JP2007051261A - Thixotropic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous thixotropic composition which contains an oily component, can be produced without being heated, has a high thixotropic characteristic, has high product stability, and has excellent transparency. <P>SOLUTION: This thixotropic composition contains the following components (A) to (E) as essential components. (A) An oily component, (B) at least one anionic surfactant selected from sulfate type anionic surfactants and sulfonic acid type anionic surfactants, (C) a nonionic surfactant, (D) a layered clay mineral, and (E) water. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thixotropic composition. More particularly, the present invention relates to an aqueous thixotropic composition containing an oily component that can be produced without heating, has high thixotropic properties, has high product stability, and may have excellent transparency.

  At present, many products such as fragrances are distributed as toiletry products. There are various types of fragrance products, but gel fragrances are gel-like compositions that stir the fragrance around, making it difficult for the contents to leak out of the container, make it difficult to drop off, or give it a distinctive appearance. Many products with high commercial value are sold.

  In order to immobilize the fragrance component, which is an oily component, gel-like fragrances usually use gelling agents such as natural polymers (polysaccharides) such as carrageenan and agar. As an alternative, vinyl alcohol and acrylic synthetic polymers are used.

  Gel fragrances using the above natural polymers do not exhibit thixotropic properties, and because the natural polymer has a high coagulation temperature, some volatile additives such as fragrance components will volatilize and evaporate. Had problems. For example, in order to gelatinize carrageenan, a temperature of 80 ° C. or higher is necessary, and thus it is inevitable that some aromatic components are volatilized.

Various methods for solving the problem of volatilization have been studied. For example, Patent Document 1 discloses an example thereof, but it still requires a temperature of about 50 ° C. for blending the oil component, and it cannot be said that the problem has been sufficiently solved. In addition, simply mixing various components without heating may result in spattering or not being transparent.
JP-A 64-74239

On the other hand, when a vinyl alcohol-type or acrylic-type synthetic polymer is used as a gelling agent, it does not exhibit thixotropic properties like natural polymers. In addition, as described in Patent Document 1, the synthetic polymer needs to be added in a large amount of 5 to 30% by weight when used as a gelling agent, which affects other physical properties. . For example, when a large amount of synthetic polymer is used to prepare a gel-like fragrance, there are many residues after use, the appearance is poor, and the commercial value is lowered.

  In addition, it is a matter common to these gelling agents, but when the oil component is solubilized with an ionic surfactant and further gelled, it may become turbid or the gel structure may collapse and become liquid. There are things to do. Although the method of solubilizing an oil component by using a combination of an ionic surfactant and a nonionic surfactant is useful, the method described above is advantageous as a method of gelation because of the above problems. I can't say that.

Patent Document 2 discloses a method for producing a composition that exhibits thixotropic properties and contains an oil component. In this production method, when a clay mineral such as smectite is blended with a liquid or gel composition containing a cationic surfactant, a liquid or gel composition component other than the clay mineral is emulsified and dispersed in water. Alternatively, after solubilization, a blend of a clay mineral and a nonionic polymer substance mixed and dispersed in water is added.
JP 2000-159636 A

  However, in this production method, the cationic surfactant often yellows with heat or with time, and the frequency of yellowing particularly at a temperature of about 40 ° C. or higher is high.

  By imparting thixotropy, it is possible to prevent the liquid from splashing out of the container (i.e., difficult to drop off) or to be removed from the container. Therefore, although there is a market need for a composition having excellent thixotropy and containing an oil component, in reality, there is no composition that can withstand practical use, and development of such a composition is desired. .

  In the case of an aqueous composition containing an oily component, the oily component may separate due to aging or temperature change. This is because the product stability is poor, and various studies have been made on compositions with improved product stability.

  Therefore, the problem to be solved by the present invention is an aqueous system containing an oily component that can be produced without heating, has high thixotropic properties, has high product stability, and may have excellent transparency. It is to provide a thixotropic composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing an oil component, a specific surfactant, a layered clay mineral, and water can be produced without heating, and has high thixotropy. The inventors have found that it has tropic characteristics and good product stability, and has reached the present invention.

That is, the thixotropic composition according to the present invention contains the following components (A) to (E) as essential components.
(A) Oil component (B) At least one anionic surfactant selected from a sulfate ester type anionic surfactant and a sulfonic acid type anionic surfactant (C) Nonionic surfactant (D) Layered clay mineral (E) water

  The thixotropic composition of the present invention can be produced without heating, has high thixotropic properties, has high product stability, and may have excellent transparency. Since this composition has high thixotropic properties, it can also exhibit a high-viscosity fluid and a gel-like appearance, and can be fluidized by applying an impact, external force, shaking, etc. to those having a gel-like appearance. You can also

  The thixotropic composition of the present invention is used in, for example, fragrances, agricultural chemicals, repellents, deodorants, insect repellents, insecticides, disinfectants, cleaning agents, and the like.

  Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following disclosure can be made as appropriate without departing from the spirit of the present invention.

  The thixotropic composition of the present invention contains components (A) to (E) as essential components, and may further contain a component (F). Hereinafter, the components (A) to (F) constituting the thixotropic composition will be described in detail, and then the thixotropic composition and the production method thereof will be described in detail.

[Component (A)]
Component (A) is an oily component and may be either liquid or solid, but liquid is preferred. The oily component means a flammable substance that is insoluble or hardly soluble in water, and the oily component is a component that is substantially insoluble in water. In addition, the hardly soluble in the present invention means a state in which an aqueous solution having a concentration of about 0.5% by weight is not dissolved even at room temperature, particularly around 20 ° C.

  Examples of the oil component include aromatic components such as plant extract oils, blended fragrances, natural fragrances, synthetic fragrances, essential oils and terpenes; mineral oils; aliphatic hydrocarbon oils; aromatic hydrocarbon oils; ester oils; Can be mentioned. These oil components may be used alone or in combination of two or more.

  Specific examples of aromatic components include lavender oil, orange oil, lemon oil, rose extract oil, lime oil, cypress extract oil and herb extract oil; rose, citrus, lemon, coffee, apricot, floral , Peach, and other various ingredients that are made by artificially blending various ingredients; camphor white oil, cypress essential oil, turpentine oil, eucalyptus oil, light oil, etc .; p-menthadiene, d- Limonene, p-menthane, terpineol, linalool, terpinyl acetate, dihydroterpineol, dihydroterpinyl acetate, myrtenal, myrtenol, perilaldehyde, rose oxide, borneol, camphor, carbeol, carboxoxide, carbyl acetate, caryophyllene, Cine , Citronellal, citronellol, cymen, cymen-8-ol, dihydrocarbeveol, dihydrocarbon, dihydrocarbyl acetate, limonene oxide, furanoid, pyranoid, menthone, menthyl acetate, myrtenal, miltenol, miltenyl acetate, perillyl alcohol Terpene aromatic components such as perillyl acetate, pinene, pinene oxide, geraniol, isoamyl acetate, amylcinnamic aldehyde, menthol and methyl anthranilate.

  Specific examples of the mineral oil include liquid paraffin, light oil, spindle oil, and the like.

  Specific examples of the aliphatic hydrocarbon oil include hexane, heptane, isooctane, and octane, and examples of the aromatic hydrocarbon oil include toluene and xylene.

  Specific examples of ester oils include isopropyl palmitate, isopropyl myristate, methyl laurate, octyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl palmitate, isostearyl myristate, isocetyl myristate, myristine Examples include isotridecyl acid, octyldodecyl myristate, cetyl myristate, decyl myristate, butyl myristate, octyldodecyl oleate, isodecyl oleate, ethyl oleate, and butyl lactate.

  Specific examples of the amide compound include N, N-diethyltoluamide.

  The oil component is preferably at least one component selected from the aroma component, agricultural chemical component, repellent component, deodorant component, sterilizing component, and cleaning component described above.

  As used herein, the fragrance component means a fragrant component such as a fragrance, an essential oil, a plant extract oil, or a terpene. The agrochemical component is a medicinal component of a drug directly used for crops and plants, and means a component that provides various effects such as insecticide, sterilization, weeding, and plant growth adjustment. A repellent component is a component that acts on animals such as insects, arthropods, mollusks, dogs and cats that are harmful or unpleasant for humans. It means a component that prevents the entry of these insects and animals. The deodorant component means a component that eliminates an odor by absorbing, decomposing, or reacting an unpleasant odor. The sterilizing component means a component that removes the bacteria attached to the article. The cleaning component means a component that removes dirt, but excludes a water-soluble surfactant and the like. An oily component such as a surfactant that is hardly soluble in water and a solvent that dissolves dirt corresponds to the cleaning component.

[Component (B)]
Component (B) is at least one anionic surfactant selected from sulfate ester type anionic surfactants and sulfonic acid type anionic surfactants. The anionic surfactant is used in combination with a nonionic surfactant (component (C)) to solubilize the oil component over a wide temperature range (for example, in the range of 5 to 40 ° C.), and the thixotropy of the present invention. The composition has excellent transparency.

  Specific examples of these anionic surfactants include alkylbenzene sulfonates, α-olefin sulfonates, alkyl (or alkenyl) sulfates, polyoxyethylene alkyl (or alkenyl) ether sulfates, acyls. Examples thereof include methyl taurate, dialkyl (or alkenyl) sulfosuccinate, acyl isethionate, and the like. As the anionic surfactant, polyoxyethylene alkyl ether sulfate, dialkyl sulfosuccinate and the like are more preferable. These anionic surfactants may be used alone or in combination of two or more. Here, when the anionic surfactant is a salt, it indicates an alkali metal salt and / or a triethanolamine salt. Moreover, the organic group of the alkyl group, alkenyl group, and acyl group contained in the anionic surfactant may have a linear structure or a branched structure. The number of carbon atoms of the alkyl group and acyl group is not particularly limited, but 8 to 18 is preferable.

  Carboxylic acid type and phosphoric acid type anionic surfactants do not always solubilize oil components over a wide temperature range. However, in the present invention, the carboxylic acid type and phosphoric acid type anionic surfactants are not completely excluded, and may be contained as other components.

[Component (C)]
Component (C) is a nonionic surfactant, and by using it together with an anionic surfactant (component (B)), the oil component can be used over a wide temperature range (for example, a range of 5 to 40 ° C.). Solubilizes and imparts excellent transparency to the thixotropic composition of the present invention.

  There is no particular limitation on the nonionic surfactant. Specific examples of nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene castor oil, polyoxyalkylene sorbitan fatty acid esters, polyglycerin fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene ethers Examples include alkylene amino ethers, polyoxyalkylene aryl ethers, polyoxyalkylene phenyl ethers, fatty acid polyoxyalkylene sorbits, polyoxyalkylene styrenated phenyl ethers, polyoxyalkylene fatty acid alkanolamides, and the like. These nonionic surfactants may be used alone or in combination of two or more. Nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene castor oil, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene amino ethers, polyoxyalkylene phenyl ether, polyoxyalkylene fatty acid alkanolamides. Preferably, polyoxyalkylene ethers, polyoxyalkylene castor oil, and polyoxyalkylene phenyl ether are more preferable. In addition, although it does not specifically limit as preferable embodiment, It is preferable that the weight ratio is 30 / 70-70 / 30 using polyoxyalkylene ether and polyoxyalkylene castor oil.

  Polyoxyalkylene ethers mean polyoxyalkylene alkyl ethers and polyoxyalkylene alkenyl ethers. Specific examples thereof include, for example, polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene isododecyl ether , Polyoxyethylene isotetradecyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isodecyl ether, polyoxyethylene isooctyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene secondary alkyl (C12-14) ) Ether, polyoxyethylene secondary alkyl (C10-12) ether, polyoxyethylene polyoxypropylene lauryl ether, poly Oxyethylene polyoxypropylene myristyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene oleyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene polyoxypropylene Isododecyl ether, polyoxyethylene polyoxypropylene isotetradecyl ether, polyoxyethylene polyoxypropylene isocetyl ether, polyoxyethylene polyoxypropylene isodecyl ether, polyoxyethylene polyoxypropylene isooctyl ether, polyoxyethylene polyoxy Propylene-2-ethylhexyl ether, polyoxyethylene poly Carboxymethyl propylene secondary alkyl (C12-14) ether, polyoxyethylene polyoxypropylene secondary alkyl (C10~12) and ether, and the like. In addition, the part shown in the parenthesis in the above example shows the carbon number of the alkyl group described immediately before. These polyoxyalkylene ethers may be used alone or in combination of two or more.

  Although there is no limitation in particular about the kind of polyoxyalkylene group in polyoxyalkylene ethers, a polyoxyethylene group and / or a polyoxypropylene group are preferable. In addition, as a polyoxyalkylene group, for example, when a polyoxybutylene group or other long-chain polyoxyalkylene group having a larger number of carbon atoms than polyoxypropylene is introduced, the hydrophobicity is increased and the sufficient effect is obtained. It may not be obtained. These polyoxyalkylene groups are usually introduced by addition reaction of alkylene oxide. When two or more types of alkylene oxide are used, the polymerization mode is any one of block polymerization, random polymerization, and alternating polymerization. These polymerization modes may be mixed. The same applies to the polyoxyalkylene group in the nonionic surfactant shown below.

  Polyoxyalkylene castor oils are nonionic surfactants obtained by reacting, for example, castor oil and / or hydrogenated castor oil with alkylene oxide. The degree of cure of the hardened castor oil is not particularly limited, and may be completely cured (hydrogenated) or partially cured. Specific examples of the polyoxyalkylene castor oil include polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene polyoxypropylene castor oil, polyoxyethylene polyoxypropylene hydrogenated castor oil, and the like. These polyoxyalkylene castor oils may be used alone or in combination of two or more.

  Polyoxyalkylene sorbitan fatty acid esters are nonionic surfactants obtained by, for example, reacting an alkylene oxide with an ester of a fatty acid and sorbitan. Specific examples of polyoxyalkylene sorbitan fatty acid esters include polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan cocoate, polyoxyethylene sorbitan caprate, polyoxyethylene polyoxypropylene sorbitan laurate, polyoxyethylene polyoxypropylene Examples include sorbitan cocoate and polyoxyethylene polyoxypropylene sorbitancaprate. These polyoxyalkylene sorbitan fatty acid esters may be used alone or in combination of two or more.

  Polyglycerin fatty acid esters are nonionic surfactants obtained, for example, by reacting polyglycerin with fatty acids. Specific examples of polyglycerin fatty acid esters include decaglycerin laurate, decaglycerin cocoate, decaglycerin caprate, hexaglycerin caprate, hexaglycerin laurate, hexaglycerin cocoate and the like. These polyglycerin fatty acid esters may be used alone or in combination of two or more.

  Polyoxyalkylene glycerin fatty acid esters are nonionic surfactants obtained, for example, by reacting glycerin, fatty acids, and alkylene oxides. Specific examples of polyoxyalkylene glycerol fatty acid esters include polyoxyethylene glycerol laurate, polyoxyethylene glycerol cocoate, polyoxyethylene glycerol caprate, polyoxyethylene polyoxypropylene glycerol laurate, polyoxyethylene poly Examples thereof include oxypropylene glycerin cocoate and polyoxyethylene polyoxypropylene glycerin caprate. These polyoxyalkylene glycerin fatty acid esters may be used alone or in combination of two or more.

  Polyoxyalkylene amino ethers mean polyoxyalkylene alkyl amino ethers and polyoxyalkylene alkenyl amino ethers, for example, nonionic surfactants obtained by reacting alkylamines or alkenylamines with alkylene oxides. It is. Specific examples of polyoxyalkylene amino ethers include polyoxyethylene lauryl amino ether, polyoxyethylene myristyl amino ether, polyoxyethylene cetyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene decyl amino ether, polyoxyethylene decyl amino ether, Oxyethylene octyl amino ether, polyoxyethylene isododecyl amino ether, polyoxyethylene isotetradecyl amino ether, polyoxyethylene isocetyl amino ether, polyoxyethylene isodecyl amino ether, polyoxyethylene isooctyl amino ether, polyoxyethylene 2-ethylhexyl amino ether, polyoxyethylene polyoxypropylene lauryl amino ether, polyoxye Len polyoxypropylene myristyl amino ether, polyoxyethylene polyoxypropylene cetyl amino ether, polyoxyethylene polyoxypropylene oleyl amino ether, polyoxyethylene polyoxypropylene decyl amino ether, polyoxyethylene polyoxypropylene octyl amino ether, polyoxy Ethylene polyoxypropylene isododecyl amino ether, polyoxyethylene polyoxypropylene isotetradecyl amino ether, polyoxyethylene polyoxypropylene isocetyl amino ether, polyoxyethylene polyoxypropylene isodecyl amino ether, polyoxyethylene polyoxypropylene iso Octyl amino ether, polyoxyethylene polyoxypropylene - it can be mentioned hexyl amino ether. These polyoxyalkylene amino ethers may be used alone or in combination of two or more.

  The polyoxyalkylene aryl ethers mean polyoxyalkylene alkyl aryl ethers and polyoxyalkylene alkenyl aryl ethers, and specific examples thereof include, for example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyalkylene aryl ether, Examples thereof include oxyethylene polyoxypropylene nonylphenyl ether and polyoxyethylene polyoxypropylene octylphenyl ether. These polyoxyalkylene aryl ethers may be used alone or in combination of two or more.

  Specific examples of the fatty acid polyoxyalkylene sorbit include oleic acid polyoxyethylene sorbitol, lauric acid polyoxyethylene sorbit, coconut oil fatty acid polyoxyethylene sorbit, and the like. The degree of esterification can be arbitrarily set and is not limited. These fatty acid polyoxyalkylene sorbits may be used alone or in combination of two or more.

  Specific examples of the polyoxyalkylene styrenated phenyl ether include polyoxyethylene distyrenated phenyl ether, polyoxyethylene tristyrenated phenyl ether, polyoxyethylene polyoxypropylene distyrenated phenyl ether, polyoxyethylene polyoxy And propylene tristyrenated phenyl ether. These polyoxyalkylene styrenated phenyl ethers may be used alone or in combination of two or more.

  Polyoxyalkylene fatty acid alkanolamides are, for example, reaction products of fatty acid alkanolamides synthesized from fatty acids and alkanolamines with alkylene oxides. Specific examples include polyoxyethylene lauric acid monoethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, polyoxyethylene capric acid monoethanolamide, polyoxyethylene myristic acid monoethanolamide, polyoxyethylene lauric acid monoisopropanol. Amide, polyoxyethylene coconut oil fatty acid monoisopropanolamide, polyoxyethylene capric acid monoisopropanolamide, polyoxyethylene myristic acid monoisopropanolamide, polyoxyethylene lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid diethanolamide, polyoxyethylene Capric acid diethanolamide, polyoxyethylene myristic acid diethanolamide, polyoxyethylene Uric acid diisopropanolamide, polyoxyethylene palm oil fatty acid diisopropanolamide, polyoxyethylene capric acid diisopropanolamide, polyoxyethylene myristic acid diisopropanolamide, polyoxyethylene polyoxypropylene lauric acid monoethanolamide, polyoxyethylene poly Oxypropylene palm oil fatty acid monoethanolamide, polyoxyethylene polyoxypropylene capric acid monoethanolamide, polyoxyethylene polyoxypropylene myristic acid monoethanolamide, polyoxyethylene polyoxypropylene lauric acid monoisopropanolamide, polyoxyethylene polyoxy Propylene coconut oil fatty acid monoisopropanolamide, polyoxyethylene polyoxy Propylene capric acid monoisopropanolamide, polyoxyethylene polyoxypropylene myristic acid monoisopropanolamide, polyoxyethylene polyoxypropylene lauric acid diethanolamide, polyoxyethylene polyoxypropylene coconut fatty acid diethanolamide, polyoxyethylene polyoxypropylene capric acid Diethanolamide, polyoxyethylene polyoxypropylene myristic acid diethanolamide, polyoxyethylene polyoxypropylene lauric acid diisopropanolamide, polyoxyethylene polyoxypropylene coconut oil fatty acid diisopropanolamide, polyoxyethylene polyoxypropylene capric acid diisopropanolamide , Polyoxyethylene polyoxypropylene Examples thereof include ristinic acid diisopropanolamide. Polyoxyalkylene fatty acid alkanolamides are not limited to the compounds exemplified above, and useful compounds can be used as appropriate. The fatty acid residue in the polyoxyalkylene fatty acid alkanolamide is not particularly limited, but is preferably a fatty acid residue having 8 to 22 carbon atoms, more preferably a fatty acid residue having 8 to 14 carbon atoms, particularly preferably. Is a fatty acid residue having 10 to 12 carbon atoms. Further, the alkanolamine residue in the polyoxyalkylene fatty acid alkanolamide is not particularly limited, but a monoethanolamine residue, a diethanolamine residue, a monoisopropanol residue, a diisopropanolamine residue and the like are preferable. These polyoxyalkylene fatty acid alkanolamides may be used alone or in combination of two or more.

  In order to keep the thixotropic composition in a transparent state, the nonionic surfactant may have a cloud point of 20 ° C. or higher due to the essential properties of the surfactant itself. More preferably, it is 25 ° C. or more, particularly preferably 28 ° C. or more.

  In the present invention, the cloud point refers to a temperature at which an aqueous solution becomes cloudy when a 1% by weight aqueous solution of a surfactant is gradually heated. Specifically, 10 mL of the aqueous solution was added to a glass test tube having an inner diameter of 15 mm and a length of 180 mm, and a thermometer was placed in the center of the aqueous solution so as not to touch the wall of the test tube. Fix the end soaked in the aqueous solution. Next, the test tube is placed in a 1 L beaker containing 1 L of water, attached so as not to touch the wall of the beaker, and gradually heated while stirring the water in the beaker. The temperature at which the aqueous solution becomes cloudy is read as the cloud point. Here, when the temperature of the water in the beaker is sufficiently lower than the (predicted) cloud point, the heating is adjusted so that the heating rate is 2 ° C./min, and the cloud point is about 10 ° C. (predicted). After reaching a low temperature, the heating is adjusted so that the rate of temperature rise is 0.2 ° C./min.

[Component (D)]
Component (D) is a layered clay mineral and is a component that enables the production of a thixotropic composition without heating. The layered clay mineral is a component that imparts high thixotropic properties to the thixotropic composition.
In the present invention, thixotropic properties and thixotropic properties refer to properties in which the apparent viscosity temporarily decreases due to deformation in an isothermal state. Specifically, the flow resistance (apparent viscosity) increases with increasing flow velocity and shear stress. When the shear stress is reduced and the shear stress is reduced, the viscosity is restored, but it takes a long time to return to the original state and gives a phenomenon in which hysteresis is observed in the fluidity. If it illustrates concretely, it will be a property in which a difference appears in the viscosity shown by the measurement conditions of the viscometer used when measuring a viscosity. That is, for example, the viscosity shown by measuring the shear pressure applied to the rotor by rotating the rotor in the sample like a B-type viscometer depends on the rotational speed of the rotor in a sample having thixotropic characteristics. Differently shown, the viscosity is high at low rotational speeds and low at high rotational speeds. In this example, thixotropic characteristics were evaluated by the ratio (Y) / (Z) of the viscosity (Y) measured at 6 rpm and the viscosity (Z) measured at 60 rpm. That is, the larger the (Y) / (Z), the better the thixotropic characteristics.

  The layered clay mineral is not particularly limited, and specific examples include hydrophilic layered clay minerals such as smectite, laponite, montmorillonite, and bentonite.

  Component (D) imparts thixotropic properties to the composition, but also has a great influence on the appearance of the composition. Some, such as synthetic smectite and laponite, give the composition a transparent appearance, while others, such as bentonite, give an opaque appearance. Smectite or laponite is suitable when transparency is required for the appearance.

  Smectite is the name of a group of minerals known as the montmorillonite group. In 1955, the smectite was classified and named by the British clay mineral group naming subcommittee. Smectite is a type of layered clay mineral that forms a 2: 1 type layered structure with an octahedral layer sandwiched between two tetrahedral layers. More specifically, the tetrahedral structure of silicic acid is the apex. Two sheet-like structures connected in common share a silicate layer bonded by ions with octahedral coordination with the remaining vertices facing each other inward, an alkali or alkaline earth metal ion, and an arrangement thereof It has a structure in which layers of molecules that are positioned are connected in layers. In addition, the hydrophilic layered clay mineral in the present invention means a property that swells, disperses, dissolves, etc. when it is poured into a large amount of water.

  The hydrophilic layered clay mineral is preferably a smectite type hydrophilic layered clay mineral because it imparts high thixotropic properties and excellent transparency to the thixotropic composition of the present invention. The smectite-type hydrophilic layered clay mineral may be naturally produced or synthesized. Moreover, what refine | purified these and removed the impurity is preferable. A synthesized smectite-type hydrophilic layered clay mineral is particularly preferred from the viewpoint of quality stability.

[Component (E)]
Component (E) is water, in which the oily component (component (A)) is solubilized by an anionic surfactant (component (B)) and a nonionic surfactant (component (C)), The thixotropic composition of the present invention exhibits transparency. The water may be any of tap water, ion exchange water, distilled water, purified water, spring water, and the like.

[Component (F)]
Component (F) is a water-soluble organic solvent. The thixotropic composition of the present invention has high thixotropic properties and a high viscosity or a gel-like appearance. However, when gelation occurs during the production, the handling property in the production may be deteriorated. That is, it is preferable to avoid gelation during production. The water-soluble organic solvent is a gel-like substance formed when an anionic surfactant (component (B)) and a nonionic surfactant (component (C) and water (component (E)) are mixed. Softens to improve handling, and provides a hydrotrope effect during solubilization of the oil component (component (A)) to stabilize the solubilization and improve the solubilizing power.

  Specific examples of the water-soluble organic solvent include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, ethylene glycol, ethanol, methanol, propanol, 3-methoxy-3-methyl-1-butanol, Examples include methyl cellosolve, ethylsocellosolve, propylcellosolve, butylcellosolve, diethylene glycol, dipropylene glycol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol propyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like. . These water-soluble organic solvents may be used alone or in combination of two or more.

[Thixotropic composition]
The thixotropic composition according to the present invention is a composition containing the components (A) to (E) described above as essential, and may further contain a component (F).

  The weight ratio of the component (A) is not particularly limited. However, if the component (A) is too much, the thixotropic composition of the present invention has a certain amount by using the component (C) and the component (B) in combination. Gives transparency, but does not give satisfactory transparency, and if there are few oil components, the essential physical properties expected of the thixotropic composition of the present invention are not expressed, and the commercial value may be reduced. (For example, when the component (A) is an aromatic component, there may be a problem of insufficient fragrance, and when the component is a repellent component, a sufficient repellent effect may not be obtained). In consideration, it is preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight of the whole composition.

  The weight ratio of the component (D) is not particularly limited, but preferably 0.1 to 5% by weight of the entire composition in consideration of the balance between thixotropic properties and transparency of the thixotropic composition of the present invention. More preferably, it is 0.5 to 2% by weight.

  The weight ratio of the component (E) is not particularly limited. However, when the layered clay mineral is hydrophilic, it is preferably 50% by weight or more, and more preferably 80% by weight from the viewpoint that it is easier to swell, disperse and dissolve. Or more, and particularly preferably 85% by weight or more.

  The total weight of the component (B) and the component (C) is not particularly limited, but if the component (A) is too much, the thixotropic property of the present invention is obtained by using the component (C) and the component (B) in combination. The composition is transparent to some extent, but it does not give satisfactory transparency, and if there are few oil components, the essential physical properties expected of the thixotropic composition of the present invention are not expressed and the commercial value decreases. (For example, if the component (A) is a fragrance component, there is a risk of insufficient fragrance, and if it is a repellent component, sufficient repellent effect may not be obtained) ), The amount is preferably 1 to 10 times the weight of the component (A), more preferably 2 to 5 times, particularly preferably 2 to 4 times.

  The ratio of the component (B) and the component (C) (component (B) / component (C), weight ratio) is not particularly limited, but the transparency of the thixotropic composition of the present invention is maintained even at a high temperature, Regardless of the amount of component (D), it is preferably in the range of 10/90 to 70/30, more preferably in the range of 15/85 to 50/50, particularly preferably 15 / It is in the range of 85 to 35/65.

  By satisfying the above blending conditions and the like, the composition of the present invention is in a state where the oil component is solubilized in water. Solubilization is to make the oily component appear to be transparently dissolved in water by the surfactant. Specifically, by the action of the surfactant, the oily component and the surfactant are minute micelles in water. And the micelles are sufficiently small so that they appear to melt. Solubilization is a thermodynamically stable system and is effective in preventing separation of oily components. In addition, the transparent appearance also provides the advantage of adding value to the product.

  The thixotropic composition of the present invention is preferably a composition having transparency. The term “having transparency” in the present invention does not need to be completely transparent, but refers to a state in which the opposite side of the container can be seen through. Specifically, a sample is placed in a glass cylindrical container (manufactured by Maruemu Co., Ltd., screw bottle, No. 7) with a body diameter of 35 mm, a total length of 78 mm, and a capacity of 50 ml, and black magic characters and printed characters having a thickness of about 25 mm are recorded. When the printed paper is placed just outside the container and the character is viewed from the opposite side of the container, the character can be read. As used herein, the immediate outer side refers to a point of 0 to 3 cm on the outer side of the glass cylindrical container.

  The thixotropic composition of the present invention can have a gel appearance by adjusting the viscosity of the composition by adjusting the amount of layered clay mineral added, and can also have fluidity. In the former case, it is difficult for the contents to come out of the container, and the commercial value can be increased with a characteristic appearance. In the latter case, the handling property can be adjusted by providing fluidity. For example, when the composition is too low in viscosity and splashes, the amount of layered clay mineral added can be increased to increase the viscosity and prevent splashing. Similarly, the dripping of the cleaning agent can be prevented.

Since the thixotropic composition of the present invention has thixotropic properties, it has the characteristics of good elongation and the characteristics of flowing through a thin tube even at high viscosity.
In the thixotropic composition of the present invention, other components than the above-described components may be contained within a range not impairing the physical properties. Examples of such components include antibacterial agents, preservatives, pigments, dyes, antifoaming agents, viscosity modifiers, thickeners, humectants, surfactants other than those described above, and the like. These components may be used alone or in combination of two or more.

  In some cases, the thixotropic composition of the present invention may cause water separation (a phenomenon in which water or a solubilizate leaks from a composition hardened in a gel state). The problem of water separation can be solved, for example, by using a thickener together.

[Method for producing thixotropic composition]
As a manufacturing method of the thixotropic composition of this invention, the method of mixing suitably the component (A)-(E) or component (A)-(F) demonstrated above can be mentioned, for example. There is no limitation in particular about the order etc. which mix each component. Further, a part of the components may be mixed in advance, and the mixture may be mixed with another mixture or component, and such a mixing operation may be repeated. In the individual steps of this method, the composition in the course of production may be heated. However, in most cases, the appearance of the resulting thixotropic composition is not different depending on the presence or absence of heating. On the contrary, when the component (A) is a volatile compound such as a fragrance, the volatile compound may be volatilized and lost by heating. On the other hand, in the gel-like fragrance using the natural polymer described in detail in the background art, for example, heating at 80 ° C. or higher is indispensable for gelation, so that volatilization of component (A) is avoided. There is a disadvantage of not.

  As a method for producing the thixotropic composition of the present invention, the step of solubilizing the component (A) in the component (E) using the component (B) and the component (C) and further using the component (F) as appropriate. A production method including (solubilization step) and a step of adding component (D) to the mixture obtained after or during the step (addition step) is preferable.

  In the solubilization step, the oil phase and the aqueous phase are mixed and the component (A) is solubilized in the component (E). In addition to the component (A), the component (B) and the component (C ), Component (F), and the like. In addition to the component (E), the aqueous phase can contain the component (B), the component (C), the component (F), and the like. That is, component (B), component (C), and component (F) may be added to either the oil phase or the aqueous phase. Moreover, when mix | blending another component, it can mix | blend arbitrarily with respect to any phase, and after making it solubilize, you may add separately.

  Although an addition process is a process of adding a component (D) to the mixture obtained after the solubilization process or during the solubilization process, Preferably a component (D) is added after a solubilization process. In that case, since the micelle in which the component (D) is solubilized is uniformly absorbed, it is preferable.

[Product stability]
The composition obtained by the above explanation has good product stability. “Good product stability” means that there is no change or little change in appearance, physical properties, etc. when the composition is compared immediately after preparation and after storage. If changes in appearance and physical properties appear, there is no commercial value. In the case of the composition in the present invention, the component (A) is solubilized in the component (E) to contain the oil component in the aqueous composition, but the component (A) is composed of the component (B) and the component ( It is solubilized in component (E) by the action of C). The thixotropic property is imparted by the component (D). To improve the product stability, the solubilization is not destabilized by the component (D), and the solubilized product is combined with the component (D). It is essential not to separate due to poor affinity, or to essentially stabilize solubilization. In order to satisfy these, the roles of the component (B) and the component (C) are important and essential. In particular, the usage amount and usage ratio in the ranges detailed are suitable and preferable. In addition to improving handling, component (F) also has a hydrotrope effect, which is thought to contribute to improved stability.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

[Examples 1 to 4]
In each example, first, a predetermined amount of each component shown in Table 1 was prepared, and each composition was prepared by the following manufacturing method.
While mixing and stirring oil component (component (A)), anionic surfactant (component (B)), nonionic surfactant (component (C)) and water-soluble organic solvent (component (F)) Water (component (E)) was slowly added so that the total amount was 100 parts by weight. After confirming that the oil component was uniformly solubilized in water, smectite-type hydrophilic layered clay mineral (component (D)) was added little by little while continuing to stir vigorously. The mixture was further stirred vigorously for 30 minutes to sufficiently disperse, swell and dissolve the smectite-type hydrophilic layered clay mineral, and then allowed to stand overnight to obtain a composition. During this period, the solid nonionic surfactant was heated and melted in order to blend in a predetermined amount, but heating was not performed otherwise, and the components were mixed and heated to prepare the composition. There wasn't.

The cloud point of the 1 wt% aqueous solution of component (C) was 56 ° C. for POE (9) secondary alkyl (C12-14) ether and 95 ° C. or higher for POE (60) hydrogenated castor oil.
About each obtained composition, the physical-property evaluation of 1-4 was performed below. These evaluation results are also shown in Table 1.

1. Evaluation of thixotropy The thixotropy of the composition was evaluated using a B-type viscometer. The viscosity of the composition was measured by changing the number of rotations (rotation speed) while keeping the type of the rotor constant. When the viscosity at 6 rpm was (Y) mPa · s and the viscosity at 60 rpm was (Z) mPa · s, thixotropy was evaluated based on the following evaluation criteria (Exhibit A to V). The rotor type was selected appropriately for each sample.
Party A: (Y) / (Z) ≧ 5
B: 2 <(Y) / (Z) <5
丙: (Y) / (Z) ≦ 2

2. The product stability evaluation composition was stored at each temperature, and the state after one month was observed. Product stability was evaluated based on the following evaluation criteria (I to III).
I: There is no difference in appearance after starting the test and after storing for 1 month.
II: A decrease in viscosity was confirmed after storage for 1 month.
III: What was transparent at the start of the test became cloudy. Alternatively, the layered clay mineral or gelling agent was separated.

3. Evaluation of Transparency The obtained composition was subjected to glass cylindrical containers (bore diameter 35 mm, total length 78 mm, capacity 50 ml, manufactured by Marum Co., Ltd., screw bottle, No. 7 at 5 ° C., room temperature and 40 ° C. ) For 3 days. Transparency was evaluated based on the following evaluation criteria (◯ to ×).
○: Transparency.
Δ: No transparency.
X: Not a uniform composition but separated.

4). Evaluation of Appearance Flow State After evaluating the transparency, the container containing the composition was inverted and the appearance flow state was evaluated based on the following evaluation criteria (A to C).
A: Gel-like and does not flow for 5 minutes or more even when the container is inverted.
B: Although it is a gel, it flows within 5 minutes after the container is inverted.
C: Flows.

FIG. 1 is a photograph of the container inverted after storage of the composition of Example 1 at room temperature for 3 days. The composition of Example 1 had transparency and was readable through the letters behind. It was the same transparency also about Examples 2-4. However, since the fragrance | flavor of Example 2 was yellow, the composition was also colored yellow, but the character behind was transparent and was readable.
As is apparent from Table 1 and FIG. 1, each composition of Examples 1 to 4 prepared without heating has thixotropic characteristics and transparency over a wide temperature range, and has a gel-like appearance and product stability. The property was good.

[Comparative Examples 1-4 and Examples 5-6]
In each comparative example and example, a predetermined amount of each component shown in Table 2 was prepared, and in the same manner as in the production method of Example 1, compositions were prepared and evaluated for physical properties. These evaluation results are also shown in Table 2.
In Comparative Examples 1 to 3, carrageenan (2 parts by weight), gellan gum (2 parts by weight), and carrageenan (1 part by weight), which are representative gelling agents that are not layered clay minerals, were used as the component (D). .

In Examples 5 and 6, laponite and bentonite, which are layered clay minerals, were used as the component (D).
In Comparative Example 4, smectite was used as the layered clay mineral, but no anionic surfactant was used.
FIG. 2 is a photograph of the container inverted after storage of the composition of Comparative Example 1 at room temperature for 3 days. In Comparative Example 1, the transparency was insufficient and the characters behind were not visible.

  As is apparent from Table 2 and FIG. 2, the compositions of Comparative Examples 1 to 3 have no thixotropic properties, and in most cases the transparency is not so much when not heated during preparation. Further, the composition of Comparative Example 4 was poor in product stability.

*: “Lucentite SWF” manufactured by Cape Chemical Co., Ltd.
1) In the component names in Table 1, “POE” represents “polyoxyethylene”. The same applies to the following tables.
2) The numbers shown in parentheses in the names of the components in Table 1 indicate the average degree of polymerization of ethylene oxide if the immediately preceding point is “POE”. Moreover, C and a number shown in parentheses indicate the number of carbons constituting the immediately preceding alkyl group. The same applies to the following tables.

It is the photograph which inverted the container after preserve | saving the composition of Example 1 at room temperature for 3 days. It is the photograph which inverted the container after preserve | saving the composition of the comparative example 1 at room temperature for 3 days.

Claims (7)

A thixotropic composition comprising the following components (A) to (E) as essential components.
(A) Oil component (B) At least one anionic surfactant selected from a sulfate ester type anionic surfactant and a sulfonic acid type anionic surfactant (C) Nonionic surfactant (D) Layered clay mineral (E) water   The thixotropic composition according to claim 1, which has transparency.   The thixotropic composition according to claim 1 or 2, wherein the component (D) is a smectite-type hydrophilic layered clay mineral.   The thixotropic composition according to any one of claims 1 to 3, wherein the component (C) has a 1% by weight aqueous solution having a cloud point of 20 ° C or higher. The weight ratio of the component (A) is 0.5 to 10% by weight of the whole composition, the weight ratio of the component (D) is 0.1 to 5% by weight of the whole composition, and the weight ratio of the component (E). Is 50% by weight or more of the total composition,
The total weight of the component (B) and the component (C) is 1 to 10 times the weight of the component (A), and the component (B) / component (C) is 10/90 to 70/30 ( Weight ratio)
The thixotropic composition according to any one of claims 1 to 4, wherein the clouding point of the 1% by weight aqueous solution of the component (C) is 20 ° C or higher.   The said component (A) contains at least 1 sort (s) of component selected from the aromatic component, the agrochemical component, the repellent component, the deodorant component, the insect repellent component, the insecticidal component, the disinfecting component, and the cleaning component. The thixotropic composition according to any one of the above. The thixotropic composition according to any one of claims 1 to 6, further comprising a component (F) shown below.
(F) Water-soluble organic solvent