JP2020050738A - Spray composition - Google Patents

Abstract

To provide a spray composition which can be sprayed suitably in spite of being gelatinous.SOLUTION: The spray composition comprises (A) a sulfated cellulose fiber and water, where a content ratio of (A) the sulfated cellulose fiber is 0.1 to 3.0 mass%, the maximum value (ηmax) of viscosity of the spray composition, as measured at 20°C according to measurement by a corn plate type rotary viscometer in a shear rate range of 1×10Sto 1×10S, is ηmax≥1×10mPa s and the minimum value (ηmin) is ηmin≤1×10mPa s, (A) the chemically modified cellulose fiber has a cellulose I type crystal structure, a part of hydroxyl groups of cellulose is substituted with a substituent represented by a specific general formula, (A) the chemically modified cellulose fiber contains 0.01 mmol to 3.0 mmol of the substituent per 1 g of (A) the chemically modified cellulose, and an average degree of polymerization of (A) the chemically modified cellulose fiber is 100 to 3000.SELECTED DRAWING: None

Description

The present invention relates to a composition for spraying.

  By chemically modifying the cellulose fibers, the cellulose fibers can be easily dispersed in water or the like. Such a chemically modified cellulose fiber, when dispersed in water or the like, exhibits characteristic functions such as high thixotropy and viscosity, and can be applied to various uses.

  Examples of chemically modified cellulose include sulfated cellulose. For example, Patent Literature 1 discloses particulate sulfated cellulose in which cellulose is sulfated using sulfuric anhydride as a sulfate esterification reagent. Patent Literature 2 discloses a technique for producing a sulfated cellulose having a cellulose II crystal structure having a degree of polymerization of 60 or less by using a sulfuric acid aqueous solution as a sulfate esterification reagent.

  Here, Patent Document 3 discloses a composition for spraying using TEMPO oxidized cellulose. Since the spray composition has a high thixotropic property, it can be sprayed, for example, as a low-viscosity liquid despite being gel-like in a nebulizer container.

JP 2007-92034 A JP, 2012-526156, A JP 2010-37200 A

Cellulose (2017) 24: 1295-1305 “Complete nanofibrillation of cellulose prepared by phosphorylation”

  However, in the technique of Patent Document 3 using a complicated reaction process, fine adjustment of the pH at the time of the reaction and the like are necessary, and there is a problem that the manufacturing process is complicated. Further, in the techniques of Patent Literature 1 and Patent Literature 2 using a sulfuric anhydride and a high-concentration sulfuric acid aqueous solution, respectively, the degree of polymerization of glucose in cellulose tends to be low. There is a problem that the composition gelled using such a cellulose fiber having a low degree of polymerization cannot be suitably sprayed.

  The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a spray composition which can be sprayed properly in spite of being a gel.

(1) In order to solve the above problems, a spray composition according to an aspect of the present invention contains (A) sulfated cellulose fiber and water, and the content of (A) the sulfated cellulose fiber is 0%. 0.1 to 3.0% by mass and a viscosity measured at 20 ° C. in a shear rate range of 1 × 10 ⁻² S ⁻¹ to 1 × 10 ³ S ⁻¹ as measured by a cone and plate rotational viscometer. Has a maximum value (ηmax) of ηmax ≧ 1 × 10 ⁴ mPa · s, a minimum value (ηmin) of ηmin ≦ 1 × 10 ² mPa · s, and the (A) chemically modified cellulose fiber is cellulose I type. It has a crystal structure, and a part of the hydroxyl groups of cellulose is substituted by a substituent represented by the following general formula (1), and the substitution (A) of 0.01 to 3.0 mmol per 1 g of the chemically modified cellulose fiber. Having the group (A) The composition for spraying, wherein the average degree of polymerization of the decorative cellulose fiber is 100 to 3000. Here, in the general formula (1), M represents a cation having 1 to 3 valences.

  ADVANTAGE OF THE INVENTION According to this invention, the spray composition which can be sprayed suitably although it is a gel-like can be provided.

  First, the contents of the embodiment of the present invention will be listed and described.

(1) The composition for spraying according to the embodiment of the present invention contains (A) sulfated cellulose fiber and water, and the content of (A) the sulfated cellulose fiber is 0.1 to 3.0 mass%. %, And the maximum value (ηmax) of the viscosity measured at 20 ° C. in a shear rate range of 1 × 10 ⁻² S ⁻¹ to 1 × 10 ³ S ⁻¹ as measured by a cone and plate rotational viscometer. ηmax ≧ 1 × 10 ⁴ mPa · s, the minimum value (ηmin) is ηmin ≦ 1 × 10 ² mPa · s, and the (A) chemically modified cellulose fiber has a cellulose I type crystal structure, Is partially substituted with a substituent represented by the following general formula (1), and has (A) 0.01 mmol to 3.0 mmol of the substituent per 1 g of the chemically modified cellulose fiber; A) Average polymerization of chemically modified cellulose fiber The composition for spraying, wherein the degree is 100 to 3000. Here, in the general formula (1), M represents a cation having 1 to 3 valences.

  With such a configuration, it is an object of the present invention to provide a spray composition that can be suitably sprayed despite being in a gel form.

  (2) Preferably, the average fiber width of the (A) chemically modified cellulose fiber is 3 nm to 5000 nm.

  With such a configuration, the spray composition can be sprayed more suitably.

  (3) Preferably, the composition further comprises (B) a functional additive, wherein the (B) functional additive comprises an electrolyte, an ionic substance, a surfactant, an oil, a humectant, organic fine particles, inorganic fine particles, It is at least one selected from the group consisting of preservatives, deodorants and fragrances.

  With such a configuration, the spray composition can have various functions.

  Hereinafter, the background according to the embodiment of the present invention and the effects compared with the related art will be described in more detail.

  In a conventional method of introducing a sulfate group (for example, a functional group represented by the general formula (1)) into cellulose fibers, sulfuric anhydride or the like having a high acidity is used as a sulfation reagent. However, in this method, there is a concern about a decrease in the degree of polymerization of cellulose and danger in production.

  On the other hand, other chemical modification methods for cellulose fibers include a method of introducing a carboxy group to the fiber surface using a TEMPO catalyst (eg, Patent Document 3) and a method of introducing a phosphate group to the fiber surface (eg, Non-Patent Document 1) and the like are known.

  However, in the method described in Patent Document 3, the catalyst used is expensive, and the reaction process is complicated. In addition, in the method described in Non-Patent Document 1, it is necessary to perform the treatment at a high temperature of 165 ° C. and in a short time of several seconds to 600 seconds, so that it is difficult to control the reaction conditions, and to obtain cellulose fibers having the desired physical properties. Is difficult to obtain.

  In contrast, in the method for preparing the chemically modified cellulose fiber according to the embodiment of the present invention, inexpensive sulfamic acid is used, the reaction conditions are mild, the risk is low, and the control of physical properties is easy. . Further, since a decrease in the degree of polymerization can be suppressed by mild reaction conditions, cellulose fibers having a high degree of polymerization can be obtained. In addition, since the introduced functional group is a sulfate ester, the acid dissociation constant is smaller than that of a carboxy group or a phosphate group introduced by another method, and the pH is not easily affected by water and ionic substances in water. It is also characterized by high stability.

  Hereinafter, embodiments of the present invention will be described more specifically.

[(A) Chemically modified cellulose fiber]
(Crystalline I type crystallinity)
The (A) chemically modified cellulose fiber according to this embodiment has a cellulose I-type crystal structure. Specifically, for example, the cellulose I type crystallinity of the chemically modified cellulose fiber (A) is preferably 50% or more. When the cellulose I-type crystallinity is 50% or more, a spray composition that can be sprayed while being in a gel state can be obtained. The cellulose I-type crystallinity is more preferably 60% or more, more preferably 65% or more, and further preferably 70% or more. The upper limit of the cellulose I-type crystallinity is not particularly limited, but from the viewpoint of enhancing the thixotropic property of the spray composition, the cellulose I-type crystallinity is preferably 98% or less, and more preferably 95% or less. More preferably, it is 90% or less, more preferably 85% or less.

  In addition, since the thixotropic property of the spray composition is high to some extent, the spray composition can be sprayed favorably even when a general atomizer such as a sprayer is used, for example. Specifically, since the thixotropic property of the spray composition is high to some extent, the spray composition can be sprayed in a mist state.

  Further, since the thixotropic property of the spray composition is high to some extent, it is possible to prevent the spray composition from dripping on the surface of the object to which the spray is applied. In addition, the higher the thixotropic property of the spray composition, the better the spray composition can be sprayed with a small force.

In the present disclosure, the cellulose I-type crystallinity is the cellulose I-type crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following formula (2).
Cellulose type I crystallinity (%) = [(I _22.6 −I _18.5 ) / I _22.6 ] × 100 (2)
In the formula (2), I _22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I _18.5 is the amorphous portion (diffraction angle 2θ = 18.5 °). Shows the diffraction intensity. In addition, the cellulose I type is a crystal form of natural cellulose, and the cellulose I type crystallinity means a ratio of a crystal region amount to a whole cellulose fiber.

(Substituent)
The chemically modified cellulose fiber (A) according to the present embodiment is obtained by, for example, sulfating the cellulose fiber with sulfamic acid as described later. Specifically, in the chemically modified cellulose fiber (A), a part of the hydroxyl groups of the cellulose is substituted by a substituent represented by the following general formula (1). In other words, (A) chemically modified cellulosic fibers, for example -SO 3 on behalf of the hydrogen atom to the oxygen atom of the hydroxyl groups of cellulose _- have ^M is bonded structure. That is, (A) a sulfate group is introduced into the chemically modified cellulose fiber. Here, in the general formula (1), M represents a cation having 1 to 3 valences.

In the general formula (1), examples of the trivalent cation represented by M include a hydrogen ion, a metal ion, and an ammonium ion. Note that when the M is a divalent or trivalent cation, the cation can be, for example, 2 or 3 -OSO ₃ ^- to form a ionic bond with the.

  Examples of the metal ion include an alkali metal ion, an alkaline earth metal ion, a transition metal ion, and other metal ions. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include calcium and strontium. Transition metals include iron, nickel, palladium, copper, and silver. Other metals include beryllium, magnesium, zinc, aluminum and the like.

Examples of the ammonium ion include not only NH ₄ ⁺ but also ammonium ions derived from various amines formed by replacing one or more hydrogen atoms of NH ₄ ⁺ with an organic group. Specifically, examples of the ammonium ion include NH ₄ ⁺ , a quaternary ammonium cation, an alkanolamine ion, and a pyridinium ion.

  The cation represented by M in the general formula (1) is not particularly limited, but from the viewpoint of enhancing the thixotropic property of the composition for spraying, metal ions such as sodium ion, potassium ion, and calcium ion, or quaternary. Ammonium cations are preferred. The cation may be any one kind or a combination of two or more kinds.

(Amount of substituent)
(A) The amount of the substituent of the general formula (1) per 1 g of the chemically modified cellulose fiber (hereinafter, also referred to as “introduction amount”) is preferably 0.01 to 3.0 mmol. When the amount is 3.0 mmol / g or less, the cellulose crystal structure can be maintained, so that the thixotropic property of the spray composition can be increased. The introduction amount is more preferably 2.8 mmol / g or less, further preferably 2.5 mmol / g or less. Further, when the entire surface of the cellulose fiber is covered with the substituent, the dispersibility of the cellulose fiber in water is improved, and the thixotropic property of the spray composition can be increased. / G, more preferably 0.05 mmol / g or more, and even more preferably 0.1 mmol / g or more.

  In the present disclosure, the amount of substituent introduced is a value calculated by measuring a potential difference. For example, it can be calculated by removing unreacted materials of the raw materials and by-products such as hydrolysates thereof by washing, and then analyzing the potential difference measurement. Specifically, it can be measured by the method described in Examples described later.

(Average degree of polymerization)
The average degree of polymerization of the (A) chemically modified cellulose fiber according to this embodiment (that is, the average value of the number of repeating glucose units) is 100 or more. When the average degree of polymerization is 100 or more, the thixotropic property of the composition for spraying can be enhanced. The average degree of polymerization is preferably 200 or more, more preferably 300 or more, and more preferably 400 or more. The average fiber length of the chemically modified cellulose fiber (A) tends to increase as the average polymerization degree of the chemically modified cellulose fiber (A) increases.

  The upper limit of the average degree of polymerization is not particularly limited, but the average degree of polymerization is preferably 3000 or less, more preferably 2500 or less, and further preferably 2000 or less.

In the present disclosure, the average degree of polymerization is a value measured by a viscosity method. Specifically, the average degree of polymerization is obtained by the following equation (3) using the limiting viscosity number [η] measured according to JIS-P8215.
Average degree of polymerization = (1 / Km) × [η] (3)
However, in equation (3), Km is a coefficient and is a value specific to cellulose (1 / Km = 156).

(Average fiber length)
The average fiber length of the chemically modified cellulose fiber (A) according to this embodiment is preferably 0.1 μm or more, more preferably 1 μm or more, and more preferably 10 μm or more from the viewpoint of enhancing the thixotropic property of the spray composition. Is more preferable. Also. The upper limit is not particularly limited, but is preferably 500 μm or less, may be 300 μm or less, or may be 200 μm or less.

  In the present disclosure, the average fiber length of (A) the chemically modified cellulose fibers is an average value of each fiber length measured by microscopic observation of 50 cellulose fibers.

(Average fiber width)
(A) The average fiber width of the chemically modified cellulose fiber is preferably 3 nm or more, more preferably 5 nm or more, and more preferably 8 nm or more, from the viewpoint of enhancing the thixotropic property of the composition for spraying. And more preferably 10 nm or more. In addition, the average fiber width is preferably 5 μm or less, more preferably 1 μm or less, more preferably 0.5 μm, and more preferably 0.3 μm or less, from the viewpoint of enhancing the thixotropy of the composition for spraying. Is more preferable, and further preferably 0.1 μm or less.

  In the present disclosure, the average fiber width of (A) the chemically modified cellulose fibers is an average value of each fiber width measured by microscopic observation of 50 cellulose fibers.

[(A) Method for producing chemically modified cellulose fiber]
The method for producing the chemically modified cellulose fiber (A) according to the present embodiment is not particularly limited, and includes, for example, a step of reacting a cellulose raw material with sulfamic acid to sulfate esterify the cellulose fiber (chemical modification step). .

(Cellulose raw material)
Specific examples of the cellulose raw material used in the chemical modification step include plants (for example, wood, cotton, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp, recycled pulp, waste paper), animals (for example, ascidians), algae , Microorganisms (for example, acetic acid bacteria), products derived from microorganisms, and the like. As the cellulose raw material, plant-derived pulp is mentioned as a preferable raw material.

  Examples of plant-derived pulp include chemical pulp (kraft pulp (KP), sulfite pulp (SP)), semi-chemical pulp (SCP), chemical ground pulp (CGP), and chemical mechanical pulp obtained from wood chips and the like. (CMP), ground wood pulp (GP), refiner mechanical pulp (RMP), thermomechanical pulp (TMP), and chemithermomechanical pulp (CTMP) are preferred.

  In addition, as the cellulose raw material, chemically modified pulp that has been chemically modified within a range that does not impair the purpose of the present embodiment may be used. Specifically, for example, the cellulose raw material to be used may be one in which some of the hydroxyl groups present on the surface of the cellulose fiber are esterified with an oxo acid such as acetic acid or nitrate, or methyl ether or hydroxy. It may be etherified such as ethyl ether, hydroxypropyl ether, hydroxybutyl ether, carboxymethyl ether, cyanoethyl ether and the like. Further, the cellulose raw material to be used may have been subjected to a TEMPO oxidation treatment.

  As the cellulose raw material, it is preferable to use a cellulose raw material having cellulose I type crystal and having a cellulose I type crystallinity of 50% or more. The value of the cellulose I type crystallinity of the cellulose raw material is more preferably 60% or more, and further preferably 70% or more. The upper limit of the degree of crystallinity of cellulose I of the cellulose raw material is not particularly limited, but may be, for example, 98% or less, 95% or less, or 90% or less.

  The shape of the cellulose raw material is not particularly limited, but is preferably fibrous, sheet-like, cotton-like, powder-like, chip-like, or flake-like from the viewpoint of improving handleability.

(Pretreatment step)
When a cellulose raw material having a high bulk density is used, the bulk density may be reduced by performing a pretreatment prior to the chemical modification step. By performing such a pretreatment, sulfate esterification can be performed more efficiently in the chemical modification step.

The pretreatment method is not particularly limited. For example, by performing mechanical treatment, the cellulose raw material can be adjusted to an appropriate bulk density. The type of the machine to be used and the processing conditions are not particularly limited, but examples of the machine to be used include a shredder, a ball mill, a vibration mill, a stone mill, a grinder, a blender, a high-speed rotating mixer, a pulper, a cutter mill, and a disc refiner. Can be The bulk density is not particularly limited, but is preferably, for example, 0.1 to 5.0 kg / m ³ , more preferably 0.1 to 3.0 kg / m ³ , and 0.1 to 1.0 kg / m ³ . More preferably, it is 0 kg / m ³ .

(Chemical modification step)
In the chemical modification step, the cellulose fiber contained in the cellulose raw material is sulfated by treating the cellulose raw material with sulfamic acid. Specifically, for example, by immersing a cellulose raw material in a chemical solution containing sulfamic acid and reacting the cellulose fiber with the sulfamic acid, the cellulose fiber can be sulfated.

  The chemical solution for performing the sulfate esterification reaction contains, for example, sulfamic acid and a solvent. Examples of the solvent include, but are not particularly limited to, water and linear or branched alcohols having 1 to 12 carbon atoms such as methanol, ethanol, propanol, butanol, octanol, and dodecanol; carbons such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. A ketone having 3 to 6 carbon atoms; a linear or branched saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms; an aromatic hydrocarbon such as benzene and toluene; a halogenated hydrocarbon such as methylene chloride and chloroform; Lower alkyl ethers of formulas 2 to 5; dioxane, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine and the like. These can be used alone or in combination of two or more.

  Here, when a polar organic solvent is used as a solvent, the swelling of the cellulose raw material is promoted, and the reaction rate of sulfuric esterification can be increased. Since it can be introduced, the thixotropy of the composition for spraying can be enhanced. Examples of the polar organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine and the like.

  The amount of the solvent used is not particularly limited, but is, for example, preferably 10 to 10,000 mass%, more preferably 20 to 5000 mass%, and more preferably 50 to 2000 mass%, based on the dry mass of the cellulose raw material. It is more preferred that there be.

  The chemical solution may further include a catalyst. Examples of the catalyst include urea, amides, tertiary amines and the like, and it is preferable to use urea from the viewpoint of inexpensiveness and easy handling. The amount of the catalyst used is not particularly limited, but is preferably, for example, 0.001 to 5 mol, more preferably 0.005 to 2.5 mol, and more preferably 0.01 to 2 mol per mol of anhydroglucose unit in the cellulose molecule. 0.0 mol is more preferred. As the catalyst, a catalyst having a high concentration may be used as it is, or may be used after being diluted with a solvent. The method for adding the basic catalyst can be performed by batch addition, divided addition, continuous addition, or a combination thereof.

  The temperature of the chemical solution at the time of sulfate esterification of the cellulose fiber is preferably from 0 to 100C, more preferably from 10 to 80C, even more preferably from 20 to 70C. If the temperature of the chemical solution is too high, the glycoside bond in the cellulose molecule will be broken, thereby lowering the average degree of polymerization of the chemically modified cellulose fiber (A). On the other hand, when the temperature of the chemical solution is too low, the reaction requires time. The time required for the sulfate esterification is usually about 30 minutes to 5 hours.

  The amount of sulfamic acid used can be appropriately adjusted in consideration of the amount of the substituent introduced into the cellulose fiber. For example, the sulfamic acid is preferably used in an amount of 0.01 to 50 mol, more preferably 0.1 to 30 mol, per 1 mol of anhydroglucose unit in the cellulose molecule.

  In order to obtain a product with less coloring, an inert gas such as nitrogen gas, neon gas, argon gas, helium gas or carbon dioxide gas may be introduced during the sulfuric acid esterification reaction. As a method for introducing these inert gases and the like, a method in which the reaction is performed while blowing the inert gas or the like into the reaction tank, a method in which the inside of the reaction tank is replaced with an inert gas or the like before the reaction, and the reaction tank is hermetically sealed. And any other method.

  Sulfamic acid has a large acid dissociation constant (pKa) and a small amount of hydrogen ions in the reaction solution as compared with sulfuric anhydride or an aqueous sulfuric acid solution, and thus maintains the polymerization state of glucose without breaking glycoside bonds in cellulose. It is possible to That is, by subjecting the cellulose fiber to sulfate esterification using sulfamic acid, it is possible to obtain the chemically modified cellulose fiber (A) having a high average degree of polymerization.

Also, sulfamic acid is
Unlike sulfuric anhydride or sulfuric acid aqueous solution, which has strong acidity and high corrosiveness, there is no restriction on handling, and as can be seen from the fact that it is not specified as a specific substance under the Air Pollution Control Law, the burden on the environment is small. . That is, the production cost including various management costs can be suppressed by sulphating the cellulose fibers using sulfamic acid.

  After the chemical modification step, another chemical modification step may be provided as necessary. The other chemical modification step may be, for example, a step of esterifying a part of hydroxyl groups present on the surface of the cellulose fiber which has not been subjected to sulfate esterification with an oxo acid such as acetic acid or nitric acid. May be a step of etherifying a part of the hydroxyl groups such as methyl ether, hydroxyethyl ether, hydroxypropyl ether, hydroxybutyl ether, carboxymethyl ether, cyanoethyl ether, etc., or a step of subjecting the cellulose fiber to a TEMPO oxidation treatment. Is also good.

(Neutralization step)
For example, after the chemical modification step, the chemically modified cellulose fibers are separated from the solvent by filtration or the like, and the obtained swollen chemically modified cellulose fibers are dispersed in water. Then, the dispersion is neutralized by adding a basic compound to the dispersion of the cellulose fibers. Thus, -OSO ₃ having a chemically modified cellulose fibers ^- and a cation derived from the basic compound to form an ionic bond.

  By adjusting the pH value to neutral or alkaline by adding a basic compound to the dispersion in this way, the storage stability of the chemically modified cellulose fiber itself can be improved. Specifically, by performing the neutralization step, the average polymerization degree of the chemically modified cellulose fiber (A) can be kept high.

  The basic compound used for the neutralization is not particularly limited, and examples thereof include an alkali metal hydroxide, an alkaline earth metal hydroxide, other inorganic salts, and amines. Specifically, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium acetate, calcium lactate, calcium oxalate, magnesium hydroxide, magnesium acetate, magnesium lactate, magnesium oxalate, basic aluminum lactate, basic aluminum chloride , Ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine and triethanolamine. In the neutralization, one kind of basic compound may be used alone, or two or more kinds of basic compounds may be used in combination.

(Washing process)
For example, a step of washing the chemically modified cellulose fiber may be provided for the purpose of removing a sulfate esterification reagent residue, a residual catalyst, a solvent, and the like, or for stopping the reaction. In the washing step, the chemically modified cellulose fiber is preferably washed with water.

  The washing method is not particularly limited, but the chemically modified cellulose fibers are separated from the dispersion medium water by filtration or the like, and the obtained swollen chemically modified cellulose fibers are dispersed again in separately prepared water. By performing such a step one or more times, the chemically modified cellulose fiber can be washed. The chemically modified cellulose fibers may be separated from the dispersion medium by a centrifugal sedimentation method, a press treatment, or the like. Here, the method of washing chemically modified cellulose fibers with water has been described as an example, but may be washed with another liquid such as an organic solvent.

(Miniaturization process)
When the fiber length of the cellulose fiber is relatively small, the cellulose raw material is defibrated to some extent by performing a chemical modification step or the like without performing a mechanical defibration treatment. On the other hand, when the fiber length of the cellulose fiber is relatively large, the cellulose raw material is hardly defibrated only through a chemical modification step or the like. In such a case, for example, the cellulose raw material having undergone the neutralization step and the washing step is dehydrated to adjust the amount of water, and then subjected to a mechanical fibrillation treatment (refinement treatment step) to thereby obtain a defibrated chemical. A modified cellulose fiber can be obtained. The (A) chemically modified cellulose fiber according to the present embodiment may or may not have undergone a fine processing step.

Examples of devices used in the micronization process include, for example, a microfluidizer, a refiner, a twin-screw kneader (a twin-screw extruder), a high-pressure homogenizer, and a medium stirring mill (specifically, a rocking mill, a ball mill, a bead mill, and the like). , A stone mill, a grinder, a vibration mill, a sand grinder and the like.

  The content of the chemically modified cellulose fiber (A) in the gel composition according to the present embodiment is preferably 0.01% to 3%, and more preferably 0.05% to 1%, from the viewpoint of enhancing the thixotropic properties of the composition for spraying. Is more preferable, and 0.08 to 0.5% is still more preferable.

[(B) Functional additive]
The spray composition according to the present embodiment may include, for example, (B) a functional additive. (B) Examples of the functional additive include electrolytes, ionic substances, surfactants, oils, humectants, organic fine particles, inorganic fine particles, preservatives, deodorants, fragrances, organic solvents, and the like. it can. In particular, the composition for spraying according to the present example has a high viscosity showing a gel state even when an electrolyte or an ionic substance (including an ionic surfactant) is blended, and also has a separation or water separation. Because of the characteristic that the gel state is maintained without causing the occurrence, excellent performance can be exhibited in a spray composition in which these functional additives are required materials.

  Examples of electrolytes and ionic substances include alkali metals, alkaline earth metals, transition metals such as sodium chloride, sodium edetate and sodium ascorbate, and hydrogen halide, sulfuric acid, carbonic acid, and carboxyl groups in the molecule. Salts comprising one or more organic acids, etc., sulfonic acid surfactants such as sodium alkyl sulfosuccinate, sodium alkyl sulfonate, alkyl sulfate, polyoxyethylene alkyl sulfate, alkylbenzene sulfonate, etc. Phosphate-based surfactants such as ethylene alkyl phosphate, which can be dissolved and dispersed in a dispersion medium such as water, are used.

  As nonionic surfactants, 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 hardened castor oil, polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene lanolin, polyoxy Ethylene lanolin alcohol, polyoxyethylene beeswax derivative, polyoxy Polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensates and the like.

  Examples of oils include jojoba oil, macadamia nut oil, avocado oil, evening primrose oil, mink oil, rapeseed oil, castor oil, sunflower oil, corn oil, cocoa oil, coconut oil, rice bran oil, olive oil, almond oil, sesame oil, sa Flower oil, soybean oil, camellia oil, persic oil, mink oil, cottonseed oil, mocro, palm oil, palm kernel oil, egg yolk oil, lanolin, squalene, and other natural animal and vegetable oils, synthetic triglycerides, squalane, liquid paraffin, vaseline, ceresin, Hydrocarbons such as microcrystalline wax and isoparaffin, waxes such as carnauba wax, paraffin wax, spermaceti, beeswax, candelilla wax, lanolin, and higher alcohols (cetanol, stearyl alcohol, lauryl alcohol, setosteryl alcohol) Oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol, etc.), lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, linolenic acid, linoleic acid, oxylic acid Higher fatty acids such as stearic acid, undecylenic acid, lanolin fatty acid, hard lanolin fatty acid, and soft lanolin fatty acid, cholesterol such as cholesteryl-octyldodecyl-behenyl and derivatives thereof, isopropyl myristate, isopropyl palmitate, isopropyl stearate, and 2-ethylhexane Esters such as glycerol acid, butylstearic acid, diethylene glycol monopropyl ether, polyoxyethylene polyoxypropylene pen Polar oils such as erythritol ether, polyoxypropylene butyl ether and ethyl linoleate, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, and one-terminal reactive silicone Silicones such as silicone modified with different functional groups, 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. And the like. These may be used alone or in combination of two or more.

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

  Examples of the humectant include polyhydric alcohols such as glyceryl trioctanoate, maltitol, sorbitol, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, and glycol; organic acids such as sodium pyrrolidone carboxylate, sodium lactate, and sodium citrate. And its salts, hyaluronic acid and its salts such as sodium hyaluronate, hydrolysates of yeast and yeast extract, yeast culture, fermentation metabolites such as lactic acid bacteria culture, collagen, elastin, keratin, water-soluble proteins such as sericin, collagen Hydrolysates, casein hydrolysates, silk hydrolysates, peptides such as sodium polyaspartate and salts thereof, trehalose, xylobiose, maltose, sucrose, glucose, saccharides and polysaccharides such as vegetable mucopolysaccharides and the like Derivative Water-soluble chitin, chitosan, pectin, glycosaminoglycans such as chondroitin sulfate and salts thereof and salts thereof, glycine, serine, threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine, amino acids such as prophosphoric acid, Sugar amino acid compounds such as aminocarbonyl reactants, plant extracts such as aloe and malonie, trimethylglycine, urea, uric acid, ammonia, lecithin, lanolin, squalane, squalene, glucosamine, creatinine, DNA, RNA and other nucleic acid-related substances. can give. These may be used alone or in combination of two or more.

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

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

  Examples of the deodorant and fragrance include D-limonene, decylaldehyde, menthol, pulegone, eugenol, cinnamaldehyde, benzaldehyde, menthol, peppermint oil, lemon oil, orange oil, and deodorant active ingredients extracted from various organs of plants (for example, Deodorant active components extracted from oxalis, ginkgo, gingko, black pine, larch, Japanese red pine, kiri, holly mokusai, lilac, chinmokusei, butterbur, tsubaki, and forsythia by water, water and hydrophilic organic solvents ) And the like. These may be used alone or in combination of two or more.

  Examples of the organic solvent include water-soluble alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, glycerin, etc.), and ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone), N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more.

  The functional additive (B) is used alone or in combination of two or more in accordance with the field of use and required performance of the spray composition of the present invention, and the amount of the functional additive also depends on the required performance. Used in an appropriate range.

  The spray composition according to the present embodiment is prepared, for example, by adding (B) a functional additive to an aqueous dispersion of (A) a chemically modified cellulose fiber and dispersing the same with a disperser. In addition, (B) a functional additive may be added during the preparation of (A) the chemically modified cellulose fiber.

  In addition, since the chemically modified cellulose fiber (A) also has a function as an emulsion stabilizer, when oils are blended into the spray composition according to the present embodiment, a conventional O / W emulsion emulsion is used. It may be prepared according to the adjustment method. At that time, a nonionic surfactant or the like serving as an emulsion stabilizer may be used in combination. The amount of the cellulose fiber is determined in consideration of emulsion stability and sprayability.

  In the spray composition according to the present embodiment, the content ratio of (A) the chemically modified cellulose fiber is 0.1% from the viewpoint of making the spray composition in a static state not giving shear stress a suitable gel state. It is preferably from 5.0 to 5.0% by weight, more preferably from 0.2 to 3.0% by weight.

Further, the composition for spraying according to the present embodiment is defined by a viscosity measured by a cone and plate type viscometer. Specifically, when a shearing stress is applied to the spray composition at 20 ° C. to change the shear rate in the range of 1 × 10 ⁻² S ⁻¹ to 1 × 10 ³ S ⁻¹ , The maximum value of the viscosity (ηmax) of the composition is ηmax ≧ 1 × 10 ⁴ mPa · s. This makes it possible to prevent the composition for spray from dripping on the surface of the object to which the spray is applied. The minimum value of the viscosity (ηmin) is ηmin ≦ 1 × 10 ² mPa · s. Thereby, the composition for spraying can be sprayed in the form of a mist.

On the other hand, when ηmax is less than 1 × 10 ⁴ mPa · s, the above-mentioned ability to prevent dripping is reduced. On the other hand, when ηmin exceeds 1 × 10 ² mPa · s, the composition for spraying cannot be sprayed in the form of a mist, which may cause uneven spraying. In the case where the application density of the spray coating is relatively low, the above-mentioned dripping prevention can be sufficiently expected if ηmax ≧ 1 × 10 ⁴ mPa · s is satisfied. Even if satisfies ηmax ≧ 1 × 10 ⁴ mPa · s, it is possible that the prevention of liquid dripping cannot be prevented. Therefore, it is preferable that ηmax ≧ 5 × 10 ⁴ mPa · s.

In addition, in a normal application density, if ηmin ≦ 1 × 10 ² mPa · s is satisfied, there is no unevenness in spraying. However, if a very thin and uniform spray is desired, ηmin ≦ 5 × 10 ¹ mPa · s. Is preferred. In order to stably spray the composition for spraying according to the present embodiment, ηmax preferably does not exceed 1 × 10 ⁹ mPa · s.

[water]
As the water used in the composition for spraying according to the present embodiment, ion-exchanged water, distilled water and the like can be mentioned. Further, the content of water in the gel composition according to the present embodiment is preferably 50% by mass or more, and more preferably 75% by mass.

  Since the spray composition according to the present embodiment has high thixotropy, the viscosity during spraying is reduced, so that the spray composition can be sprayed well. Then, the viscosity of the droplet ejected from the nozzle is recovered before or immediately after the droplet adheres to the surface of the object to be sprayed, so that dripping on the surface hardly occurs. Further, the spray composition attached to the surface has excellent spreadability. Further, the composition for spraying according to the present embodiment has excellent temperature stability without a decrease in viscosity even at a high temperature of 50 ° C. or more, and is sticky as in the case of thickening using a water-soluble polymer. There is no feeling.

  The sprayer used in the present embodiment is not particularly limited as long as it can easily fill the above composition and enables spraying, but in consideration of versatility and high accuracy of spraying performance, the following three It is preferably in the form (1) to (3).

(1) Dispenser type sprayer equipped with a pump type nozzle capable of spraying: This sprayer can operate spraying at atmospheric pressure, does not require pressurized gas, etc., and has a relatively simple container structure, which is safe. It is a high and portable spraying device. The structure consists of an extrusion pump type nozzle equipped with a suction tube, and a screw type container which fixes the nozzle and fills the above composition. The dispenser type spraying device here includes all devices in which the structure of a pump type nozzle is improved in order to enhance the spraying performance. The spray characteristics depend on the hole diameter of the ejection nozzle, the pumping volume per pump, etc., and these conditions are selected according to the purpose.

(2) Trigger-type sprayer: The trigger-type sprayer is a sprayer for household detergent, clothing paste, kitchen detergent, etc., and a pistol-type trigger-type sprayer is attached to the mouth of a container body for filling the above composition. It can operate spraying at atmospheric pressure and is highly versatile as a liquid sprayer. The trigger type sprayer mentioned here includes all the improved types of the trigger type spray device in order to improve the spraying performance.

(3) Aerosol sprayer: The aerosol sprayer enables continuous atomization or continuous foam formation that cannot be realized by the above two spraying devices by filling a propellant into a container. The aerosol sprayer referred to here includes all those in which the injection device portion of the aerosol container is improved. Generally, in atomization using the present atomizer, finer atomization can be performed as compared with the above two atomizations performed under atmospheric pressure. As the propellant used in the aerosol spray, dimethyl ether, liquefied petroleum gas, carbon dioxide gas, nitrogen gas, argon gas, air, oxygen gas, chlorofluorocarbon gas, etc. can be used, and these can be used alone or in combination of two or more. Can be

  The spray composition is in a gel state in a container of the sprayer, for example, and does not flow even when tilted. This allows spraying, for example, even when the sprayer is greatly inclined or turned upside down.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

[(A) Preparation of chemically modified cellulose fiber]
First, each chemically modified cellulose fiber (A) used in Examples is prepared according to Production Examples 1 to 3 below.

(Production Example 1)
52.8 g of sulfamic acid and 620 g of N, N-dimethylformamide (DMF) were charged into a separable flask and stirred for 30 minutes. Thereafter, at room temperature, 20.0 g of softwood kraft pulp (crystallinity: 85%) was charged as a cellulose raw material. Here, the amount of sulfamic acid used as the sulfate esterification reagent was 4.4 mol per 1 mol of anhydroglucose unit in the cellulose molecule. After reacting at 55 ° C. for 4 hours, it was cooled to room temperature. Next, the fiber is taken out and washed with water, and then poured into a 2N aqueous sodium hydroxide solution as a neutralizing agent to adjust the pH to 7.6. After dehydration, water is added so that the solid concentration becomes 1.0%. Diluted. Thereafter, a microfluidizer treatment (150 MPa, 1 pass) was performed as a micronization treatment step, to obtain an aqueous dispersion of chemically modified cellulose fibers A1 (denoted as “A1” in the table).

(Production Example 2)
An aqueous dispersion of a chemically modified cellulose fiber A2 (denoted as "A2" in the table) was obtained by the same procedure as in Production Example 1 except that the charged amount of sulfamic acid was 26.4 g.

(Production Example 3)
An aqueous dispersion having a solid content of 1.0% was obtained in the same procedure as in Production Example 2 except that the micronization process was not performed. 150 g of this aqueous dispersion was transferred to a separable flask, and 0.25 g of sodium bromide and 0.025 g of 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) were added and stirred. 6.6 g of 13% sodium hypochlorite was added dropwise while adding an appropriate amount of a 0.5N aqueous sodium hydroxide solution so that the pH became 10-11. After performing an oxidation reaction for 45 minutes and confirming that there was no change in pH, 0.1N hydrochloric acid was added to adjust the pH to 7.0. After dehydration, it was diluted with water so that the solid concentration became 1.0%. Thereafter, a water treatment of a chemically modified cellulose fiber A3 (denoted as “A3” in the table) was obtained by performing a treatment (150 MPa, one pass) with a microfluidizer as a micronization treatment step.

For each (A) chemically modified cellulose fiber obtained in Production Examples 1 to 3,
(1) (A) Sulfate group content of 1 g of chemically modified cellulose fiber,
(2) (A) the amount of carboxy groups contained in 1 g of the chemically modified cellulose fiber,
(3) average degree of polymerization,
(4) Average fiber width and (5) crystallinity were measured.
Table 1 shows the measurement results. Details of each measurement are shown below.

(1) Sulfate group amount (mmol / g)
The amount of sulfate group was calculated by potentiometric measurement. Specifically, from a sulfated cellulose fiber sample whose dry weight was precisely weighed, 60 ml of an aqueous dispersion of sulfated cellulose fiber adjusted to a solid content of 0.5% by mass was prepared, and the pH was adjusted with a 0.1N hydrochloric acid aqueous solution. After adjusting to about 1.5, the mixture was filtered, washed with water, and the fibers were redispersed in water so as to have a solid content of 0.5% by mass. A 0.1N aqueous potassium hydroxide solution was added dropwise to perform potentiometric titration. . The amount of sulfate groups was calculated from the amount of 0.1N potassium hydroxide added dropwise.

(2) Carboxyl group amount (mmol / g)

The carboxy group content was calculated by potentiometric measurement. Details were performed in the same manner as in (1) Measurement of Sulfate Group Amount. The calculation of the amount of carboxy groups is based on the difference between the amount of 0.1N potassium hydroxide dripped in the sample subjected to TEMPO oxidation and the amount of 0.1N potassium hydroxide dripped in the sample before TEMPO oxidation (after sulfate esterification). Was calculated.

(3) Average polymerization degree (A) The average polymerization degree of the chemically modified cellulose fiber was calculated by a viscosity method. Specifically, the limiting viscosity number [η] was measured according to JIS-P8215, and the average degree of polymerization (DP) was determined from the following equation (3). However, in equation (3), Km is a coefficient and is a value specific to cellulose (1 / Km = 156).
DP = (1 / Km) × [η] (3)
(Km is a coefficient and a value specific to cellulose. 1 / Km = 156)

(4) Average fiber width (nm)
(A) The average fiber width of the chemically modified cellulose fibers was measured by an electron microscope (TEM). In detail, the average of the fiber widths of 50 fibers observed in a TEM image (magnification: 1000 to 10,000 times) negatively stained with 2% uranyl acetate after casting the hydrophilized carbon film coating in a grit shape The value was calculated and taken as the average fiber width.

(5) Crystallinity (Crystalline I-type crystallinity) (%)
(A) The X-ray diffraction intensity of the chemically modified cellulose fiber was measured by the X-ray diffraction method, and the measurement result was calculated by the following equation (2) using the Segal method.
Cellulose type I crystallinity (%) = [(I _22.6 −I _18.5 ) / I _22.6 ] × 100 (2)
In the formula (2), I _22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I _18.5 is the amorphous portion (diffraction angle 2θ = 18.5 °). Shows the diffraction intensity. In addition, measurement of the X-ray diffraction intensity of the sample was performed using “RINT2200” manufactured by Rigaku Corporation under the following conditions:
X-ray source: Cu / Kα-radiation
Tube voltage: 40Kv
Tube current: 30 mA
Measurement range: diffraction angle 2θ = 5-35 °
X-ray scan speed: 10 ° / min
The crystallinity of the cellulose raw material was measured in the same manner.

(Preparation of composition)
A spray composition was prepared using the aqueous dispersion of the chemically modified cellulose fiber (A) obtained in Production Examples 1 to 3. Specifically, (A) an aqueous dispersion of chemically modified cellulose fibers, an aqueous dispersion of cellulose nanocrystals (CNC), or an aqueous dispersion of carboxymethyl cellulose (CMC) so as to have a mixing ratio shown in Table 2. By mixing with water and performing a dispersion treatment at 8000 rpm for 10 minutes using a homomixer, spray compositions according to Examples and Comparative Examples in Table 2 were prepared. Note that CNC and CMC are comparative materials for (A) the chemically modified cellulose fiber.

  The CNC used in the comparative example was prepared by the following procedure. That is, 100 mL of 64% sulfuric acid and 2 g of softwood kraft pulp were charged into a separable flask and heated at 50 ° C. for 1 hour. After sufficiently cooling, the reaction solution was charged little by little into a separable flask containing another 1000 mL of water. After centrifugation, the mixture was neutralized with 1N sodium hydroxide and dehydrated. The coarse fibers were removed by filtration through a metal mesh to obtain cellulose nanocrystals. The average degree of polymerization of cellulose of the CNC was 90, and the average fiber width was 40 nm. The average degree of polymerization and the average fiber width were measured in the same manner as in (A) the chemically modified cellulose fiber.

The CMC used in the comparative example is as follows.
・ Delogen WS-A manufactured by Daiichi Kogyo Seiyaku

  Table 2 also shows the ratio of the components in the composition for spraying and the evaluation results of the gel composition. Specifically, Table 2 shows, as the ratio, the solid content (% by mass) of (A) the chemically modified cellulose fiber, CNC or CMC in the composition for spraying. Table 2 shows the viscoelastic properties of the composition for spray described later, whether or not it is in a gel state at rest, and the spray state as the evaluation results.

(Evaluation)
[Viscoelastic properties]
The composition for spraying according to each Example and each Comparative Example was prepared at 20 ° C., and the viscoelastic properties of each composition for spraying were measured using a cone and plate type rotational viscometer (MCR302, manufactured by Anton Paar). did. Specifically, the maximum value (ηmax) and the minimum value (ηmin) of the viscosity in the shear rate range of 1 × 10 ⁻² S ⁻¹ to 1 × 10 ³ S ⁻¹ are measured using the cone-plate type rotational viscometer. ) Was measured.

[Gel state (at rest)]
100 g of the spray composition according to each example and each comparative example was placed in a 200 ml beaker, adjusted to 20 ° C., and the state of the spray composition when the beaker was inverted was visually observed, and the spray was observed. It was determined whether the composition for use was a gel. The criteria for the determination are shown below.
Gel (〇): The liquid surface does not flow.
Not gel (x): The liquid surface flows.

[Spray state]
The spray compositions according to the examples and the comparative examples were tried to be sprayed using a sprayer, and when the spray compositions could be sprayed, the state was visually observed. Specifically, this evaluation was carried out using a commercially available dispenser type spray container (dispensing bottle (spray type) S-50, manufactured by Sunplate Tech Co., Ltd., S-50) with a capacity of 50 ml for the spray composition. The criteria for the determination are shown below.
〇: The spray composition is sprayed from the nozzle in the form of a mist.
×: The spray composition cannot be sprayed from the nozzle, or the spray composition sprayed is not in the form of a mist.

Referring to Table 2, the spray compositions according to the examples could be sprayed well despite being in a gel state. On the other hand, in Comparative Example 2, a gel composition was prepared using CMC, but the composition could not be sprayed well.

Claims (3)

(A) containing sulfated cellulose fibers and water;
(A) the content of sulfated cellulose fibers is 0.1 to 3.0% by mass,
In a shear rate range of 1 × 10 ⁻² S ⁻¹ to 1 × 10 ³ S ⁻¹ measured by a cone and plate type rotary viscometer, the maximum value of viscosity (ηmax) measured at 20 ° C. is ηmax ≧ 1 ×. 10 ⁴ mPa · s, and the minimum value (ηmin) is ηmin ≦ 1 × 10 ² mPa · s;
The (A) chemically modified cellulose fiber has a cellulose I type crystal structure, and a part of the hydroxyl groups of the cellulose is substituted by a substituent represented by the following general formula (1). Having 0.01 to 3.0 mmol of the substituent per 1 g of fiber,
The composition for spraying, wherein the average degree of polymerization of the chemically modified cellulose fiber (A) is 100 to 3000. Here, in the general formula (1), M represents a cation having 1 to 3 valences.

  The spray composition according to claim 1, wherein the average fiber width of the (A) chemically modified cellulose fiber is 3 nm to 5000 nm. Further, (B) contains a functional additive,
The functional additive (B) is at least one selected from the group consisting of electrolytes, ionic substances, surfactants, oils, humectants, organic fine particles, inorganic fine particles, preservatives, deodorants and fragrances. The spray composition according to claim 1, wherein the composition is a spray composition.