyl acetate, alkyl vinyl ether / maleic anhydride copolymer, polyvinyl alcohol, poly N-vinylacetamide, polymethoxy polyethylene glycol (meth) acrylate, polyphenoxy polyethylene glycol (meth) acrylate, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl Examples include one or more polymers selected from the group consisting of (meth) acrylates, polyacrylamides, and mixtures thereof. Further, these polymers may be a crosslinked body in which a part thereof is crosslinked.

The above hydroxypropyl cellulose preferably has a substitution degree of 50% or more. Here, the degree of substitution refers to the mass% of the content of etherified hydroxypropoxyl group based on the mass of hydroxypropylcellulose. A higher degree of substitution is preferred because sufficient compatibility with the polyhydric alcohol can be obtained. In addition, hydroxypropyl cellulose has, for example, a hydroxypropoxyl group content of 20 to 90%, preferably 50 to 80%. The polyvinylpyrrolidone may be a copolymer containing a vinylpyrrolidone monomer as a main component, for example, 2-ethylhexyl acrylate / vinylpyrrolidone copolymer, vinylpyrrolidone / vinyl acetate copolymer and vinylpyrrolidone / vinylcaprolactone / vinylimidazole copolymer. Is mentioned. Examples of the (meth) acrylic acid / (meth) acrylic acid ester copolymer include, for example, methacrylic acid / methyl acrylate copolymer, methacrylic acid / ethyl acrylate copolymer, acrylic acid / octyl acrylate copolymer, and methacrylic acid / acrylic acid n -Butyl copolymer and the like. The N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine polymer is a copolymer containing N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monomer as a main component. For example, N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / octadecyl methacrylate copolymer and N-methacryloylethyl-N, N-dimethylammonium-α-N-methyl And carboxybetaine / 2-ethylhexyl methacrylate copolymer.

The polyacrylic acid may be unneutralized or partially neutralized. A partially neutralized polyacrylic acid having a neutralization ratio of less than 20 mol% is suitable because it is easily dissolved in a polyhydric alcohol. More preferably,
Unneutralized polyacrylic acid. The polyvinyl acetate may be a copolymer containing a vinyl acetate monomer as a main component. For example, vinyl acetate / crotonic acid copolymer, vinyl acetate / itaconic acid copolymer and the like can be mentioned. Examples of the polyvinyl alcohol include fully / partially saponified polyvinyl acetate. The alkyl vinyl ether / maleic anhydride copolymer is
It may be an alkyl vinyl ether / maleic anhydride copolymer and its hydrolyzate or half ester. An example is a methyl vinyl ether / maleic anhydride copolymer. In the above-mentioned polymethoxypolyethylene glycol (meth) acrylate and polyphenoxypolyethylene glycol (meth) acrylate, the number of moles of ethylene glycol added to the side chain of polyethylene glycol contained in methoxypolyethylene glycol (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate (n ) Is, for example, preferably n = 2 to 50, preferably n = 2 to 23. Also,
The polymethoxy polyethylene glycol (meth) acrylate and the polyphenoxy polyethylene glycol (meth) acrylate may be, for example, a copolymer with an alkyl (meth) acrylate.

The molecular weight of the polymer of the present invention is preferably high enough to obtain good gel-forming properties.
It is 10,000 to 10,000,000, preferably 100,000 to 5,000,000.
The blending amount of the polymer with respect to the thermal gel composition of the present invention is, for example, 10 to 70% by mass, and preferably 15 to 6% by mass.
It is 5% by mass, more preferably 20 to 60% by mass. In addition, the mass ratio of the total amount of the polymer and the polyhydric alcohol to the thermogel composition of the present invention is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more.
It is desirable that the content be not less than mass%.

The thermal gel composition of the present invention may optionally contain additives such as active ingredients and medicinal ingredients.
The additive used in the present invention is not particularly limited as long as it can be dissolved or dispersed in polyhydric alcohols. As the active ingredient, for example, an active ingredient for warmth sensation, a peripheral circulation promoting agent, an anti-inflammatory analgesic component, a blood circulation promoting agent, a local anesthetic, a sweat enhancer, an athlete's foot drug, an antibacterial / sterilizing agent, a whitening component, a sebum suppressant, There are keratolytic agents, activators, solvents, fragrances, pigments and the like.

The active ingredients for warming sensation include, for example, pepper extract, capsicum tincture, capsaicin, Obaku extract, cinnamon ginger extract, ginger extract, ginger alcohol extract, cantaritis tincture, nicotinic acid benzyl ester, vitamin E, borneol, dl- Camphor, l-menthol, peppermint oil, eucalyptus oil, methyl salicylate, glycol salicylate, vanillyl alcohol derivatives, nonylate vanillylamide, vanillyl alcohol alkyl ether, pepper extract, extract of thistle plant extract, extract of genus Athisaria plant , Clove oil, eugenol derivatives and the like. When these components are added, blood circulation is promoted by using local stimulation or induced stimulation on the skin, and a secondary warm feeling can be obtained.

The peripheral circulation promoting agent includes, for example, tocopherol acetate. Anti-inflammatory analgesics include, for example,
(Salicylic acid) diphenhydramine, chlorpheniramine maleate, ammonium glycyrrhizinate, dipotassium glycyrrhizinate, glycyrrhizic acid, stearyl glycyrrhizinate, β-glycyrrhetinic acid, allantoin, azulene, ε-aminocaproic acid, hydrocortisone, calcium pantothenate, ethyl pantothenate , Hydrocortisone acetate, nonyl acid vanilamide,
Examples include diphenylhydramine, indomethacin, arnica tincture, licorice, orchid, ricinus, western sawtooth grass, hillock grass, aloe, glycol salicylate, vitamin E acetate, methyl salicylate, and the like. Examples of the active ingredient for cervical spine sprain include aminoalkoxybibenzyls.

[0014] The blood circulation promoting agents include, for example, assembly extract, cepharanthin, vitamin E and its derivatives, γ
-Oryzanol, peppermint oil, turpentine oil, clove oil, geraniol oil, thymol oil, fennel oil, bergamot oil, anise oil, lavender oil, black pepper oil, safflower oil, arnica extract, malonie extract, emperor extract, bodaiju extract, melissa Extract, N-ethyl-p-3-menthan-carboxamide and the like. Local anesthetics include, for example, funnel extract. For the astringent component, a tannin-containing component is preferably used, for example, zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, aluminum sulfate, zinc sulfocarbonate, tannic acid, citric acid, lactic acid, powdered oubaku, hamamelis, odoriko There are grass, birch and rhubarb. Inorganic salts are preferably used for the antiperspirant. For example, calcined gypsum, calcium chloride, anhydrous calcium chloride, magnesium chloride, anhydrous magnesium chloride, calcium carbonate, anhydrous calcium carbonate,
Examples include sodium sulfate, anhydrous sodium sulfate, magnesium sulfate, anhydrous magnesium sulfate, sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, zeolite, montmorillonite, smectite, kaolin, talc, clay minerals, and various other salts.

[0015] Disinfecting and antibacterial components include pirocton olamine, ciclopirox olamine, benzalkonium chloride,
Benzethonium chloride, halocarban, chlorohexidine hydrochloride, zinc pyrithione, phenol, trichlorocarbanilide, chlorhexidine gluconate, cetylpyridinium chloride, isopropylmethylphenol, allantoin, antiplasmin agents (ε-aminocaproic acid, tranexamic acid), dihydrocholesterol, tokito There are extracts, chamomile (containing azulene), essential oils such as eucalyptus oil, hinokitiol and the like. As the athlete's foot medicine, a medicinal component such as a water extract of golden fin (Callophyllis flabellulata), miconazole nitrate, and other antipruritic agents such as diphenhydramine hydrochloride, chlorpheniramine maleate, camphor and lapolite are used.

Examples of antibacterial and bactericides include zinc pyrithione, trichlorocarbanilide, triclosan, aloe extract, carrot extract, licorice extract, psyllium extract, chamomile extract, loquat extract, water-soluble cerium salt, abietic acid, pimaric acid, Bis (2-pyridinethiol-1-oxide) zinc, pyridinethione salt, histamine 2 receptor antagonist, vitamin E acetate,
Sulfur-containing amino acids such as pantothenyl ethyl ether, triethyl citrate, methionine, cystine, cysteine and their hydrochlorides, cinnamon clove thyme penzoin oakmoss vanilla extract, zinc pyrithione, 10-aryl-1, 8-dihydroxyanthrone, triclosan, sodium benzoate, anthocyanins, anthocyanidins, piperazine derivatives, uric acid, petanes, rutin, 1-hydroxy-2-pyridones, sulfite ion generating water-soluble salts, sodium aluminosilicate, oil-soluble licorice extract Objects and Lapolite. The antibacterial / bactericide can generally be used as an anti-dandruff agent.

The whitening component, sebum inhibitor, keratolytic agent, etc.
It can be mainly used for cosmetics. Examples of the skin lightening component include arbutin, ellagic acid, kojic acid, vitamin C, placenta extract, titanium oxide, water extract of Callophyllis japonica, and water extract of Callophyllis adhaerens. In addition, sebum suppressants and keratolytic agents include estradiol, estrone, ethinyl estradiol, vitamin B6, sulfur, resorcinol, benzalkonium chloride,
Benzethonium chloride, halocarbane, 2,4,4-trichloro-2-hydroxyphenol, selenium sulfide, pentadecanoic acid, pentadecanoic acid derivatives, various vitamins, and the like. The active agents, for example, fatty acids (C ₁₂ ~C ₂₀₎ salt,
Examples include alkyl ether sulfates, alkyl sulfate esters, amino acid-based activators, higher alcohols, and polyoxyethylene alkyl ethers. More specifically, for example,
Glycerin monostearate, polyoxyethylene (2
0) cetyl ether, polyoxyethylene (20) sorbitan monolaurate, laurylamine oxide, polyoxyethylene (10) phenyl ether and polyoxyethylene (7) glyceryl monolaurate.
Examples of the solvent include a 1,3-dioxolan-2-one derivative,
Alkylene glycol ethers such as butyl carbitol, liquid paraffin, squalene, cetanol, cetostearyl alcohol, beeswax, glycolic acid, ethyl oleate, trimethylglycine, glabridine, squalane, polyoxyethylene (20) sorbitan oleate, dimethylpolysiloxane (30 cst), jojoba oil, isoparaffin, stearyl dimethicone, monoethanolamine and the like. These activators and solvents are used when the thermal gel composition of the present invention is used for a cleaning sheet, a cleaning sheet around a microwave oven, and the like.

Examples of the fragrance include amylcinnamic aldehyde, benzyl acetate, p-tertbutylcyclohexyl acetate, cyclaset, cyclaprop, garaki solid, bedion, orange oil and the like. The dyes include, for example, Red No. 2, Green No. 3, Blue No. 1,
No. 402, yellow 401, purple 401 and the like. By coating the non-aqueous thermal gel composition of the present invention on a support, it can be used as a thermal sheet such as a real-temperature patch. In particular, by applying the non-aqueous thermal gel composition of the present invention to which an additive such as the above-mentioned active ingredient is added, the composition can be used as a cosmetic sheet, a disease treatment sheet, a cleaning sheet, and the like. Here, the support used is not limited to the type, for example, paper, knitted fabric, woven fabric, non-woven fabric, plastic film and the like, for example, rayon non-woven fabric,
Polyester non-woven fabric and knitted fabric, polypropylene non-woven fabric,
There are polyurethane films and the like. The support may have a weight per unit area of 20 to 50, depending on its type.
0 g / m ^2, preferably used are those elongated 50 to 300 g / m ^2.

For the purpose of preventing the adsorption of water, preventing the volatilization of the drug, and protecting the adhesive surface, a facing layer may be provided on the non-aqueous thermal gel composition side of the thermal sheet, if necessary. The facing layer may be anything as long as it covers the thermal sheet. For example, a polypropylene film, a polyvinyl chloride film, a polyethylene film, a polyethylene terephthalate film or the like is used. The film used for the facing layer is not limited to a size or the like, but may have a thickness of 1 to 100, for example.
0 μm, preferably 5 to 500 μm, weight per unit area of 1 to 200 g / m ² , preferably 10 to 100 g
/ M ² . The thermal sheet of the present invention may be further provided with a hydrogel layer. The hydrogel layer is provided to supply sufficient water to the polyhydric alcohol to ensure heat generation due to heat of hydration. As the hydrogel, a known hydrogel can be used. For example, a polyanionic polymer or a salt thereof is crosslinked with a polyvalent metal ion or a polycationic polymer. The hydrogel layer may be provided above the non-aqueous thermal gel composition or between the support and the thermal gel composition. The hydrated gel layer may be installed by any method.For example, the hydrated gel layer may be installed in a state where the hydrated gel layer and the hot gel composition are in contact with each other, or may be installed after being covered with a facing layer, and may be installed in use. You may contact by peeling a thing layer. In addition, a thermal sheet comprising a support and a non-aqueous thermal gel composition and a hydrogel sheet may be bonded together at the time of use.

In the present invention, the above polymer is dissolved in a polyhydric alcohol.
Or swell with polyhydric alcohol to form gel
As long as the ratio between the polyhydric alcohol and the polymer is arbitrary,
But the mass of the polyhydric alcohol / polymer
The ratio is, for example, from 9/1 to 1/1, from the viewpoint of gel form retention.
9, preferably 8/2 to 2/8, more preferably 7
/ 3 to 3/7. In addition to the above manufacturing method,
Crosslinks the bright polymer to form a gel or sheet
After making the polyhydric alcohol of the present invention into the above-mentioned mass ratio,
May be impregnated. As a crosslinking agent used here
Depends on the type of polymer.
Divinyl such as nilbenzene and methylenebisacrylamide
Polymerization by adding
Depending on the method of cross-linking by reacting epoxy type cross-linking
Crosslinked. In the present invention, the polymer is a polyhydric alcohol.
Heat treatment to promote the dissolution of
May be performed. Heating is performed by mixing the polymer and polyhydric alcohol.
May be carried out at the same time, or in combination with a polymer and a polyhydric alcohol.
After applying a slurry consisting of
It may be heat-treated with a oven or the like. The heating temperature is, for example, room temperature
To 150 ° C, preferably 40 ° C to 120 ° C, more preferably
More preferably, the temperature is about 50C to 100C.
The heating sheet of the present invention is a non-aqueous sheet prepared by the above method.
It is manufactured by applying the thermal gel composition on the support.
Build. The mass of the gel composition per unit area is
Although it depends on the type of the thermal gel composition, for example, 0.01
-10 g / cm ^Two, Preferably 0.05 to 5 g / cm^Two
And the mass per unit of the entire heating sheet is 0.0
3 to 20 g / cm^Two, Preferably 0.05 to 10 g / c
m^TwoIt is.

The hydrogel layer arbitrarily provided on the thermal sheet of the present invention may be formed by applying a hydrogel on the support or the thermogel composition, or laminating the hydrogel sheet in a sheet form. It is provided by. Although the mass of the hydrogel layer per unit area depends on the type of hydrogel, for example, 0.01 to 10 g / cm ² ,
Preferably, it is 0.05 to 5 g / cm ² .

Further, in order to prevent the adsorption of water and the volatilization of the drug, it is coated with a facing layer as required.
The heating sheet is then cut into a suitable shape and size.
As a cutting method, any cutting method such as cutting by a slitter, cutting by push-cutting, a combination thereof, or a punching cutting method may be used. For example, when cutting into a rectangle, the cutting is usually performed so that the ratio of the length of the long side to the length of the short side is 1 to 5, preferably 1 to 3.
An example will be described below. These do not limit the present invention at all.

[0023]

EXAMPLES Synthesis of Polymer 1 In a 1-liter four-neck separable flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 30 g of methoxypolyethylene glycol methacrylate (n = 9) (manufactured by Shin-Nakamura Chemical Industry) was added. After 50 g of ethanol was added and uniformly dissolved, nitrogen gas was introduced from a nitrogen inlet tube and stirred under a nitrogen atmosphere. After 20 minutes, 2,2′-azobis (2-
An initiator solution obtained by dissolving 0.02 g of methyl-butyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) in 20 g of ethanol was added, and solution polymerization was performed while heating to 90 ° C. in an oil bath. After polymerizing at 90 ° C. for 6 hours under a nitrogen atmosphere while introducing nitrogen,
The solvent was removed, and the unreacted monomer and the odorous residue were removed by a vacuum dryer to obtain Polymer 1 (average molecular weight: about 120,000).

Synthesis of Polymer 2 Methoxy polyethylene glycol methacrylate (n =
9) Except that 30 g of hydroxyethyl methacrylate (manufactured by Junsei Chemical) was used instead of 30 g,
Polymer 2 was obtained in the same manner as in the above synthesis method (average molecular weight: about 300,000).

Synthesis of Polymer 3 Methoxy polyethylene glycol methacrylate (n =
9) 25 g of methoxypolyethylene glycol methacrylate (n = 4) (manufactured by Shin-Nakamura Chemical) instead of 30 g
And lauryl acrylate (manufactured by Osaka Organic Chemical Industry) except that 5 g was used in the same manner as in the synthesis method of Polymer 1 above.
Polymer 3 was obtained (average molecular weight: about 240,000).

Synthesis of Polymer 4 Polymer 4 was synthesized by adding 0.3 g of methylene bisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) to a monomer solution to the synthesis recipe of Polymer 1 described above (molecular weight unknown).

Production of Non-Aqueous Thermal Gel Composition Various polyhydric alcohols and polymers were mixed to produce a non-aqueous thermal gel composition. Polyhydric alcohol, polyethylene glycol (manufactured by Lion) with a molecular weight of 200, 4
00, 600 (PEG200, PEG, respectively)
400, PEG600), ethylene glycol (manufactured by Tokyo Chemical Industry), and diethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry). As a polymer,
In addition to the above polymers 1 to 4, polyvinyl alcohol (manufactured by Nippon Gosei Kagaku, GH-17), hydroxypropyl cellulose (manufactured by Nippon Soda, HPC-H (hydroxypropoxyl group content 73%, molecular weight = 330,000), and HPC- M (hydroxypropoxyl group content 73%, molecular weight = 13
10,000)), carboxyvinyl polymer (Junron PW110, manufactured by Nippon Junyaku), polyvinylpyrrolidone (BASF
Manufactured by Koridon 90F), polyacrylic acid (Nippon Pure Chemical Industries, Julimer 10SHP), methacrylic acid / methyl methacrylate copolymer (manufactured by ROHM, Eudragit L100)
It was used. In the comparative examples, as the polymer, sodium polyacrylate (Aronbis S, manufactured by Nippon Pure Chemical Industries, Ltd.), sodium carboxymethyl cellulose (manufactured by Junsei Chemical Co., reagent grade CMC), hydroxyethyl cellulose (manufactured by Hercules, Inc.) NATROSOL2
50 LR), xanthan gum (Tricrystal, XANTUR)
AL180) was used.

Evaluation The evaluation was performed on the mixed state of the polyhydric alcohol and the polymer, the evaluation of the gel forming property, and the presence or absence of heat generation. The mixed state is
100 g of polyhydric alcohol and 1 g of polymer are mixed to obtain 2
The mixture was left at 5 ° C. for 30 minutes to “dissolve” the polymer dissolved therein. The mixture was further allowed to stand on a 100-mesh wire net for 10 minutes, and then the mass of the mixture was measured. When the amount was less than 2 g and the polymer did not swell and settled in the polyhydric alcohol solution, it was evaluated as “x”. The gel-forming property was evaluated by visually observing the state in which the same amount of the polyhydric alcohol and the polymer were mixed. The polymer which remained in a solid state as it was was evaluated as "x". For the evaluation of the presence or absence of heat generation, 10 g of water was added to 10 g of a mixture of polyhydric alcohol / polymer at a mass ratio of 1/1, and the presence or absence of temperature rise after 5 seconds was evaluated. Heat generation was not evaluated for those not mixed. The results are shown in Tables 1 and 2.

Table 1 Table 2

Examples 12 to 17 (heating sheet) Glycerin, dipropylene glycol and PEG 300 or 400 were used as polyhydric alcohols, and polymers 1, polymer 4, hydroxypropylcellulose (HPC-H), polyacrylic acid, Polyvinylpyrrolidone or methacrylic acid / methyl methacrylate copolymer was used and mixed with the following composition to obtain a mixture having good gel-forming properties. In the tables,% indicates mass% unless otherwise specified (the same applies hereinafter). This mixture was applied to a rayon nonwoven fabric to obtain a 0.1 g / cm ² warming patch. 10 g (10 × 10 cm) of the skin was attached to the arm, and the temperature of the skin surface was measured at 25 ° C. and 50% relative humidity. The rise temperature of the skin surface is + 3 ° C 1 minute after application
And a favorable temperature increasing effect was confirmed. Table 3

Table 4

Examples 18 and 19 (Athlete's foot drug) Glycerin, 1,3-butanediol, and PEG400 were used as polyhydric alcohols, polyacrylic acid was used as a polymer, and the following components were mixed. An athlete's foot drug having gel-forming properties was obtained. 10 g of this was applied to 10 × 10 cm of the skin of the foot wet with water, and the temperature of the skin surface was measured under the conditions of 25 ° C. and 50% relative humidity. The rising temperature of the skin surface was + 5 ° C. one minute after application, confirming a favorable temperature rising effect. Table 5

Examples 20 and 21 (gel for treating acne) Diglycerin and PEG 300 were used as polyhydric alcohol, and hydroxypropyl cellulose (H
Using PC-M) and mixing with the following composition, a gel for acne treatment having good gel-forming properties was obtained. 10 g of this was applied to 10 × 10 cm of the arm skin, and the temperature of the skin surface was measured at 25 ° C. and 50% relative humidity. The rising temperature of the skin surface was + 2 ° C. 0.5 minutes after application, confirming a favorable temperature increasing effect. Table 6

Example 22 (Hair-growing hair pack) Hair-growing hair having good gel-forming properties by using diethylene glycol monobutyl ether as a polyhydric alcohol, using polyvinyl alcohol as a polymer, and mixing with the following composition. Got a pack. 10 g of this was applied to 5 × 5 cm of the skin of the arm, and the relative humidity was 50 ° C. at 25 ° C.
%, The temperature of the skin surface was measured. The rising temperature of the skin surface was + 3 ° C 0.5 minutes after application, confirming a favorable effect of increasing the temperature. Table 7

Example 23 (Whitening sheet) Glycerin, PEG 600, sorbitol and 1,3-butanediol were used as polyhydric alcohols, and hydroxypropyl cellulose (HPC-M) was used as a polymer. After mixing, a mixture having good gel-forming properties was obtained. This was applied to a spunbond rayon nonwoven fabric to obtain a whitening sheet of 0.05 g / cm ² . This was affixed to the arm skin wetted with water in an amount of 1 g (4 × 5 cm), and the temperature of the skin surface was measured at 25 ° C. and 50% relative humidity. The rising temperature of the skin surface is + 2 ° C. for 0.5 minutes after application, + 1 ° C. for 3 minutes after application, and + 1 ° C. for 3 minutes.
It was confirmed that the above was maintained. Table 8

Example 24 (Moisturizing sheet) Using 1,3-butanediol, glycerin, PEG400 and sorbitol as the polyhydric alcohol, polyvinylpyrrolidone as the polymer, and mixing with the following composition, a good gel was obtained. A formable mixture was obtained. This was applied to a spun-pond rayon nonwoven fabric to obtain a 0.05 g / cm ² moisturizing sheet. 1 g (4 × 5 cm) of this was applied to the skin moistened with water on the arm, and the temperature of the skin surface was measured at 25 ° C. and 50% relative humidity. The rise temperature of the skin surface is + 3 ° C in 0.5 minutes after application and 3 after application.
It was confirmed that the temperature was maintained at + 1 ° C. for 3 minutes. Table 9 (Note) EDTA-4Na: added as a chelating agent

Example 25 (Cleaning sheet for microwave oven) Using PEG 400 as a polyhydric alcohol, polymer 2 as a polymer and other components having the following composition, a mixture having a good gel-forming property was obtained. . This was applied to a polyurethane film to obtain a cleaning sheet for range rotation of 1 g / cm ² . This was affixed to 10 g (10 × 10 cm) of stainless steel wetted with water, and the temperature of the stainless steel surface was measured at 25 ° C. and 50% relative humidity. The rising temperature of the surface is + 10 ° C 0.1 minutes after application, and 10 minutes after application.
It was confirmed that the temperature was maintained at + 5 ° C. for 10 minutes. Table 10

Example 26 (Heat sensation type makeup remover sheet) PEG300 was used as a polyhydric alcohol, hydroxypropylcellulose (HPC-M) was used as a polymer, and other components were mixed as shown below to form a good gel. A mixture having properties was obtained. This was applied to a 0.8d rayon nonwoven fabric to obtain a warm-type makeup removing sheet (Example 26). The gel content at this time was 3.0 in the mass ratio of the mixture / nonwoven fabric. As a comparative example, a commercially available makeup remover facial cleanser was used. Wet the inside of the forearm with a commercially available lipstick in a circular shape and wet it with water. One piece of the make-up remover sheet (5 × 5 cm) was stuck on it, and the temperature was 25 ° C. and the relative humidity was 5
Under the condition of 0%, it was evaluated whether or not a sense of warmth was felt. Example 26
The makeup remover sheet felt a slightly stronger warm feeling than the comparative example (warm feeling evaluation ◎). In addition, the makeup was wiped off after 30 minutes of application, and its removability and feeling of use were evaluated. As a result, it was confirmed that the lipstick residue was thinner than the comparative example (makeup removability evaluation ○). At this time, the use feeling was good (use feeling evaluation 使用). Table 11

Example 25 (Heat-sensing type nail polish remover sheet) Using PEG300 as a polyhydric alcohol, using hydroxypropylcellulose (HPC-M) as a polymer, adding a fragrance and a dye as needed, mixing, A formable mixture was obtained. 0.8d rayon non-woven fabric
(Example 27) and 0.8d polypropylene nonwoven fabric (Example 28) were applied to obtain a warm type nail polish remover sheet. The gel content at this time was 3.0 in the mass ratio of the mixture / nonwoven fabric. Wet nails with a commercially available nail polish on the nails and wet them with water. One piece of the above-mentioned warm type nail polish remover sheet (5 × 5 cm) is stuck on the nails and heated at 25 ° C. and 50% relative humidity. When the user felt or evaluated, he felt a strong sense of warmth (warmth evaluation ◎). When the nail polish was wiped off with a sheet after the test, the nail polish was completely removed. Table 12

[0040]

EFFECT OF THE INVENTION By containing a polyhydric alcohol and a polymer which is soluble in the polyhydric alcohol or swells with the polyhydric alcohol, it has good form retention and water Heat generation by sum heat was realized. The non-aqueous thermal gel composition of the present invention has a good compatibility with the polyhydric alcohol as a base, so that a liquid exothermic component (polyhydric alcohol) can be attached to a gel sheet. Because of its property, a good feel can be obtained during coating. Therefore, for example, when applied on the skin, it can be expected to activate the skin by promoting blood circulation by contacting with moisture on the skin, and also to expand the pores by warming the skin surface, thereby allowing penetration of the active ingredient. It is possible to expect effects such as acceleration and removal of skin stains. Further, when used for oil stains around a microwave oven or a ventilation fan, the stains can be more easily removed by softening the denatured oily stain and raising the stain. Since the non-aqueous thermal gel composition of the present invention is gelled by a polymer base, it can maintain its moldability even when spread into a sheet, and can be provided on a support. Therefore, since this heat sheet can be stuck for a long time, it can be used on the body to maintain a warm feeling, or it can be expected to have a warming / moisturizing effect by covering the skin surface and promote the penetration of active ingredients. It becomes possible. On the other hand, the thermal gel composition of the present invention generates heat by water, and thus can be used when a small amount of water is to be evaporated and dried in a short time. In addition, by bonding the exothermic gel and a normal hydrogel, a suitable exotherm can be obtained irrespective of the amount of water at the application site. Examples of the use of the composition according to the present invention include a warm-type patch such as a real-temperature patch, a therapeutic drug gel containing a medicinal component, a drug such as a therapeutic sheet, a gel for acne treatment, a cosmetic sheet, and a horn plug. Body makeup such as taking sheet, whitening sheet, moisturizing sheet, hot esthetic products, pack, moisturizing pack, moisturizing gel, warming type makeup remover sheet, warming type nail polish remover sheet, hair pack, hair gel, hair cream, etc. It is used for cleaning sheets such as a cleaning sheet for cleaning around a range, a cleaning sheet for a ventilation fan, an insole for shoes, clothing for winterization, and the like.

Continuation of front page (72) Inventor Yoshifumi Yamagata 1-3-7 Honjo, Sumida-ku, Tokyo Inside Rion Co., Ltd. (72) Inventor Miyuki Miyake 1-3-7 Honjo, Sumida-ku, Tokyo Lion stock In-company (72) Inventor Toshiyuki Kashii 1-3-7, Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (4)

[Claims] 1. A non-aqueous thermogel composition comprising a polyhydric alcohol and a polymer that dissolves in or swells with the polyhydric alcohol. 2. The polymer according to claim 1, wherein the polymer is hydroxypropylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, (meth) acrylic acid / (meth) acrylate copolymer, N-methacryloylethyl-N, N-
Dimethylammonium-α-N-methylcarboxybetaine polymer, polyacrylic acid, polyvinyl acetate, alkyl vinyl ether / maleic anhydride copolymer, polyvinyl alcohol, poly N-vinyl acetamide, polymethoxy polyethylene glycol (meth) acrylate,
Polyphenoxy polyethylene glycol (meth) acrylate, polyhydroxyethyl (meth) acrylate,
The non-aqueous thermal gel composition according to claim 1, which is one or more polymers selected from the group consisting of polyhydroxypropyl (meth) acrylate, polyacrylamide, and a mixture thereof. 3. The non-aqueous thermal gel composition according to claim 1, which comprises polyethylene glycol and hydroxypropyl cellulose. 4. The support according to claim 1, wherein said support is provided on said support.
A thermal sheet comprising the non-aqueous thermal gel composition according to any one of Items 1 to 3.