JPS6254344B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a rubber-based hydrous composite and a method for producing the same. More specifically, the present invention relates to a rubber-based water-containing composite suitable for plasters or cold packs, and a method for producing the same. Water-containing composites in which water is dispersed in rubber are highly flexible and are expected to be used as highly functional flame retardants, moisture conditioning agents, cold insulation materials, fragrance preservatives, and base materials for poultices. Conventionally, methods for manufacturing the same have been proposed. For example, an emulsifier and water are added to a system in which an ABA type teleblock copolymer elastomer is dissolved in an excess amount of a plasticizer under heating, and the water is emulsified and dispersed. A continuous phase consisting of 15-95% by weight and an emulsified water-dispersed phase of 85% by weight
Japanese Patent Publication No. 52-48895 describes a method for producing a water-containing gel by forming a W/O emulsion containing ~5% by weight and then gelling it by cooling it to room temperature.
It is known from the specification of the publication No. The hydrous gel obtained by this method is highly flexible and is expected to be widely used in the fields of cold insulation materials, heat insulation materials, heat absorption materials, sound absorption materials, fire prevention materials, etc. Hydrogels had various drawbacks. In other words, in order to obtain a stable W/O emulsion, a large amount of plasticizer is required to achieve a viscosity suitable for emulsification, and emulsification must be performed at high temperatures, making the operation extremely complicated. It was hot. Furthermore, when fillers such as calcium carbonate, clay, magnesium carbonate, calcium oxide, or calcium sulfate are added, the viscosity of the emulsion system may become even higher, and depending on the filler, W/O emulsion may be formed. This destroyed the water particles and made the emulsion unstable. The resulting hydrogel also contains a large amount of plasticizer, so if it is left at 40-50°C for a long time, the water will separate and the gel will no longer be stable. It was something I couldn't get. As a result, the hydrous gel itself becomes hard due to uneven distribution of the plasticizer and rapid evaporation of water. For example, when such a hydrogel is made into a poultice by adding medicinal ingredients, it can be prepared by adding an aqueous solution of a water-soluble polymer (e.g. gelatin, carboxymethyl cellulose, sodium polyacrylate or polyvinyl alcohol, etc.), a humectant (e.g. glycerin, ethylene glycol or diethylene glycol, etc.),
Fillers with endothermic action (e.g. kaolin clay, bentonite, zinc white or titanium oxide)
Some disadvantages of conventional poultices, which are made by applying a mixture of medicinal ingredients and, in some cases, tackifying resins (e.g. rosin or polyterpene) to a fabric such as a lint cloth (e.g. Disadvantages include the fact that the medicinal ingredients of the medicinal agent are hydrophobic and therefore do not mix well with the hydrophilic base component of the poultice, resulting in the transfer of the medicinal ingredient of the poultice too quickly; the initial adhesion to the skin is poor;
Furthermore, it becomes too hard at low temperatures)
is improved, but the following drawbacks still remain. The disadvantage is that since it contains a large amount of plasticizer, water and plasticizer become unevenly distributed due to heat, etc., and the water evaporates extremely quickly, making the poultice base hard. , the adhesion to the skin is impaired, which reduces the pharmacological effect, and in some cases it may even be removed from the skin.On the other hand, in environments with a lot of moisture, such as in the bathroom or when there is a lot of sweating in midsummer. At the bottom, water absorption is too large and the poultice base material flows. Some of these drawbacks are
This was also approved for cold insulating materials that require flexibility and are not significantly affected by temperature and humidity. In view of the drawbacks observed in conventional water-containing composites, the present inventors have conducted various studies and found that a flexible and stable water-containing complex that freely contains functional ingredients can be produced by using a normal stirrer. They have also found that they can be produced extremely easily, and by incorporating the medicinal ingredient of a poultice into the water-containing complex, they have overcome the drawbacks of poultices made of water-soluble polymers.
We have discovered that it is possible to obtain a poultice that has excellent flexibility, adhesion to the skin, and pharmacological effects, and is less affected by temperature and humidity.We have also obtained a cold pack that has excellent flexibility and is less affected by temperature and humidity. The present invention was completed based on the discovery that the present invention is possible. According to the present invention, the above-mentioned technical problem can be solved by a water-containing composite obtained by dispersing microhydrogel in a matrix mainly composed of liquid rubber, particularly liquid polydiene rubber produced by an anionic polymerization method, and subjecting it to crosslinking treatment. Furthermore, this can be achieved by incorporating the medicinal ingredients of a cataplasm into the matrix component to form a cataplasm, or by creating a cold insulating material using the same. In addition, such a water-containing composite contains 10 to 1000 times its own weight of water in a liquid rubber containing a crosslinking agent at a ratio such that the water content in the liquid rubber is 10 to 80% by weight. By dispersing and then crosslinking a microhydrogel made of
It can be produced at relatively low temperatures. The liquid rubber used as the main component of the matrix component in the present invention means a fluid vulcanized rubber that is liquid or semi-liquid at room temperature. Such liquid rubbers include liquid polymers of conjugated diene compounds such as butadiene, isoprene, dimethylbutadiene, piperylene or chloroprene, liquid polymers thereof, the conjugated diene compounds and styrene, methylstyrene, acrylonitrile, methacrylonitrile, Examples include liquid copolymers of ethylene, propylene, butylene, or isobutylene and other conjugated diene compounds with vinyl compounds that can be copolymerized, and liquid thiocol. Also natural rubber (NR), synthetic polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene (random) copolymer rubber (SBR), styrene-isoprene (random) copolymer rubber (SIR), acrylonitrile-butadiene It also includes liquid rubbers obtained by depolymerizing solid rubbers such as copolymer rubber (NBR), acrylonitrile-isoprene copolymer rubber (NIR), and butyl rubber (IIR). Note that a modified liquid rubber in which a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, or an acid anhydride group is introduced into the liquid rubber may also be used. Among these liquid rubbers, the amount of vinyl bonds (i.e.,
1,2 bond amount, or the sum of 1,2 bond amount and 3,4 bond amount) is 35% or less, and [intrinsic viscosity in toluene at 30°C] = 1.21 × 10 ^-4 × (viscosity average molecular weight ⁾ Liquid polybutadiene rubber, liquid polyisoprene rubber (i.e., liquid poly-2-methyl-1,3-butadiene) whose viscosity average molecular weight ( ^hereinafter simply referred to as average molecular weight) calculated by A liquid butadiene rubber selected from the group consisting of rubber) and liquid butadiene-isoprene copolymer rubber is preferably used. It is thought that if the amount of vinyl bonds is too large, the molecular chain of the liquid butadiene rubber itself becomes hard, but not only does the dispersibility of the microhydrogel deteriorate, but also the low-temperature properties of the resulting hydrous composite deteriorate. From this point of view, it is desirable that the amount of vinyl bonds be 25% or less.
In addition, if the molecular weight is too high than the above range, it will be difficult to disperse the microhydrogel and it will be difficult to easily obtain a stable and uniform water-containing complex.On the other hand, if the molecular weight is too low, the crosslinking efficiency between rubbers will decrease significantly. The resulting water-containing composite becomes easy to flow and does not retain its shape. From this point of view, the molecular weight is preferably 10,000 to 60,000. especially
A molecular weight of 60,000 or less is recommended because the microhydrogel can be easily and uniformly dispersed even at room temperature. Note that when the molecular weight exceeds 100,000, a uniform water-containing composite can be obtained by adding a relatively small amount of plasticizer, but the amount of plasticizer used does not affect the performance of the water-containing composite. Liquid polybutadiene rubber, liquid polyisoprene rubber, or liquid butadiene-isoprene copolymer rubber having a specific vinyl bond weight molecular weight can be obtained by polymerizing butadiene monomer or/and butadiene, isoprene, and monomers by Ziegler polymerization, anionic polymerization, etc. It can be obtained by polymerization using a known polymerization method. Among these, anionic polymerization methods, especially anionic polymerization methods using lithium-based catalysts, produce a small proportion of vinyl bonds that reduce rubber elasticity, and carbon-carbon double bonds in the main chain that have a large effect on rubber elasticity and vulcanizability. Furthermore, it is most preferable because it has a high content of cis-1,4 bonds that provide flexibility and is easy to polymerize. Here, the anionic polymerization method using a lithium-based catalyst will be explained as follows. Using metallic lithium or organic lithium such as methyllithium, propyllithium, butyllithium, and distyrenyllithium as a catalyst, butadiene monomer or isoprene monomer is polymerized individually in the presence or absence of a solvent, Alternatively, butadiene monomer and isoprene monomer are copolymerized. As is well known, the molecular weight is easily controlled by the ratio of monomers and catalyst used. Generally, it is appropriate to use a polymerization solvent since it is easier to control the polymerization. Furthermore, when a lithium-based catalyst is used, various types of copolymers, from block copolymers with arbitrary block units to random copolymers, can be produced by devising the addition procedure of butadiene monomer and isoprene monomer. is preferable because it can be easily obtained. Among these liquid butadiene rubbers, cis-1,4
Liquid cis-1,4-polyisoprene rubber, which has a bonding amount of 70%, preferably 80%, is flexible, has high rubber elasticity, and has good vulcanizability is preferably used. These liquid butadiene rubbers include not only themselves but also various modified liquid butadiene rubbers. Typical examples of such modified liquid butadiene rubber include unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, crotonic acid, and citraconic acid, or their anhydrides, etc. Examples include those in which a derivative of the above is added, those in which an epoxy group is introduced into the liquid butadiene rubber, and those in which a carboxyl group or a hydroxyl group is added to the molecular terminal of the liquid butadiene rubber. By introducing such various functional groups, the types of crosslinking agents that can be used are greatly increased, but from the viewpoint of crosslinking efficiency, maleic anhydride-modified liquid butadiene with maleic anhydride and/or its derivatives added. Preferred are rubbers and epoxy-modified liquid butadiene-based rubbers into which epoxy groups have been introduced. The above-mentioned maleic anhydride-modified liquid butadiene rubber is composed of the liquid butadiene rubber and maleic anhydride, maleic acid, maleic acid ester,
In addition to adducts of maleic anhydride (derivatives) obtained by reacting with maleic anhydride derivatives such as maleic acid amide or maleic imide, for example, P-toluene sulfur methanol, ethanol, in the presence or absence of a catalyst such as a foonic acid.
One or both carboxyl groups based on maleic anhydride groups are made into an ester by reacting alcohol such as n-propanol, or anhydrous by reacting with amines such as ammonia, n-propylamine, n-butylamine, etc. It includes those in which a carboxyl group based on a maleic acid group is amidated, and also one in which a carboxyl group is imidized. In particular, from the viewpoint of viscosity stability when the modified liquid butadiene rubber is stored for a long period of time, it is better to use an alcohol derivative or an amine compound derivative of the modified liquid butadiene rubber than a modified liquid butadiene rubber with maleic anhydride added. Modified liquid butadiene rubber is preferably used. The addition reaction of maleic anhydride or its derivatives to liquid butadiene-based rubber can be carried out, for example, by adding maleic anhydride or its derivatives to a liquid rubber having a predetermined molecular weight and heating the mixture in the presence or absence of a solvent. This can be easily done. The solvents used here generally include hydrocarbons, halogenated hydrocarbons, etc.
More preferred are inert solvents such as n-heptane, n-hexane, n-butane, cyclohexane, benzene, toluene, and xylene. The amount of maleic anhydride and its derivatives added to the liquid butadiene rubber must be 15 mol % or less per monomer unit of the liquid butadiene rubber. If the amount added is too large, the viscosity of the liquid butadiene rubber will become too high, and the dispersion workability of the microhydrogel will deteriorate. Furthermore, in order to make a water-containing composite by utilizing the functional groups added to the modified liquid butadiene rubber, the amount added must be 0.1 mol % or more. From this point of view, the additional amount is 0.3
It is desirable that the amount is 7 mol %. In addition, epoxy-modified liquid butadiene rubber is
It is prepared by a known method using the liquid butadiene rubber, peracid or hydrogen peroxide, and a carboxylic acid. For example, a method is adopted in which unmodified liquid butadiene rubber is dissolved in a hydrocarbon solvent, hydrogen peroxide and lower carboxylic acid are added thereto, and the mixture is reacted at 50 to 150°C for 15 minutes to 5 hours. The degree of epoxidation is preferably within a range of 20 mol % or less per monomer unit of the liquid butadiene rubber. Further, in order to prepare a hydrogel by crosslinking using epoxy groups, it is desirable that the content be at least 0.3 mol % or more. From this point of view, the epoxidation ratio is preferably in the range of 3 to 15 mol%. As mentioned above, the present invention is based on liquid rubber, and by appropriately selecting the liquid rubber, microhydrogel can be easily dispersed in a greenhouse.
A homogeneous and stable water-containing composite is obtained, but if it is difficult to disperse at room temperature, the microhydrogel may be dispersed by heating to a temperature below the evaporation of water to lower the viscosity. Further, a plasticizer may be added within a range that does not cause problems of bleat or localization. The plasticizer used here is an oily substance that is liquid at room temperature, such as process oil, liquid paraffin, machine oil, cylinder oil, transformer oil, or rosin oil. In the present invention, a crosslinking treatment is performed, and the crosslinking agent for the liquid rubber used here includes those used in conventional vulcanization methods, such as sulfur, peroxide, and quinoid. These are added with vulcanizing chemicals such as vulcanization accelerators and subjected to crosslinking by conventional methods. In addition to the above-mentioned vulcanizing agents, the crosslinking agents for the maleic anhydride-modified liquid butadiene rubber that are preferably used include metal compounds,
Examples include amine compounds, amide compounds, epoxy compounds, glycol compounds, and isocyanate compounds. The metal compound is a metal compound of group ~, preferably group ~ of the periodic table, and preferred examples include lead compounds such as lead oxide, calcium compounds such as calcium oxide, calcium hydroxide, and calcium resinate, and zinc oxide. , zinc compounds such as zinc acetate or zinc resinate. As the amine compound, monoamines such as dibutylamine, n-propylamine, tripropanolamine, triethylenetetramine, polyethyleneimine, methylolmelamine, polyvalent amines, and aziridinyl compounds are preferably used. Examples of epoxy compounds include epoxy compounds obtained by condensing epihalohydrin with a polyhydric alcohol such as diphenylolpropane (bisphenol A) or tetrahydroxyphenylethane. In particular, an epoxy compound obtained by condensation of epichlorohydrin and bisphenol A and having an epoxy equivalent of about 150 to 700 is preferred. In this case, an amine compound or the like is used as the curing accelerator.
Among these, sulfur, metal compounds, amine compounds and epoxy compounds are preferably used. The amount of these crosslinking agents to be used varies depending on the type, temperature of use, etc., and cannot be generalized, but in the case of crosslinking using the polar group of added maleic anhydride (or its derivatives), the amount of added anhydride The amount is 0.5 equivalent or more with respect to maleic acid (or its derivative), but considering that it functions as a filler, it should be 100 parts by weight or less per 100 weight of liquid butadiene rubber. It is. In addition to the above-mentioned rubber vulcanizing agents such as sulfur, amine compounds, acid anhydrides, imidazole compounds and amide compounds are used as crosslinking agents for the epoxy-modified liquid butadiene rubber. Examples of amine compounds include diethylenetriamine, triethylenetetramine, metaphenylenediamine, piperidine, 2,4,6-tris(dimethylaminomethyl)phenol, butylated urea resin,
Mention may be made of butylated melamine resins or dicyandiamide. Examples of the acid anhydride include phthalic anhydride, maleic anhydride, succinic anhydride, and methylnadic anhydride. Imidazole compounds include 2-methylimidazole, 2-ethyl-
Examples include imidazole compounds such as 4-methylimidazole, 2-methylimidazoline, and 2-ethyl-4-methylimidazoline. Examples of the amide compound include polyamide resins such as a condensate of dimer acid and polyethylene polyamine. These crosslinking agents may be used alone or in combination of two or more, but good results are often obtained when a small amount of an epoxy compound is used in combination. The microhydrogel used in the present invention is produced by absorbing water into superabsorbent resin powder. The super absorbent resin used here is
Water absorption rate when using distilled water is 10 to 1000 of its own weight
About twice (weight), preferably 50~
It is in the 500x range. The super absorbent resin powder does not necessarily need to be used in a state where it has absorbed the maximum amount of water, but it is cost-effective if the amount of super absorbent resin contained in the final water-containing composite is small. It is appropriate to use it in a water absorption state of 10 to 1000 times, preferably 50 to 500 times. The volume of the individual microhydrogel is less than or equal to 0.25 ^cm3 , more preferably
It is desirable that it is ^0.1cm3 or less. If the volume of the microhydrogel is too large, it will be difficult to uniformly disperse the microhydrogel into the matrix component, which is not preferable. If the strength of the microhydrogel is low, even if a large volume of microhydrogel is used, the microhydrogel may be broken into small pieces during stirring during dispersion into the matrix component, but manufacturing conditions such as stirring conditions etc. This is not preferable in principle because it has many and strict restrictions. In addition, when making a poultice by incorporating a medicinal ingredient into a water-containing complex,
The said volume is below ^0.08cm3 , more preferably ^0.03cm3
It is desirable to use the following microhydrogel. If the volume is too large, not only will it be difficult to uniformly disperse the powder into the matrix component, but the smoothness of the surface of the poultice will deteriorate, and in extreme cases, the surface of the poultice will become so uneven that it will not adhere closely to the skin. As a result, the function as a poultice often ceases to be expressed. The super absorbent resin used here includes hydroxyl groups,
It refers to a water-insoluble hydrophilic resin in which a suitable amount of intermolecular crosslinking is introduced into a water-soluble polymer having a hydrophilic group such as a carboxyl group or a salt thereof using a crosslinking agent, radiation, etc. Examples include (1) ethylene, propylene; , butene-1, isobutylene or diisobutylene, preferably an α-olefin having 2 to 12 carbon atoms, and maleic anhydride or a derivative thereof (e.g. maleic acid, maleic acid amide, maleic acid imide). A crosslinked copolymer or its alkali neutralized product (methods for producing such super absorbent resins are described in Japanese Patent Application Laid-Open No. 56-36504 and Japanese Patent Application No. 1987-
It has already been filed as No. 113194. ) (2) A copolymer of a polymerizable vinyl compound such as methyl vinyl ether, vinyl acetate, or styrene and maleic anhydride or its derivative, or a crosslinked product of its alkali neutralized product (the method for producing such a super absorbent resin is , same as above (1), JP-A-56-
No. 36504 and Japanese Patent Application No. 113194 (1984). ), (3) polymers of acrylic acid or methacrylic acid,
(4) Self-crosslinking alkali metal acrylate polymers obtained from alkali metal acrylates or alkali metal methacrylates; (5) Combination of vinyl ester and (meth)acrylic acid ester. Saponified products of polymers (such super absorbent resins are produced by the method disclosed in, for example, Japanese Patent Publication No. 53-37994). Commercially available products include "Sumikagel" manufactured by Sumitomo Chemical Co., Ltd. ) (6) Starch graft-polymerized with (meth)acrylonitrile or alkali-neutralized cross-linked products (such highly water-absorbent resins are, for example,
This is disclosed in the specification of Publication No. -43395. ) (7) Starch graft-polymerized with acrylic acid, methacrylic acid, or maleic anhydride, or a crosslinked product of its alkali neutralized product (such super absorbent resins are described in, for example, Japanese Patent Publication No. 53-46199, etc.) (8) Starch is carboxymethylated with monochloroacetic acid, etc., and then cross-linked with formalin, etc. thing. (9) Crosslinked cellulose grafted with (meth)acrylonitrile or its alkali neutralized product, (10) Crosslinked cellulose carboxymethylated with monochloroacetic acid, etc., (11) Polyoxyethylene treated with radiation, etc. (12) polyvinyl alcohol crosslinked with dialdehyde or radiation, and (13) polyvinyl alcohol modified with maleic anhydride, itaconic acid, or crotonic acid. The above α-
A crosslinked product of a copolymer of olefin and maleic anhydride or an alkali neutralized product thereof, a crosslinked product of a copolymer of the polymerizable vinyl compound and maleic anhydride or an alkali neutralized product of the above (2), 3) A polymer of acrylic acid or (meth)acrylic acid, a copolymer containing these monomers, or a crosslinked product of an alkali neutralized product of these (co)polymers, and the acrylic acid described in (4) above. Self-crosslinking alkali metal salt polymers obtained from acid alkali metal salts are preferably used, and among them, α-
By reacting a crosslinked product of an alkali-neutralized product of a copolymer of olefin and maleic anhydride, specifically, a neutralized product of sodium hydroxide of an isobutylene-maleic anhydride copolymer with an epoxy compound or a polyvalent amine. The thus obtained crosslinked product is preferably used. This cross-linked product of an alkali-neutralized copolymer of α-olefin and maleic anhydride is produced by combining α-olefin such as ethylene, propylene, butene-1, isobutylene, or diisobutylene with maleic anhydride using a radical polymerization catalyst or the like. Polymerization and the resulting copolymer are combined into alkali metal hydroxides, alkaline earth metal hydroxides,
Ammonia or an alkaline substance, particularly preferably sodium hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, is allowed to act, for example in the form of an aqueous solution, to form an alkali neutralized product, and then an epoxy compound, a polyvalent amine, etc. Manufactured by reacting a crosslinking agent. Note that using a non-crosslinked water-soluble polymer instead of the superabsorbent resin essentially creates a W/O emulsion, which increases the complexity of emulsion formation and the problems pointed out earlier. This is unavoidable, and depending on the type of water-soluble polymer, even a stable W/O emulsion may not be obtained, which is often undesirable. However, there is no problem in using it as an auxiliary to the above superabsorbent resin or a combination of two or more thereof. The above superabsorbent resin is used in powder or flake form, and the shape of the powder or flake is as follows:
They may be spherical, scale-like, rod-like, fibrous, or a mixture thereof, but considering the volume of the microhydrogel formed by absorbing water, the particle size should be 1 mm or less, more preferably 0.5 mm or less. A certain powder or granule-like material, and a scale-like material with a length of 2 mm or less, more preferably 1 mm or less, are suitable. Microhydrogel is preferably produced by adding the superabsorbent resin powder or flakes to water in an amount of 10 to 1000 times its own weight, preferably 50 to 500 times, but the stirring operation and stirring time are If this is not taken into account, it may sometimes be possible to adopt a method in which water is added to the matrix component at the time of mixing the superabsorbent resin powder or flakes, or immediately after, to form a microhydrogel. Note that distilled water is most preferably used as water for producing microhydrogel, but tap water or well water can also be used. The amount of microhydrogel used is preferably such that the water content is 10 to 80% by weight based on the water-containing composite. If the water content is too low, it cannot be used as a plaster or ice pack, and if it is too high, a stable water-containing complex cannot be obtained. In the present invention, it is preferable to use a surfactant having an HLB value of 2 to 15 in order to uniformly disperse the microhydrogel in the matrix component and obtain a stable water-containing composite. Specific examples that are preferably used include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene oleate, polyoxypropylene polyoxyethylene ether, sorbitan oleate, and sorbitan stear. sorbitan laurate, glycerin fatty acid ester, polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan laurate, and the like. Among them, polyoxyethylene nonyl phenyl ether and polyoxyethylene oleyl ether having an HLB value of 4 to 10 are preferably used. These can be used alone or in combination of two or more. The amount used is preferably 25 parts by weight or less, preferably 1 to 15 parts by weight, based on 100 parts by weight of the matrix component. In the present invention, in addition to the matrix component and microhydrogel component described above, various functional additives and conventional additives are added depending on the use of the obtained water-containing composite. For example, when used as a poultice, its medicinal ingredients include salicylic acid, methyl salicylate, glycol salicylate,
Capsicum extract, diphenhydramine, l-menthol, camphor, thymol, peppermint oil, funnel oil, funnel extract, benzyl nicotyl ester, capsaicin, hormones or vitamins, etc. are 0.1 to 25% by weight of the water-containing complex. In proportion, it also contains glycerin, ethylene glycol, diethylene glycol, triethylene glycol,
A polyhydric alcohol such as polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol or 1,3,5-pentanetriol is appropriately added. Furthermore, when used as a fragrance preservative, various fragrances are added. As usual compounding agents, fillers such as kaolin clay, bentonite, silica, calcium carbonate, zinc white or titanium oxide, dyes, pigments, and even oxidative deterioration inhibitors may be added, and the amount It is determined as appropriate depending on the usage. A typical example of the method for producing a water-containing composite according to the present invention is as follows. First, the liquid rubber component is placed in a stirrer. In this case, heating may be performed or a plasticizer may be added to reduce the viscosity. Note that the liquid rubber component must be at least 80,000 poise or less at 90°C. Otherwise, commonly used stirrers will not be able to uniformly disperse the microhydrogel, and the intended purpose will not be achieved. On the other hand, adding 10 to 1000 times its own weight of water to super absorbent resin (powder),
A microhydrogel containing 10 to 1000 times its own weight of water is prepared by dispersing it. The microhydrogel thus obtained is dispersed in the liquid rubber component in a stirrer. Functional compounding agents, crosslinking agents, fillers,
Colorants, flame retardants, fragrances, other conventional rubber compounding agents, glass beads or glass fibers, etc. are added and mixed when preparing the matrix component, when adding the microhydrogel to the matrix component, or afterward. The mixture consisting of the liquid rubber component, microhydrogel component, or crosslinking agent thus obtained is subjected to a crosslinking treatment by a conventional method. The stirring device for mixing and dispersing the microhydrogel in the matrix may be any commonly used stirrer, and preferred ones include propeller blades, turbine blades, anchor blades, and spiral blades. An example is a stirrer with a . In some cases, a kneader type stirrer may be used. However, the high-speed, high-shear type stirrer required when preparing a W/O emulsion is not only unnecessary, but also undesirable in some cases. The water-containing composite obtained in this way can be used as a cold insulator,
It is preferably used as a heat insulating material, a sound insulating material, a buffering material, a fragrance preserving material, a flame retardant material, a temperature control material, or a poultice. Among these, it is preferably used as a poultice or cold pack, since the properties of the water-containing complex can be fully utilized. When used as a poultice, the water-containing complex containing the medicinal ingredients of the poultice is applied to a fabric, crosslinked and cured. When used as a cold insulating material, the water-containing composite is put into practical use by being molded into a desired shape and hardened. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In the Examples and Comparative Examples, "parts" means "parts by weight" unless otherwise specified. Example 1 The molecular weight is 47000, the amount of vinyl bonds is 6% (the amount of cis 1,4 bonds is 82%), and (weight average molecular weight)/
Add and mix 15 parts of clay to 30 parts of liquid polyisoprene rubber (polyisoprene rubber produced by anionic polymerization method using a lithium catalyst: Kuraprene LIR-50, manufactured by Clareisoprene Chemical Co., Ltd.) with a (number average molecular weight) of 2.0, and mix at 90°C. A matrix component consisting of a mixture having a viscosity of 3100 poise was prepared. In addition to this matrix component, 1 part of sulfur, 2 parts of zinc white (zinc oxide), 0.5 part of stearic acid, and a vulcanization accelerator (butyl xanthate zinc [Ouchi Shinko Chemical Co., Ltd.
Noxela Co., Ltd. ZBX] 0.5 part, 2-mercaptobenzothiazole [Noxel M] 0.2 part, dibenzothiazole disulfide [Noxeler
After adding and mixing a crosslinking agent component consisting of 1.2 parts of DM]0.5 parts), 5 parts of a surfactant (polyoxyethylene nonyl phenyl ether having an HLB value of 7.8) was added and mixed. On the other hand, isobutylene-maleic anhydride copolymer (an alternating copolymer with an intrinsic viscosity of 1.00 in a dimethylformamide solution at 30°C and a composition of isobutylene and maleic anhydride of 1:1; manufactured by Clareisoprene Chemical Co., Ltd.) 100 times the amount of water (distilled water) is added to the super water absorbent resin powder, which is obtained by crosslinking the partial sodium salt of isobane-10) with glycerin diglycidyl ether and has a maximum water absorption capacity of 150 times its own weight. microhydrogel with an average volume of 0.009 cm ³ was prepared. 45.3 parts of this microhydrogel was added to 54.7 parts of the above mixture consisting of a matrix component, a crosslinking agent component, and a surfactant, and the mixture was mixed and stirred at a rotation speed of 200 rpm using a turbine blade stirrer in an atmosphere of 60°C. . The resulting mixture was uniformly dispersed. After pouring this mixture into a container of the desired shape, heat treatment is performed at 80°C for 30 minutes.
A hydrous complex was obtained. The water-containing composite thus obtained had excellent shape stability and was highly flexible. Example 2 In Example 1, the molecular weight was prepared by polymerizing butadiene monomer using a butyllithium catalyst instead of liquid polyisoprene rubber.
A water-containing composite was prepared in the same manner as in Example 1, except that liquid polybutadiene rubber having a vinyl bond content of 16% was used. This water-containing composite had excellent morphological stability and high flexibility, and could be sufficiently applied to cold packs or plasters. Comparative Example 1 In Example 1, instead of using microhydrogel, 44 parts of water was gradually added while increasing the rotational speed.
Stir vigorously at a high speed of 1500 rpm, and
A mold emulsion was prepared. This emulsion was unstable, with large amounts of water separating out several minutes after it was prepared. Therefore, it was not possible to crosslink and produce a water-containing composite. Comparative Example 2 In Example 1, instead of using a microhydrogel swollen with water, a microhydrogel was obtained by crosslinking the partial sodium of the isobutylene-maleic anhydride copolymer used to prepare the microhydrogel with glycerin diglycidyl ether. The super absorbent resin powder (maximum water absorption capacity: 150 times) was added and mixed with the matrix component, and molded and hardened. When a composite containing this super-absorbent resin powder was left in water and made into a water-containing composite by utilizing the water-absorbing ability of the super-absorbent resin, the water content was only a few percent at most, making it suitable for cold insulation materials, etc. It was practically impossible to apply. Furthermore, if this water-containing composite was left at a high temperature, the water would easily evaporate and the water content would decrease. Example 3 [Example of application as a plaster] The molecular weight is 29000, the vinyl bond amount is 6% (cis-1,4 bond amount 82%), and (weight average molecular weight) /
Liquid polyisoprene rubber (number average molecular weight) of 2.0 (polyisoprene rubber obtained by anionic polymerization using a lithium catalyst; Kuraprene LIR-30 manufactured by Clareisoprene Chemical Co., Ltd.), liquid paraffin, and kaolin. Clay was added and mixed in the proportions shown in Table 1 to form a matrix component. The viscosity of this matrix component at 90°C was 92 poise, and the viscosity at room temperature (25°C) was 620 poise. The crosslinking agent components shown in Table 1 were added to this matrix component and mixed using a propeller type stirrer at room temperature. The medicinal ingredients shown in Table 1 and a surfactant (polyoxyethylene oleyl ether with an HLB value of 8) were similarly thoroughly mixed into this mixture. On the other hand, 0.7 parts of powder of super absorbent resin (Sunwet IM-300 manufactured by Sanyo Kasei Co., Ltd.), which is a crosslinked product of hydrolyzed modified starch obtained by graft polymerization of acrylic acid, was added to 35
of water (distilled water) was added to prepare a microhydrogel that absorbed 50 times the amount of water. The individual particles of this microhydrogel have an average volume of 0.05 cm ³
Even the largest ones were about ^0.25cm3 at most. 35 parts of the microhydrogel was added to 65 parts of the mixture consisting of the pack agent base component, crosslinking agent component, medicinal ingredient, and surfactant, and the mixture was rotated at 200 revolutions per minute at room temperature.
Stir for 1 minute to obtain a homogeneous mixture. In this mixture, the microhydrogel was uniformly dispersed and remained stable even after being left at room temperature for a day and a night. Spread this mixture on a lint cloth to a thickness of about 2 mm.
After coating, the coated surface is coated with a polyester film, which is then placed in an aluminum foil bag and left in an oven at 45℃ for 24 hours to vulcanize, and then cooled to room temperature. A poultice was prepared. Table 1 Compounding part <Matrix component> Liquid polyisoprene rubber 23.0 Liquid paraffin 23.0 Kaolin clay 9.0 <Crosslinking agent component> Sulfur 0.2 Zinc stearate 0.4 Vulcanization accelerator A ¹⁾ 0.6 〃 B ²⁾ 0.5 〃 C ^{3 )} 0.4 <Medicinal ingredients> Methyl salicylate 2.0 l-menthol 1.0 Camphor 0.8 Thymol 0.2 <Surfactant> 4.0 <Microhydrogel> 35.0 (Total 100 parts) 1 Ethyl phenyl dithiocarbamate zinc;
Noxela-PX 2, manufactured by Ouchi Shinko Chemical Co., Ltd. 2-mercaptobenzothiazole; Noxela-M 3, dibenzothiazyl disulfide; Noxela DM, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. Moisture retention rate when left for 20 hours in an atmosphere with a temperature of 35℃ and humidity of 95℃
We investigated water performance such as water absorption rate when left for 20 hours, observed morphological stability when left in an atmosphere at a temperature of 50°C, and observed the size of drips seen in the bathroom with poultice applied. Sensory tests were conducted on the adhesion to the skin when the poultice was applied or 4 hours after application, the cooling sensation on the skin, and the flexibility when left indoors for 8 hours or at -15℃ for 3 hours. The results are shown in Table 3, and the poultices obtained in this example exhibited excellent properties overall. Comparative Example 3 [Poultice] For comparison, a conventionally used water-soluble polymer poultice having the formulation shown in Table 2 was manufactured by a conventional method. When the obtained poultice was subjected to various tests similar to those in Example 3, the results shown in Table 3 were obtained. Table 2 Compound Example: Gelatin 7 Carboxymethyl cellulose 2 Polyvinyl alcohol 2 Kaolin clay 25 Glycerin 25 Methyl salicylate 2 L-menthol 1 Camphor 0.8 Thymol 0.2 Water 35 (Total 100 parts)

[Put agent]

Liquid polyisoprene rubber with a molecular weight of 24,000 and a vinyl bond content of 12% was prepared by anionic polymerization of isoprene monomer. This liquid polyisoprene rubber and maleic anhydride were heated and reacted at 180°C to obtain a modified liquid polyisoprene rubber in which 1 mol% of maleic anhydride was added per isoprene monomer unit of the liquid polyisoprene rubber. This modified liquid polyisoprene rubber is heated at 90°C.
and room temperature viscosity of 28 poise and
It cost 700 points. To 36 parts of this modified liquid polyisoprene rubber, 2 parts of zinc white, 0.5 part of calcium hydroxide, and 1.5 parts of glycerin.
5.5 parts of a crosslinking agent paste consisting of 1.5 parts and 1.5 parts of polypropylene glycol, 4 parts of the medicinal ingredient used in Example 3, and a surfactant (polyoxyethylene nonyl phenyl ether with an HLB value of 7.8).
4 parts were added and the mixture was stirred with a turbine type stirrer at room temperature. On the other hand, isobutylene-maleic anhydride copolymer (an alternating copolymer with an intrinsic viscosity of about 1.0 in dimethylformamide at 30°C and a copolymerization composition of 1:1 of isobutylene and maleic anhydride; manufactured by Clareisoprene Chemical Co., Ltd. ) Glycerin diglycidyl ether was added to the partial sodium salt of isobane-10) and crosslinked to prepare a super absorbent resin powder with a water absorption capacity of 150 times its own weight in distilled water. This super absorbent resin powder was made to absorb 100 times the amount of water (distilled water) to prepare microhydrogel with an average volume of 0.009 cm ³ . A poultice base was prepared by mixing 50.5 parts of this microhydrogel with 49.5 parts of the mixture consisting of the modified liquid polyisoprene rubber, a crosslinking agent, a medicinal ingredient, and a surfactant at room temperature. The mixture was applied to a nonwoven fabric, and then a polyethylene sheet was attached thereto, and the mixture was placed in an aluminum foil bag and left at room temperature for one week to complete crosslinking, thereby obtaining a poultice. The poultices thus obtained were left at a temperature of 45°C along with commercially available poultices, and their flowability, coolness, adhesion, and flexibility were examined to suit the affected area. Compared to commercially available plasters, the plaster prepared in the above was less likely to flow, and was significantly superior in terms of cooling sensation, adhesion, and flexibility. Also,
When this poultice was compared with the poultice obtained in Example 3, it was found to be somewhat superior in various properties at high temperatures (especially adhesion, sagging, etc.). Comparative Example 4 [Pulp Agent] In Example 5, instead of using a microhydrogel that absorbed 100 times its own weight of water, 30 parts of water was used to obtain a cataplasm base consisting of a W/O emulsion, and each component was changed. When the containing mixture was subjected to emulsification with water, a W/O emulsion could not be obtained, probably due to the presence of kaolin clay. Therefore, when we removed the kaolin clay from the above mixture and subjected it to emulsification, we were unable to obtain a stable W/O emulsion unless the conditions were severe, such as a high temperature of 75°C and high-speed stirring of 1600 rpm. . When kaolin clay was added to this emulsion, the emulsion particles were destroyed and water separated, making it unsuitable for use as a poultice base. Example 6 [Cold Insulating Material] A liquid polyisoprene rubber having a molecular weight of 32,000 and a vinyl bond content of 11% was prepared by anionically polymerizing isoprene monomer. This liquid polyisoprene rubber and maleic anhydride are reacted by heating at 180°C, and then methanol is added to perform a half-esterification reaction, resulting in a modified liquid polyisoprene rubber containing 4.0 mol% of maleic acid monoester per isoprene monomer unit. Isoprene rubber was prepared.
The viscosity of this modified liquid polyisoprene rubber is 90℃.
It was 250 poise and 10,000 poise at room temperature.
To 100 parts of this modified liquid polyisoprene rubber, 5 parts of epoxy resin (Epicoat 828 manufactured by Ciel), 0.5 parts of tris(dimethylaminomethyl)phenol, and a surfactant (polyoxyethylene nonyl phenyl ether with an HLB value of 6) 10 parts were mixed at room temperature to prepare a matrix component for a cold insulation material. On the other hand, isobutylene-maleic anhydride copolymer (an alternating copolymer with an intrinsic viscosity of 1.00 (molecular weight 160,000) in dimethylformamide solution at 30°C and a composition of 1:1 of isobutylene and maleic anhydride; clareisoprene 50 times the amount of water (distilled water) was absorbed into a super water-absorbent resin powder (maximum water absorption capacity is 120 times its own weight) made by cross-linking the partial sodium salt of Isoban-10 (manufactured by Chemical Co., Ltd.) with glycerin diglycidyl ether. Microhydrogels each having an average volume of 0.004 cm ³ were prepared. 100 parts of this microhydrogel was added to 115.5 parts of the above-mentioned cold insulator matrix, and the mixture was stirred and mixed using a turbine type stirrer with a blade diameter of 60 mm at a gentle speed of 270 revolutions/minute. This mixture was sealed in a PVC bag and then heated at 45℃.
By heat-treating for 20 hours, the modified liquid polyisoprene rubber was crosslinked with epoxy resin to obtain a pillow-shaped cold insulator. The thus obtained cold insulator was left overnight in a -20°C freezer to freeze the water in the cold insulator. Even immediately after being removed from the -20°C freezer, this cold insulator maintained sufficient flexibility. Also, when I inserted a thermometer into the ice pack and looked at the temperature change, I found that there was no difference even if I left it at room temperature for 4 hours.
The temperature was around ℃, and it had an excellent cold retention effect.

Claims (1)

[Scope of Claims] 1. A water-containing composite obtained by dispersing microhydrogel in a matrix containing liquid rubber as a main component and subjecting it to crosslinking treatment. 2. The water-containing composite according to claim 1, wherein the liquid rubber is a liquid polydiene rubber produced by an anionic polymerization method. 3. The water-containing composite according to claim 1, wherein the microhydrogel is a crosslinked product of an alkali-neutralized isobutylene-maleic anhydride copolymer that absorbs water. 4. The water-containing complex according to claim 1, wherein the water-containing complex is a base material for a poultice containing a medicinal ingredient for a poultice in its matrix. 5. The water-containing composite according to claim 1, which is a base material for a cold insulation material. 6 Disperse microhydrogel containing 10 to 1000 times its own weight of water in a liquid rubber containing a crosslinking agent at a ratio such that the water content in the liquid rubber is 10 to 80% by weight, and then A method for producing a water-containing composite characterized by crosslinking.