JP6425518B2 - Spray composition and spray apparatus using the same - Google Patents

Description

  The present invention relates to a spray composition and a spray apparatus using the same.

  Spray products are used in a wide range of products such as hair care products, skin care products, fragrances, cleaning agents, various coatings, and agrochemicals. And many spray products are commercialized by filling a liquid composition into a spray device. The properties desired for a spray product are that it can be sprayed under a wide range of environmental conditions (temperature, humidity etc.) using a common spray container, and the spray droplets are of suitable size depending on the application used, and Non-uniform spraying may not occur, and dripping may be less likely to occur when spraying on a vertical surface or an inclined surface.

  By the way, many sprayable gel-like compositions have been proposed in recent years (see Patent Documents 1 to 4). These sprayable gel-like compositions exhibit the excellent property that no dripping occurs when they are sprayed on vertical surfaces or inclined surfaces.

  For example, Patent Document 1 proposes a gel-like mist cosmetic product using smectite which is a clay mineral, and Patent Document 2 gives a gel-like spray composition using hectorite which is also a clay mineral. Things have been proposed. These clay minerals have very small particles, so they swell with water and other solvents and disperse to form sol-gel. Dispersions of these clay minerals have thixotropic properties, and therefore, they exhibit a property of liquefying when pressure (force) is applied at a certain level or more and gelling immediately when pressure (force) is removed. By using this property unique to clay minerals, it becomes possible to spray without generating drips by combining the above-mentioned spray composition with a spray container.

  Further, Patent Document 3 proposes an aerosol composition in which a high-viscosity aqueous stock solution is sprayed in the form of a mist to adhere uniformly without dripping. Cellulose thickeners and crosslinkable acrylic thickeners are used in this aqueous stock solution, and these thickeners do not exhibit stringiness (stringiness) even at high viscosity, and It can be an excellent gel-like spray composition because it exhibits high thixotropy.

Further, in Patent Document 4, the average degree of polymerization (DP) is 100 or less, the fraction of cellulose I-type crystal component is 0.1 or less, and the fraction of cellulose II-type crystal component is 0.4 or less, A composition comprising cellulose fine particles having an average particle size of 2 μm or less and a liquid dispersion medium, wherein the concentration of cellulose in the composition is 0.1 to 5.0% by weight, and the composition Maximum viscosity in a viscosity-shear stress curve measured at 25 ° C in the shear rate region including at least 1 × 10 ^-3 S ^-1 to 1 × 10 ² S ^-1 measured using a cone-plate type rotational viscometer of Compositions for sprays have been proposed which are characterized in that the value (η _max ) is _{max max} 11 × 10 ³ mPa · s. The cellulose fine particles used in the spray composition can be obtained by acid hydrolysis treatment of natural cellulose or regenerated cellulose. The composition for spray using cellulose particles as described above is transparent in an aqueous medium, the mother liquid drops are well fixed on the sprayed surface, and the uneven spray hardly occurs, and the vertical surface and the inclined surface of the mother liquid drop Have excellent properties such as no occurrence of liquid dripping.

Japanese Patent Application Laid-Open No. 9-241115 JP-A-2000-51682 JP, 2006-321760, A JP 2003-73229

  However, the spray compositions described in Patent Document 1 and Patent Document 2 are used for applications where transparency is required because the dispersion is opaque due to the dispersion of the clay mineral and the coloring unique to the clay mineral is observed. There is a problem that it can not do. In addition, there is also a problem that powder spray is likely to occur when the sprayed coating is dried. Furthermore, when alcohol is present in the solvent, there is also a problem that the clay mineral coagulates and the spray characteristics (spray characteristics) are greatly reduced.

  Further, the spray composition of Patent Document 3 is characterized in that the thickener (in particular, a crosslinkable acrylic thickener) decreases in function in the presence of a salt such as an electrolyte or an ionic substance, The viscosity is greatly reduced. Therefore, there is a problem that there is a limitation in functional additives (electrolytes, ionic substances, etc.) which can be blended when used as a spray composition requiring viscosity.

  Further, in the spray composition of Patent Document 4, when a substance having an ionic property such as an anionic surfactant, an inorganic salt, carboxymethylcellulose, etc. is added, hydration of cellulose molecules is caused even if a small amount is added. Is inhibited to cause aggregation and sedimentation. Although various functional additives such as ionic substances are usually blended into the composition for spray and commercialized, the cellulose fine particles described in Patent Document 4 can be blended with functional additives from the above circumstances. There is a problem that there is a limitation in

As described above, the sprayable gel compositions proposed conventionally have problems as shown in the following (1) and (2).
(1) The application to be used is limited, and powder spray occurs when the sprayed coating is dried.
(2) In the presence of an ionic substance, an electrolyte, etc., the viscosity is greatly reduced and the gel state can not be maintained, or the aggregation and sedimentation of the thickener itself are observed.

  The present invention has been made in view of such circumstances, and the viscosity does not decrease even in the presence of functional additives such as electrolytes and ionic substances, and the gel shape is maintained with stability over time, and spraying is performed. It is an object of the present invention to provide a spray composition that can be used and a spray apparatus using the composition.

[1] Containing the following components (A) and (B), the content ratio of the cellulose fiber of the component (A) is 1.0 mass% or more and 2.0 mass% or less, and a cone and plate type rotation by measurement of the ^{viscometer, 1 × 10 -3 S -1 ~1} × 10 3 in the shear rate region including the S ^-1, the maximum value of the viscosity measured at 20 ℃ (η _max) is η _max ≧ 5 × 10 ⁴ A spray composition characterized by having a mPa · s and a minimum value (η _min ) of η _min ≦ 1 × 10 ² mPa · s.
(A) Cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced to a hydroxyl group in a cellulose molecule, a substitution degree is 0.01 or more and 0.5 or less, And / or a cellulose fiber having a crystal structure of type II and an aspect ratio of 50 or more.
(B) water.
[2] A spray composition containing the following component (C) together with the components (A) and (B) as a preferred embodiment.
(C) functional additive.
[3] As a preferred embodiment, the functional additive of the component (C) is an electrolyte, an ionic substance, a surfactant, an oil, a moisturizer, an organic fine particle, an inorganic fine particle, an antiseptic, a deodorant and a fragrance The composition for spray which is at least one chosen from the group which consists of.
[4] A spray spray apparatus containing the above-mentioned spray composition.

  The spray composition of the present invention contains special cellulose fibers and water as essential components, and also contains functional additives (electrolyte, ionic substance, etc.) according to the purpose and necessity. Thus, the above-mentioned composition of the present invention can be maintained in a stable gel state with time even when it contains functional additives such as electrolytes and ionic substances, and so is required for its use. Various functional additives can be blended without any problem. Moreover, since the composition for spraying of this invention is liquefied immediately by the spray pressure when spraying, it can spray-coat favorably. And since the mother droplets thus spray-coated are gelled again, the fixability is also good, non-uniform spray is difficult to occur, and no dripping occurs on the vertical surfaces or inclined surfaces of the mother droplets. Moreover, the coating film formed by the composition for spray of this invention does not produce powder blowing even if it dries.

  And the spray apparatus which accommodates the said composition for sprays can exhibit the effect peculiar to the above composition for sprays of this invention more effectively.

  Next, embodiments of the present invention will be described in detail.

As described above, the spray composition of the present invention contains the following components (A) and (B), and the content ratio of the cellulose fiber of the component (A) is 0.1 to 3.0% by weight , and the and, by the measurement of the cone and plate rotational viscometer, at shear rate region including the ^{1 × 10 -3 S -1 ~1 ×} 10 3 S -1, the maximum value of the viscosity measured at 20 ° C. (eta _max ) is η _max 11 × 10 ⁴ mPa · s, and the minimum value (η _min ) is η _min ≦ 1 × 10 ² mPa · s.
(A) Cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced to a hydroxyl group in a cellulose molecule, a substitution degree is 0.01 or more and 0.5 or less, And / or a cellulose fiber having a crystal structure of type II and an aspect ratio of 50 or more.
(B) water.

  The number average fiber diameter of (A) of the present invention is 2 nm or more and 500 nm or less, and a substituent is introduced to the hydroxyl group in the cellulose molecule, and the degree of substitution is 0.01 or more and 0.5 or less. It is a cellulose fiber which has a crystal structure of a type | mold and / or a type II, and an aspect ratio of 50 or more.

  The number average fiber diameter is 2 nm or more and 500 nm or less, more preferably 2 nm or more and 150 nm or less. If the number average fiber diameter is more than 500 nm, the cellulose fibers will precipitate, so that it will not be in a uniform gel state.

  Here, the analysis of the number average fiber diameter can be performed, for example, as follows. That is, an aqueous dispersion of cellulose fiber of 0.05 to 0.1% by mass in solid content ratio is prepared, and the dispersion is cast on a hydrophilized carbon film-coated grid to obtain a transmission electron microscope Let it be a sample for observation of (TEM). In addition, when the fiber of the big fiber diameter besides this invention is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times or 50000 times depending on the size of the fibers to be constructed. At this time, an axis of an arbitrary image width in the vertical and horizontal directions is assumed in the obtained image, and the sample and observation conditions (such as magnification) are adjusted such that 20 or more fibers intersect with the axis. Then, after obtaining an observation image that satisfies this condition, a random axis is drawn for each image of two vertical and horizontal lines per image, and the fiber diameter of fibers intersecting with the axis is read visually. In this way, images of at least three non-overlapping surface portions are taken with an electron microscope, and the fiber diameter values of fibers intersecting each other on two axes are read (thus, at least 20 x 2 x 3 = 120) Information on the fiber diameter of the book is obtained). The number average fiber diameter is calculated from the data of the fiber diameter obtained in this manner.

  The above-mentioned substituent is not particularly limited as long as it has a substituent that produces an ether bond with the hydroxyl group in the cellulose molecule. Specifically, carboxymethyl group, methyl group, ethyl group, cyanoethyl group, hydroxyethyl group, hydroxypropyl group, ethylhydroxyethyl group, hydroxypropylmethyl group and the like can be mentioned. Among these, a carboxymethyl group is preferable.

  The degree of substitution represents the average value of the number of moles of substituents per mole of anhydroglucose unit.

  The degree of substitution of the (A) cellulose fiber of the present invention is 0.01 or more and 0.5 or less, more preferably 0.01 or more and 0.25 or less. If the degree of substitution is less than 0.01, it is difficult to disintegrate the cellulose fiber, and if it is more than 0.5, it is difficult to express the effects of the present invention because the thickening property and the dispersion stability decrease.

  The (A) cellulose fiber of the present invention has a crystal structure of type I and / or type II. Having a crystal structure is, for example, an X-ray diffraction pattern typical for cellulose type I or type II (type I: diffraction angle 2θ = 14.8 °, 16 in a diffraction profile obtained by wide-angle X-ray diffraction image measurement) It can be confirmed from the fact that it has 8 °, 22.6 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °).

  The (A) cellulose fiber of the present invention has an aspect ratio of 50 or more. More preferably, it is 100 or more. When the aspect ratio is less than 50, there is a problem that it is difficult for the gel composition to maintain the gel-like properties.

The aspect ratio of the above-mentioned cellulose can be measured, for example, by the following method. That is, after casting cellulose onto a hydrophilized carbon film-coated grid, the number average width and length of the narrow width of cellulose are obtained from a TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate. The number average width of the width was observed. That is, the number average width of the short width and the number average width of the long width were calculated according to each of the methods described above, and the aspect ratio was calculated according to the following equation (1) using these values. .

本発明の（Ａ）セルロース繊維を得るためには、下記に例示するセルロースを公知の方法を用いてアニオン変性させることが必要である。その一例として次のような製造方法をあげることができる。セルロースを原料とし、溶媒に重量で３〜２０倍の低級アルコール、具体的にはメタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｔ−ブチルアルコール等の単独、又は２種以上の混合物と水の混合媒体を使用する。なお、低級アルコールの混合割合は、６０〜９５質量％である。マーセル化剤としては、セルロースのグルコース残基当たり０．５〜２０倍モルの水酸化アルカリ金属、具体的には水酸化ナトリウム、水酸化カリウムを使用する。セルロースと溶媒、マーセル化剤を混合してマーセル化処理を行う。このときの反応温度は０〜７０℃、好ましくは１０〜６０℃であり、反応時間は１５分〜８時間、好ましくは３０分〜７時間である。その後、カルボキシメチル化剤をグルコース残基当たり０．０５〜１０．０倍モル添加してエーテル化反応を行う。このときの反応温度は３０〜９０℃、好ましくは４０〜８０℃であり、反応時間は３０分〜１０時間、好ましくは１時間〜４時間である。

In order to obtain the (A) cellulose fiber of the present invention, it is necessary to anionically modify the cellulose exemplified below using a known method. The following manufacturing method can be mentioned as an example. Cellulose is used as a raw material and 3 to 20 times by weight lower alcohol as solvent, specifically methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol etc. alone or Use a mixed medium of two or more mixtures and water. The mixing ratio of the lower alcohol is 60 to 95% by mass. As the mercerizing agent, 0.5 to 20 moles of alkali metal hydroxide, specifically sodium hydroxide and potassium hydroxide, are used per glucose residue of cellulose. The cellulose is mixed with a solvent and a mercerizing agent to perform mercerization treatment. The reaction temperature at this time is 0 to 70 ° C., preferably 10 to 60 ° C., and the reaction time is 15 minutes to 8 hours, preferably 30 minutes to 7 hours. After that, an etherification reaction is carried out by adding 0.05 to 10.0 times moles of a carboxymethylating agent per glucose residue. At this time, the reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is 30 minutes to 10 hours, preferably 1 hour to 4 hours.

  The cellulose raw material of the present invention dissolves cellulose in natural cellulose such as bleached or unbleached wood pulp, purified linters, cellulose produced by microorganisms such as acetic acid bacteria or the like in a copper ammonia solution, morpholine derivative, etc. Examples of the regenerated cellulose that has been spun, and fine cellulose that has been depolymerized by hydrolysis, alkaline hydrolysis, enzymatic decomposition, explosion treatment, vibration ball milling treatment or the like of the above-mentioned cellulose-based material, or fine cellulose that has been mechanically treated.

  The (A) cellulose fiber of the present invention can be obtained by defibrillating an anion-modified cellulose using a high pressure homogenizer or the like. A high pressure homogenizer is a device which pressurizes a fluid by means of a pump and ejects it from a very fine gap provided in a flow path. Emulsification, dispersion, fibrillation, pulverization, and ultra-refining can be performed by integrated energy such as collision between particles and shear force due to pressure difference.

The processing conditions by the homogenizer of the present invention are not particularly limited, but the pressure conditions are 30 MPa or more, preferably 100 MPa or more, and more preferably 140 MPa or more. In addition, prior to disintegration and dispersion treatment with a high-pressure homogenizer, if necessary, pretreatment treatment is performed on the anion-modified cellulose using known mixing, stirring, emulsifying, and dispersing equipment such as a high-speed shear mixer. Is also possible.
Next, (B) water is used together with the spray composition of the present invention and the (A) cellulose fiber.

  Examples of the functional additive (C) optionally used together with the above (A) cellulose fiber and (B) water include, for example, electrolytes, ionic substances, surfactants, oils, moisturizers, organic fine particles, inorganic There are fine particles, preservatives, deodorants, perfumes, organic solvents and the like. In particular, the spray composition of the present invention has a high viscosity indicating a gel state even when it contains an electrolyte or an ionic substance (including an ionic surfactant), and causes separation or water separation. Since it has the feature of maintaining the gel state without, it can exhibit excellent performance in a spray composition in which these functional additives are required.

  Examples of the electrolyte and ionic substance include alkali metals such as sodium chloride, sodium edetate and sodium ascorbate, alkaline earth metals, transition metals, etc., hydrogen halide, sulfuric acid, carbonic acid, and carboxyl group in the molecule. Salts with organic acids having one or more of them, sodium alkylsulfosuccinates, sodium alkylsulfonates, alkyl sulfates, sulfonates such as polyoxyethylene alkyl sulfates, alkylbenzene sulfonates, etc., poly A phosphate ester surfactant such as oxyethylene alkyl phosphate ester, which can be dissolved and dispersed in a dispersion medium such as water, is used.

  As the nonionic surfactant, for example, propylene glycol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, Polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene lanolin, polyoxyethylene Ethylene lanolin alcohol, polyoxyethylene beeswax derivative, polyvinyl alcohol Polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensates and the like.

  As oils, for example, jojoba oil, macadamia nut oil, avocado oil, evening primrose oil, mink oil, rape seed oil, castor oil, sunflower oil, corn oil, cocoa oil, coconut oil, rice bran oil, olive oil, almond oil, sesame oil, safflower oil Flower oil, soybean oil, soy sauce, persic oil, mink oil, cottonseed oil, sea cucumber oil, palm oil, palm kernel oil, egg yolk oil, lanolin, natural oil such as squalene, synthetic triglyceride, squalane, liquid paraffin, vaseline, ceresin, Hydrocarbons such as microcrystalline wax and isoparaffins, waxes such as carnauba wax, paraffin wax, spermaceti wax, beeswax, beeswax, candelilla wax, lanolin, higher alcohols (cetanol, stearyl alcohol, lauryl alcohol, cetostearyl alcohol , Oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyl dodecanol, etc.), lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, linolenic acid, linoleic acid, oxy Higher fatty acids such as stearic acid, undecylenic acid, lanolin fatty acids, hard lanolin fatty acids, soft lanolin fatty acids, cholesterol such as cholesteryl-octyldodecyl-behenyl and derivatives thereof, isopropyl myristic acid, isopropyl palmitic acid, isopropyl stearic acid, 2-ethyl hexane Acid glycerol, esters such as butyl stearic acid, diethylene glycol monopropyl ether, polyoxyethylene polyoxypropylene pen Polar oils such as erythritol ether, polyoxypropylene butyl ether, ethyl linoleate, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, one-end reactive silicone , Heterofunctionally modified silicone, polyether modified silicone, methylstyryl modified silicone, alkyl modified silicone, higher fatty acid ester modified silicone, hydrophilic special modified silicone, higher alkoxy modified silicone, higher fatty acid containing silicone, fluorine modified silicone etc. Etc. These may be used alone or in combination of two or more.

  More specifically, the silicones are dimethylpolysiloxane, methylphenylpolysiloxane, methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, methylcyclopolysiloxane, octamethyl Trisiloxane, decamethyltetrasiloxane, polyoxyethylene / methylpolysiloxane copolymer, polyoxypropylene / methylpolysiloxane copolymer, poly (oxyethylene · oxypropylene) methylpolysiloxane copolymer, methylhydrogenpolysiloxane Tetrahydrotetramethylcyclotetrasiloxane, stearoxymethylpolysiloxane, cetoxymethylpolysiloxane, methylpolysiloxane emulsion, high If methylpolysiloxane, trimethylsiloxysilicate, crosslinked methylpolysiloxane, a crosslinked methylphenyl polysiloxane.

  As a humectant, polyhydric alcohols such as glyceryl trioctanoate, maltitol, sorbitol, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycol, etc., organic acids such as sodium pyrrolidonecarboxylate, sodium lactate, sodium citrate and the like And their salts, hyaluronic acid and its salts such as sodium hyaluronate, hydrolysates of yeast and yeast extract, fermented products such as yeast culture fluid and lactic acid bacteria culture fluid, water-soluble proteins such as collagen, elastin, keratin and sericin, collagen Hydrolysates, casein hydrolysates, silk hydrolysates, peptides such as sodium polyaspartate and salts thereof, trehalose, xylobiose, maltose, sucrose, glucose, saccharides / polysaccharides such as vegetable mucus polysaccharides and the like Derivative Glycosaminoglycans and their salts such as water-soluble chitin, chitosan, pectin, chondroitin sulfate and salts thereof, amino acids such as glycine, serine, threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine, prophosphoric acid Sugar amino acid compounds such as amino carbonyl compounds, plant extracts such as aloe and maronie, trimethylglycine, urea, uric acid, ammonia, lecithin, lanolin, squalane, squalene, glucosamine, creatinine, DNA, RNA, etc. can give. These may be used alone or in combination of two or more.

  Examples of the organic fine particles include latex-emulsion obtained by emulsion polymerization of styrene-butadiene copolymer latex, acrylic emulsion and the like, and a polyurethane water dispersion. Further, examples of the inorganic fine particles include inorganic fine particles such as zeolite, montmorillonite, asbestos, smectite, mica, fumed silica, colloidal silica, titanium oxide and the like. These fine particles are desirably micronized so as to have an average particle size of 10 μm or less, preferably 5 μm or less, so as not to impair the spray characteristics.

  Examples of preservatives include methyl paraben, ethyl paraben and the like.

  Deodorants and flavors include limonene, decylaldehyde, menthone, plegon, eugenol, cinnamaldehyde, benzaldehyde, menthol, peppermint oil, lemon oil, orange oil, deodorant active ingredients extracted from each organ of plants (for example, water And deodorizing active ingredients) extracted from each organ of Scutellaria barbata, Dokudami, Tsukasa, Ginkgo biloba, Pinus sylvestris, Japanese red pine, Japanese red pine, lizards, lilacs, butterburs, Japanese persimmons, Japanese persimmons, Japanese persimmons, and forsythia Can be mentioned. These may be used alone or in combination of two or more.

  Examples of organic solvents include water-soluble alcohols (methanol, ethanol, isopropyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol, methyl cellosolve, ethyl cellosolve, ethylene glycol, glycerin, etc.), ethers (ethylene Examples include glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran and the like, ketones (acetone, methyl ethyl ketone), N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like. These may be used alone or in combination of two or more.

  These functional additives are used singly or in combination of two or more according to the application field of the spray composition of the present invention and the required performance, and the compounding amount thereof is also according to the required performance. It is used in the appropriate range.

  The spray composition of the present invention can be prepared by dispersing the components of the above (A) cellulose fiber and (B) water [and optionally, (C) functional additive etc.] with various dispersers. Be prepared. As this disperser, the same disperser as that used when preparing (A) cellulose fiber is used. Further, as described above, (B) water (dispersion medium) or (C) functional additive may be added at the time of (A) preparation of cellulose fiber (during refinement). After preparing (A) cellulose fiber, water and a functional additive may be added, and dispersion may be performed by the above-mentioned disperser. In addition, since (A) cellulose fiber also functions as an emulsion stabilizer, when the oils are blended, the cellulose fiber dispersion and the oils are prepared in advance according to the method of preparing the O / W type emulsion of a conventional method. do it. In that case, you may use together nonionic surfactant etc. which become an emulsion stabilizer, and the compounding quantity of a cellulose fiber will be determined in consideration of emulsion stability and spray property.

In the spray composition of the present invention, the viscosity and the content ratio of the (A) cellulose fiber are adjusted to a specific range from the viewpoint of the size of the mother droplet and the like. That is, in the present invention, the content of cellulose fibers of the component (A) is 0.1 to 3.0 wt%, and, by the measurement of the cone and plate rotational viscometer, 1 × 10 ^-3 S ^- The maximum value (η _max ) of the viscosity measured at 20 ° C. in the shear rate region including ¹ to 1 × 10 ³ S ⁻¹ is set as η _max 11 × 10 ⁴ mPa · s. Good spray application is possible without dripping. Further, in the present invention, since the minimum value (η _min ) of the viscosity is set as η _min 11 × 10 ² mPa · s, it is sprayed as a fine mother droplet and no unevenness occurs. On the contrary, with a low viscosity composition having a value of の_max of less than 1 × 10 ⁴ mPa · s, it is impossible to expect the dripping prevention property of the spray droplets, and the value of η _min is 1 × 10 ^When it exceeds ² mPa · s, the mother liquid drops become large and spray unevenness occurs. In addition, when the application density in spray spraying is relatively low, if 液_max 11 × 10 ⁴ mPa · s is satisfied, sufficient anti-drip properties can be expected, but in the case of thick application, etc. Even if 起_こり_max 11 × 10 ⁴ mPa · s can not be prevented from dripping prevention, the spray composition of the present invention such as dripping prevention under any conditions of spray application It is preferable that 効果_max 55 × 10 ⁴ mPa · s in order to sufficiently express the effect. In addition, at normal coating density, no spray unevenness occurs if η _min ≦ 1 × 10 ² mPa · s, but if you want to spray very thin uniformly, 薄 く_min ≦ 5 × 10 ¹ mPa · s Is preferred. Further, in the spray composition of the present invention, the value of 噴霧_max preferably does not exceed 10 ⁹ mPa · s as a range in which spraying can be stably performed.

  The spray composition of the present invention has high thixotropy, so when it is used as a spray, the viscosity can be lowered during spray spraying to achieve good spraying, but after spraying, the droplets are fixed on the coated surface Since the viscosity is recovered by then, dripping after fixing on the surface is extremely difficult to occur. Furthermore, the composition for spray according to the present invention does not decrease in viscosity even at high temperatures of 50 ° C. or higher, is excellent in temperature stability, has no stickiness unique to water-soluble polymers, and is excellent in spreadability after application. It has the nature.

  And the spray apparatus of this invention accommodates the said composition for spraying in a spray apparatus. The above-mentioned spray device can be easily filled with the above-mentioned composition, enables spray, and functions as a spray agent, but in consideration of versatility and high accuracy of spray performance, the following three forms (1) to (3) are preferable.

  (1) Dispenser-type sprayer equipped with a sprayable pump-type nozzle: This sprayer can operate the spray at atmospheric pressure, does not require pressurized gas, etc., and has a relatively simple container structure for safety. It is a high, portable sprayer. The structure consists of an extrusion pump type nozzle equipped with a suction tube and a screw type container for fixing it and filling the above composition. The dispenser-type spray device mentioned here includes all devices in which the structure of the pump-type nozzle has been improved in order to enhance the spray performance. The spray characteristics depend on the hole diameter of the discharge nozzle, the extrusion volume per one discharge of the pump, and the like, but these conditions are selected according to the purpose.

  (2) Trigger sprayer: A trigger sprayer is a sprayer for household detergents, clothing pastes, kitchen detergents, etc., and a pistol trigger sprayer is mounted on the mouth of the container body filled with the above composition. It can be operated at atmospheric pressure and is highly versatile as a liquid sprayer. The trigger sprayer referred to here includes all improvements of the trigger spray device in order to enhance the spray performance.

  (3) Aerosol sprayer: The aerosol sprayer enables continuous atomization or continuous foam formation which can not be realized by the above-mentioned two spray devices by filling the container with a propellant. The aerosol type sprayer referred to here includes all the ones in which the injection device portion of the aerosol type container is improved. In general, atomization using the present sprayer enables finer spray compared to the above two sprays performed under atmospheric pressure. Examples of the propellant used in the aerosol type spray include dimethyl ether, liquefied petroleum gas, carbon dioxide gas, nitrogen gas, argon gas, air, oxygen gas, fluorocarbon gas, etc. These may be used alone or in combination of two or more. Be

  Even when any of these spray devices is used, by using the composition for spray of the present invention as the mother liquor, the contents in the spray device become gel-like, so the mother liquor does not flow inside the container. This enables atomization in all directions of the spray device. In extreme cases, it can be sprayed upside down and will work well as a sprayer.

Next, an example will be described together with a comparative example. However, the present invention is not limited to these examples.
<Method of measuring degree of substitution per glucose unit>
A cellulose fiber is prepared in a 0.6 mass% slurry, and 0.1 M hydrochloric acid aqueous solution is added to adjust to pH 2.4, and then 0.05 N aqueous sodium hydroxide solution is dropped to adjust the electric conductivity until pH reaches 11 It measured and the carboxyl group amount was measured from the amount of sodium hydroxide consumed in the neutralization stage of the weak acid in which the change of electrical conductivity is moderate, and it computed using the following Formula. The degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.

＜数平均繊維径の測定方法＞
セルロース繊維に水を加えて２質量％のスラリーとして、ディスパー型ミキサーを用いて回転数８，０００ｒｐｍで１０分間微細化処理を行った。各セルロース繊維の最大繊維径および数平均繊維径を、透過型電子顕微鏡（ＴＥＭ）（日本電子社製、ＪＥＭ−１４００）を用いて観察した。すなわち、各セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、２％ウラニルアセテートでネガティブ染色したＴＥＭ像（倍率：１００００倍）から、先に述べた方法に従い、数平均繊維径を算出した。

<Method of measuring number average fiber diameter>
Water was added to the cellulose fiber to form a 2% by mass slurry, which was subjected to a refining treatment for 10 minutes at a rotation number of 8,000 rpm using a disper type mixer. The maximum fiber diameter and number average fiber diameter of each cellulose fiber were observed using a transmission electron microscope (TEM) (manufactured by JEOL Ltd., JEM-1400). That is, after casting each cellulose fiber on a hydrophilized carbon film-coated grid, a number average fiber diameter is obtained according to the method described above from a TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate. Was calculated.

<Method of confirming crystal structure>
A wide-angle X-ray diffraction image is measured using an X-ray diffractometer (RINT-Ultima 3 manufactured by RIGAKU Co., Ltd.), and an X-ray diffraction pattern (type I: typical of cellulose type I or type II) is shown in the diffraction profile of each cellulose fiber. If the diffraction angle 2θ = 14.8 °, 16.8 °, 22.6 °, type II: the diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °) is observed, the crystal structure is possessed. I judged.

<Method of measuring aspect ratio>
After casting cellulose onto a hydrophilized carbon film-coated grid, the number average width of the narrow width of cellulose and the width of the wide width are obtained from a TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate. The number average width of was observed. That is, the number average width of the short width and the number average width of the long width were calculated according to each of the methods described above, and the aspect ratio was calculated according to the above equation (1) using these values. .

(Production of cellulose fiber)
Production Example 1
To a stirrer, 200 g of dry pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) and 18 g of dry sodium hydroxide were added, and water was added so that the concentration of pulp solids becomes 15%. Then, after stirring at 30 ° C. for 30 minutes, the temperature was raised to 70 ° C., and 23 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a degree of substitution of 0.01 per glucose unit. Thereafter, water is added to the anion-modified pulp to make the solid concentration 5%, and treated 5 times with a high pressure homogenizer at 20 ° C. and a pressure of 140 MPa, and having a number average fiber diameter of 74 nm and an aspect ratio of 67. A dispersion of fiber 1 was obtained.

Production Example 2
A dispersion of cellulose fiber 2 was obtained in the same manner as in Production Example 1, except that 176 g of sodium hydroxide and 234 g of sodium monochloroacetate were changed (in terms of active ingredient). The degree of substitution per glucose unit of the obtained cellulose fiber was 0.10, the number average fiber diameter was 10 nm, the aspect ratio was 140, and it had a crystal structure.

Production Example 3
A dispersion of cellulose fibers 3 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 308 g and sodium monochloroacetate to 410 g (in terms of active ingredient). The degree of substitution per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter was 6 nm, the aspect ratio was 160, and it had a crystal structure.

Production Example 4
A dispersion of cellulose fibers 4 was obtained in the same manner as in Production Example 1, except that 9 g of sodium hydroxide and 12 g of sodium monochloroacetate were changed (in terms of active ingredient). The degree of substitution per glucose unit of the obtained cellulose fiber was 0.005, the number average fiber diameter was 620 nm, the aspect ratio was 18, and it had a crystal structure.

Production Example 5
A dispersion of cellulose fibers 5 was obtained in the same manner as in Production Example 1, except that 476 g of sodium hydroxide and 632 g of sodium monochloroacetate were changed (in terms of active ingredient). The degree of substitution per glucose unit of the obtained cellulose was 0.6, the number average fiber diameter could not be measured, and no crystal structure was observed.

Production Example 6
A dispersion of cellulose fiber 6 was obtained in the same manner as in Production Example 1, except that 308 g of sodium hydroxide and 410 g of sodium monochloroacetate (in terms of active ingredient) were changed to 20 treatments with a high pressure homogenizer. The degree of substitution per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter could not be measured, and no crystal structure was observed.

Production Example 7
In a stirrer, 200 g of dry pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) and 308 g of dry sodium hydroxide were added to a stirrer, and water was added so that the pulp solid concentration would be 15%. Then, after stirring at 70 ° C. for 9 hours, 410 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain an anion-modified cellulose having a degree of substitution of 0.28 per glucose unit. Thereafter, water was added to the anion-modified pulp to obtain a solid content concentration of 5%, and the dispersion was treated with a high-pressure homogenizer five times at 20 ° C. and a pressure of 140 MPa to obtain a dispersion of cellulose fibers 7. The number average fiber diameter could not be measured, and no crystal structure was found.

(Evaluation of sprayability 1)
Examples 1-1 to 1-9
Ion-exchanged water is added to the above cellulose fibers 1 to 3 and adjusted to the concentration (solid content conversion) shown in Table 1 below, and then a homomixer (manufactured by Primix, T. K Robomix, 8,000 rpm x 10 minutes) is used The sample was prepared by dispersing.

Comparative Examples 1-1 and 1-2
Ion-exchanged water is added to a commercially available thickener, carboxyvinyl polymer (product name: Carbopol 980, manufactured by BF Goodrich), adjusted to the concentration shown in Table 1 below (solid content conversion), and then homomixer (Plymix Co., Ltd. The sample was prepared by dispersing using T.K. ROVO MIX (8,000 rpm x 10 minutes).

[Comparative Examples 1-3, 1-4]
A sample was prepared by dispersing in the same manner as Comparative Examples 1-1 and 1-2 except that the carboxyvinyl polymer was changed to polyacrylamide (average molecular weight: 9,000,000 to 10,000,000, manufactured by Kishda Chemical Co., Ltd.).

[Comparative Examples 1-5, 1-6]

A sample was prepared by dispersing in the same manner as in Comparative Examples 1-1 and 1-2 except that the carboxyvinyl polymer was changed to synthetic smectite fine particles (product name: Smecton SA, manufactured by Kunimine Industries, Ltd.).
Each sample was evaluated by the following evaluation method. The evaluation results are shown in Table 1 below.

〔Evaluation method〕
[Flow characteristics]
C. in the shear rate region including 1 × 10 ^-3 S ^-1 to 1 × 10 ³ S ^-1 as measured by a cone and plate type rotational viscometer (Rheosol-G2000, manufactured by UBM) of the above sample The maximum value (ηmax) and the minimum value (ηmin) of the measured viscosity were determined.
X: η max <1 × 10 ⁴ mPa · s or min min> 1 × 10 ² mPa · s
○: max max 11 × 10 ⁴ mPa · s and min min ≦ 1 × 10 ² mPa · s.
The above samples were each filled in 20 mL in a commercially available dispenser-type spray container (manufactured by Mitani Pump, nozzle: Z-75-1, pump: H04-050) for a volume of 50 mL. The glass plate was stood vertically, and spraying was continuously performed five times from a position of 10 cm in a horizontal distance, and the spraying state and the presence or absence of dripping of the deposited droplets were observed. The spray characteristics (spray characteristics) were evaluated according to the following criteria.

[Spray state]
X: Not injected as mist, or clogged to prevent injection.
:: The one injected as the mist and the one not the mist are mixed.
○: injected as a good mist.

[Liquid drip]
X: It drips within 1 minute from spraying.
○: Do not drip for 1 minute or more from the spray.

上記表１の結果から、置換度が０．０２以上０．２５以下であり、数平均繊維径が２ｎｍ以上１５０ｎｍ以下のセルロース繊維１ないし３は各評価項目において優れた結果を示しているのに対し、市販の増粘剤は各評価項目においてセルロース繊維１ないし３に対して劣る結果となった。

From the results in Table 1 above, although the cellulose fibers 1 to 3 having a degree of substitution of 0.02 or more and 0.25 or less and a number average fiber diameter of 2 nm or more and 150 nm or less show excellent results in each evaluation item On the other hand, commercially available thickeners were inferior to cellulose fibers 1 to 3 in each evaluation item.

(Evaluation of sprayability 2)
[Examples 2-1 to 2-15]
Each concentration of cellulose fibers 1 to 3 is 1.5% by mass (in terms of solid content), water and various additives (NaCl, ethanol, dimethylpolysiloxane, (D) -limonene, titanium oxide) as shown in Table 2 Each sample was prepared by adding at a ratio shown in and dispersing using a homomixer (manufactured by Primix, T. K Robomix, 12,000 rpm x 10 minutes).

[Comparative Examples 2-1 to 2-20]
Each sample was prepared in the same manner as in Examples 2-1 to 2-15 except that cellulose fibers 1 to 3 were replaced with cellulose fibers 4 to 7, respectively.

〔Evaluation method〕
[Gel state]
After preparing each sample, it was allowed to stand at 25 ° C. for 24 hours, after which the appearance of the gel was confirmed and evaluated according to the following criteria.
Separation: separation is observed.
X: There is liquidity.
○: There is no liquidity.

The spray condition and the dripping were evaluated in the same manner as described above.
The evaluation results are shown in Table 2 below.

上記表２に示す通り、セルロース繊維１ないし３を使用した場合、各評価項目において優れた評価結果となったが、セルロース繊維４ないし７を使用した場合、いずれの添加剤を配合した場合でもゲル状を呈せず、その他の評価においても不良となった。

As shown in Table 2, when cellulose fibers 1 to 3 were used, excellent evaluation results were obtained in each evaluation item, but when cellulose fibers 4 to 7 were used, the gel was obtained when any additive was blended. It did not show a state, and became poor also in other evaluations.

The spray composition of the present invention is in the form of gel, uses a natural material as a thickener, and is highly compatible with various functional additives. In addition to substrates for toiletries, various ointments, various skin external preparations, wound healing agents, organ adhesion preventive agents, etc. can be widely and suitably used.

Claims (4)

A cone / plate type rotational viscometer containing the following components (A) and (B), and the content ratio of the cellulose fiber of the component (A) is 1.0 % by mass or more and 2.0 % by mass or less The maximum value (η _max ) of the viscosity measured at 20 ° C. in the shear rate region including 1 × 10 ⁻³ S ⁻¹ to 1 × 10 ³ S ^{−1 according} to the measurement is η _max 5 5 × 10 ⁴ mPa · s 7. A spray composition characterized in that the minimum value (η _min ) is η _min ≦ 1 × 10 ² mPa · s.
(A) Cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced to a hydroxyl group in a cellulose molecule, a substitution degree is 0.01 or more and 0.5 or less, And / or a cellulose fiber having a crystal structure of type II and an aspect ratio of 50 or more.
(B) water. The spray composition according to claim 1, which contains the following component (C) together with the components (A) and (B).
(C) functional additive.   The functional additive of the component (C) is at least one selected from the group consisting of electrolytes, ionic substances, surfactants, oils, moisturizers, organic fine particles, inorganic fine particles, preservatives, deodorants and perfumes. The spray composition according to claim 2 or 3, which is one.   A spray spray device containing the composition according to any one of claims 1 to 3.