JPH0432876B2 - - Google Patents

Description

Detailed Description of the Invention "Industrial Application Field" The present invention relates to a new exothermic agent, and more specifically to anthraquinone (hereinafter abbreviated as AQ) hydrides (hereinafter abbreviated as HAQ) or their compatibility. The present invention relates to an exothermic agent that generates heat upon contact with oxygen, which contains a mutant and a basic substance as main components.

The exothermic agent of the present invention can be used, for example, in hot compresses; in heating packaged processed foods and canned foods; in heat dissipation of insect repellents, insecticides, disinfectants, fragrances, etc.; in welding of plastic materials; in preventing and removing ice from window glass; Used to keep shoes, gloves, etc. warm; substitute for portable fuel; heat-insulating mats, etc.

"Problems to be solved by the present invention" Exothermic agents that utilize chemical exothermic phenomena have been well known, but in practical use, for example, iron powder, aluminum powder, zinc powder, tin powder, magnesium powder, Compositions have been used that contain calcium powder or a mixture thereof as a main component, use an inorganic salt or acid as a catalyst, and generate heat when brought into contact with oxygen.

Even if these inorganic exothermic agents are tried to be burned after being used, most of them remain as ash, which poses a problem in cleaning up. The present invention uses HAQs, which are organic compounds, as opposed to the conventional inorganic compounds as main ingredients.
It is an object of the present invention to provide a new exothermic agent that can be combusted after use and does not cause environmental pollution due to residual ash.

Therefore, I came up with the idea of using the property of HAQs as a heat generating agent by utilizing their reactivity with oxygen, but since HAQs alone react slowly with oxygen,
Although not suitable for the purpose of the present invention, the present invention was completed by discovering that a composition containing HAQs and a basic substance is extremely effective as a heat generating agent.

"Means and effects for solving the problems" In the present invention, used as the main component of the exothermic agent
HAQs may be substituted HAQs in which the hydrogen groups at positions 1 to 8 of the AQ skeleton are substituted with other substituents,
Of course, unsubstituted HAQs may also be used. Other substituents include, for example, alkyl groups such as methyl, ethyl, propyl, butyl; halogen groups such as chloro and bromo; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; endoalkylene such as endomethylene and endoethylene; Acyloxy groups such as acetoxy; other hydroxy, amino, nitro,
Examples include cyano group.

Regarding the hydrogenated position of the AQ skeleton in HAQs, it is necessary that at least one of the unsaturated bonds is saturated, but in particular 1,
It is preferable that at least one of the unsaturated bonds related to 4, 4a, 5, 8, 8a, 9, 9a, 10, and 10a is saturated, and furthermore, at least one of the unsaturated bonds related to 4a, 8a, 9a, and 10a is saturated. Preferably, one or more of them is saturated. For example, 1, 4, 4a, 9a−
THAQs, 1,4-dihydroanthrahydroquinone (hereinafter, dihydro is DH, anthrahydroquinone is AHQ, dihydroanthrahydroquinone is
abbreviated as DHAHQ), 1, 2, 3, 4
-THAHQs, 1,4-DHAQs, 1,2,3,
4,4a,9a-hexahydroanthraquinones,
1,2,3,4,4a,9a-hexahydroAHQ
Class, AHQ class, 1, 4, 4a, 5, 8, 8a, 9a,
10a-octahydro AQs, 1,4,4a,5,8,
9a-Hexahydro AHQs, 1,4,5,8-
Examples include THAQs, quinhydrones of the above AQs and AHQs, and alkali salts of 1,4-DHAHQs, such as disodium salts of 1,4-DHAHQs.

In particular, HAQs that can be produced industrially at low cost include 1,4,4a, 9a-THAQs, 1,4-
DHAHQ is preferred, especially 1,4,4a,9a-
THAQs are preferred. 1, 4, 4a, 9a−THAQ
Examples include 1,4,4a,9a-THAQ;
Examples include 2-methyl-, 2,3-dimethyl-, and 2-chloro-substituted 1,4,4a,9a-THAQ.

In practice, it may be a mixture of two or more of the HAQs described above. Further, in order to improve contact with oxygen, it is preferable to use HAQs in the form of fine powder.

The above HAQs can be easily produced according to conventional methods. For example, 1,4,4a,5,
8, 8a, 9a, 10a-octahydro AQs or 1,
4,4a,9a-THAQs are produced, followed by isomerization,
The above compounds can be easily produced according to known methods such as hydrogenation and oxidation.

Tautomers of HAQs include, for example, 9-hydroxyanthrones, 1,2,3,
1, for 4,4a,9a-hexahydro AHQs
Tautomers such as 2,3,4,4a,9a-hexahydro-10-hydroxyanthrones can be mentioned.

In the present invention, when using HAQs as exothermic agents, rather than using HAQ alone,
It is extremely effective to use HAQs as a main component and add or mix a basic substance, a carrier, and an aqueous medium and/or an organic solvent thereto for rapidly absorbing oxygen in the atmosphere.

The reactions in which HAQs absorb oxygen are as follows 1, 4,
As shown in the examples of 4a and 9a-THAQ, this is thought to be due to the reaction between hydrogen and oxygen that saturated the AQ skeleton, and heat is thought to be generated during this reaction.

THAQ+1/2O ₂ =DHAQ+H ₂ O (1) DHAQ+1/2O ₂ =AQ+H ₂ O (2) (However, THAQ: 1, 4, 4a, 9a−THAQ,
DHAQ: indicates 1,4-DHAQ) The reaction (1) proceeds relatively easily, but the reaction (2) tends to be relatively slower than the reaction (1).

Basic substances include, for example, alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, silicates, borates, sulfites, thiosulfates,
Examples include inorganic weak acid salts such as tertiary phosphate, polyphosphate, tripolyphosphate, and organic weak acid salts.
Particularly preferred are carbonates. Specifically, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium borate, potassium borate, sodium sulfite. , potassium sulfite, sodium thiosulfate, sodium triphosphate, sodium phthalate, potassium phthalate, sodium citrate, potassium citrate, sodium acetate, potassium acetate, sodium succinate, potassium succinate, sodium propionate, potassium propionate , sodium fumarate, potassium fumarate, sodium malate, potassium malate, and the like. In addition, alcoholates such as sodium ethoxide, quaternary ammonium hydroxide or its weak acid salts, amines, etc. may also be used, if necessary. Particularly preferred are sodium hydroxide, sodium carbonate, and potassium carbonate, which are inexpensive and easy to handle.

The amount of these basic substances used should be more than the catalytic amount,
Usually 0.0001 to 10 times the weight of HAQs, preferably 0.001 to 5.0 times, more preferably 0.01 to 5.0 times the weight
Selected from 2.0 times the weight.

In the present invention, using a carrier is HAQ
It is extremely effective in increasing the contact area between substances and oxygen and reducing the amount of basic substances and media used. Examples of the carrier include porous carriers such as activated carbon, silica, silica gel, silica alumina, zeolite, and diatomaceous earth; and pulp, soybean protein, popcorn powder, polyurethane, sawdust, defatted rice bran, and the like. In particular, a porous carrier, preferably activated carbon, is effective in effectively exhibiting the exothermic performance of HAQs.

The amount of carrier used varies depending on the type of carrier, but
Generally more than 0.01 times the weight of HAQ type, usually
The amount is 0.1 times to 10 times by weight, preferably 0.2 times to 8 times by weight, and more preferably 0.3 times to 5 times by weight. When the amount of carrier decreases, the exothermic performance tends to decrease when the amount of medium such as an aqueous medium used is relatively small. If the amount of carrier used is too large, the ability as a heat generating agent per unit volume will be reduced.

In the present invention, HAQ, which is the main component of the exothermic agent,
In order to effectively exhibit the same exothermic performance, it is preferable to simultaneously contain a medium such as an aqueous medium and/or an organic solvent.

As the aqueous medium, water is usually used, but salts or water-soluble substances may be dissolved in an organic solvent, or a hygroscopic compound may be added without substantially water present in the exothermic agent, or It may be moisture contained in the carrier or the atmosphere, or moisture absorbed from objects such as foods, or it may be in the form of water of crystallization of the bases and other salts mentioned above. Examples of compounds having water of crystallization include, for example, Na ₂ CO ₃・10H ₂ O, Na ₂ SO ₄・10H ₂ O
etc. can be mentioned. The amount of aqueous medium used is as water
It is usually 3 times or less by weight, preferably 2 times or less and 0.0001 times or more by weight, and more preferably 1 time or more and 0.001 times or more by weight relative to HAQs.

The organic solvent is preferably one that can dissolve HAQs as much as possible, such as monohydric or polyhydric alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, methyl ethyl ketone, etc. , ketones such as methyl butyl ketone, esters such as ethyl acetate, and hydrocarbons such as benzene, toluene, and xylene, preferably water-soluble solvents, and more preferably alcohols. Organic solvents can be used alone as a medium, but alcohols can be used together with an aqueous medium. The amount to be used is the same as that for the aqueous medium, but when added to the aqueous medium, it may be added in an amount of 0.001 times or more, preferably 0.05 times or more by weight, relative to the aqueous medium.

The presence of organic solvents such as alcohols, even in extremely small amounts, dissolves HAQs one by one and diffuses onto the surface of the carrier to improve contact with air, thereby dissolving HAQs and oxygen. It is presumed that this will further promote the reaction.

In addition, to promote the reaction of HAQs with oxygen, 1,4-naphthoquinone sulfonate, metal phthalocyanine compounds (sodium cobalt phthalocyanine sulfonate, etc.), iron salts (iron chloride, etc.), copper salts (copper chloride, etc.) ) can also be used.

The exothermic agent of the present invention can be easily produced by sequentially mixing HAQs or their tautomers, a basic substance, an aqueous medium and/or an organic solvent, and a carrier. , the HAQs and the medium, and the basic substance and the medium are separately mixed with a predetermined amount of carrier, and the mixture is compressed into tablets, granules, or as a powder and adhered to one or both sides of a sheet, if necessary. Alternatively, it is fixed by a known fixing method such as hammering, and an oxygen permeable bag, such as a perforated polyethylene film, is made of a laminate paper bag, a perforated plastic film such as polypropylene, polybutadiene, polyester, polyvinyl chloride, cellophane, or a laminate film thereof. It can be used wrapped or stored in a perforated container. When storing these encapsulants for a long period of time, it is preferable to cover them with a film that blocks air.If the preservation film is removed when using them as a heat generating agent, they will easily react with oxygen in the atmosphere. , can generate heat. In order to make the powder sticky, a water-soluble polymer compound may be added as a binder. Examples of such compounds include sodium alginate, CMC, hydroxymethyl cellulose, ethyl cellulose, propyl cellulose, starch, and polyvinyl alcohol.

Air is the most convenient and inexpensive oxygen source, or the purpose can also be achieved by mixing pure oxygen or a substance that generates oxygen through a chemical reaction.

The exothermic agent of the present invention can be manufactured in various forms, but generally it is packaged in oxygen-impermeable packaging such as aluminum foil or a metal container, vacuum-packed in a container, or inert gas such as nitrogen or argon. is sealed and when used, it is opened and exposed to air to generate heat.

"Effects of the Invention" The present invention provides HAQ, such as THAQ, which is an organic compound.
It effectively reacts with oxygen, and the heat generated at that time is effectively used to provide extremely wide-ranging effects when making hot compresses, heating and keeping various foods warm, and heating and dissipating insect repellents, insecticides, fungicides, fragrances, etc. can be played.

Hereinafter, it will be explained in detail using examples.

Example 1 (1) (Preparation of exothermic composition) 30 g of activated carbon with a mesh size of 200 mesh was impregnated with 12 g of ethanol, while 4.2 g of caustic soda as a basic substance was dissolved in 12 g of water, and the above activated carbon was impregnated with this. Add 30 g of THAQ powder with a mesh throughput of 18 to 35 to the mixture under a nitrogen atmosphere, mix well and impregnate activated carbon to prepare a composition to be used as a heat generating agent.

(2) (Packaging the above exothermic composition) The upper surface of the package is a polypropylene microporous film [breathability (Gurley); 400 seconds/100 c.c.], and the lower surface is a nylon film [oxygen permeability]. :5
~7c.c./ ^m2・24hr.atm], the exothermic agent composition prepared above was packed into ^{a 10cm} ×
Packaged in 12 ^cm packets.

(3) (Heat fever test) Place the air-impermeable nylon film side of the package wrapped above against your skin and rub it to allow air to pass through. When the outside temperature is 20℃, the temperature inside the package is up to 60℃.
The fever persisted for approximately 10 hours.

Claims (1)

[Scope of Claims] 1. An exothermic agent that generates heat upon contact with oxygen, which is characterized by containing a hydride of anthraquinones or its tautomer and a basic substance as a main component. 2. The anthraquinone hydride has an anthraquinone skeleton of at least 1, 4, 4a, 5, 8, 8a,
The exothermic agent according to claim 1, which is a hydrogenated anthraquinone in which one or more of the unsaturated bonds at positions 9, 9a, 10, and 10a is saturated. 3. The exothermic agent according to claim 2, wherein the hydrogenated anthraquinones are substituted or unsubstituted 1,4,4a,9a-tetrahydroanthraquinones. 4. The exothermic agent according to claim 2, wherein the hydrogenated anthraquinones are substituted or unsubstituted 1,4-dihydroanthrahydroquinones. 5. An exothermic agent that generates heat upon contact with oxygen, characterized by containing a hydride of anthraquinones or a tautomer thereof, a basic substance, a carrier, and an aqueous medium and/or an organic solvent.