JP6893803B2 - Composition containing etherified cellulose fibers and water - Google Patents

Description

The present invention relates to a composition containing etherified cellulose fibers and water, and a foaming agent composed of the etherified cellulose fibers. More specifically, a composition preferably used as a dispersion composition, a skin treatment agent composition, a hair treatment agent composition, a hard surface treatment agent composition, a clothing treatment agent composition, and the like, and a foaming agent. Regarding foaming agents.

Conventionally, petroleum-derived plastic materials, which are a finite resource, have been widely used, but in recent years, technologies with less impact on the environment have come into the limelight, and under such technological background, it is a biomass that exists in large quantities in nature. Various compositions using cellulose fibers are attracting attention.

For example, Patent Document 1 discloses cellulose nanofibers obtained by defibrating by high-pressure injection treatment.

Japanese Unexamined Patent Publication No. 2015-157996

It was newly found that the cellulose fiber itself shows almost no foaming property in water, but when a specific modified cellulose fiber is used, it unexpectedly shows foaming property.

The present invention relates to a novel composition having excellent foaming properties.

The present invention relates to the following [1] to [2].
[1] A composition containing an etherified cellulose fiber and water, wherein the etherified cellulose fiber has a hydrocarbon group which may have a substituent bonded to the cellulose fiber via an ether bond. , A modified cellulose fiber having a cellulose type I crystal structure.
[2] A foaming agent comprising a modified cellulose fiber having a cellulose I-type crystal structure in which a hydrocarbon group which may have a substituent is bonded to the cellulose fiber via an ether bond.

According to the present invention, it is possible to provide a novel composition having excellent foaming property.

According to the configuration of the present invention, the foaming property is unexpectedly exhibited. Although the reason is not clear, it is presumed that the cellulose fiber according to the present invention can exhibit foaming property in an aqueous dispersion by exhibiting surface activity by having a functional group via an ether bond. ..

Further, according to the configuration of the present invention, when applied to the skin, a silky feeling and a coat feeling are exhibited, and when applied to hair, a cohesiveness, combing property and a glossy feeling are exhibited, and the application is applied to a hard surface. In some cases, the effect of increasing the contact angle of water droplets is exhibited, and when applied to clothing, the effect of suppressing wrinkles and the effect of quick-drying are exhibited. The reasons for these are not clear, but are presumed as follows.

Generally, it is known that cellulose fibers remain on the skin, hair, and fibers to form a film and have a coating effect. However, the composition using cellulose fibers according to the present invention is used for skin, hair, and hard surfaces. When treatment of clothing etc. (application, washing, etc.) is performed, the residual amount increases due to the effect of the functional group, or the residual state such as uniformly remaining on the surface changes, or the effect of the functional group. It is presumed that the above effect is obtained by improving the hydrophobicity of the cellulose fiber itself.

The composition of the present invention contains etherified cellulose fibers and water.

[Aethered cellulose fiber]
The etherified cellulose fiber in the present invention is a modified cellulose fiber having a cellulose type I crystal structure in which a hydrocarbon group which may have a substituent on the surface of the cellulose fiber is bonded via an ether bond. It is characterized by. In addition, in this specification, "bonding through an ether bond" means a state in which a modifying group reacts with a hydroxyl group on the surface of a cellulose fiber, and an ether bond is formed.

In the hydrocarbon group which may have a substituent in the present invention, the hydrocarbon group is a saturated or unsaturated linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group such as a phenyl group, or an aromatic hydrocarbon group. Examples thereof include an alicyclic hydrocarbon group such as a cyclohexyl group, which is preferably a saturated or unsaturated linear or branched aliphatic hydrocarbon group from the viewpoint of foaming property and economy, and more preferably. It is a saturated linear or branched aliphatic hydrocarbon group.
Further, among the hydrocarbon groups which may have a substituent in the present invention, examples of the substituent include an oxyalkylene group such as a halogen atom and an oxyethylene group and a hydroxyl group, and from the viewpoint of foaming property and economic efficiency. , Preferably oxyethylene groups and hydroxyl groups.

As a preferred embodiment (aspect 1) of such an etherified cellulose fiber, for example, one selected from a substituent represented by the following general formula (1) and a substituent represented by the following general formula (2) or Examples thereof include those in which two or more kinds of substituents are bonded to cellulose fibers via an ether bond and have a cellulose type I crystal structure.
-CH ₂ -CH (R ₀ ) -R ₁ (1)
-CH _2- CH (R ₀ ) -CH _2- (OA) _n- O-R ₁ (2)
_{[In the formula, R 0} in the general formula (1) and the general formula (2) _{indicates a hydrogen atom or a hydroxyl group, and R 1} in the general formula (1) and the general formula (2) independently has 3 or more carbon atoms and 30 carbon atoms. Indicates the following linear or branched alkyl, n in the general formula (2) is a number of 0 or more and 50 or less, and A is a straight or branched divalent saturated hydrocarbon group having 1 or more and 6 or less carbon atoms. Shown. ]

As a specific example of the first aspect, for example, an etherified cellulose fiber represented by the following general formula (4) is exemplified.

[In the formula, R is the same or different, and indicates hydrogen, or a substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2), and m is 20. An integer of 3000 or more is preferable, except when all Rs are hydrogen at the same time]

The etherified cellulose fibers represented by the general formula (4) have the same or different R, hydrogen, or a substituent represented by the general formula (1) and / or a substitution represented by the general formula (2). It shows a group and has a repeating structure of a cellulose unit into which the substituent is introduced. As the number of repetitions of the repeating structure, m in the general formula (4) is preferably an integer of 20 or more and 3000 or less, and more preferably 100 or more and 2000 or less, from the viewpoint of foaming property.

(Hydrocarbon group which may have a substituent)
In the etherified cellulose fiber of the first aspect, one or more substituents selected from the substituents represented by the above general formula (1) and the following general formula (2) are introduced alone or in any combination. Will be done. In addition, even if the substituent to be introduced is one of the above-mentioned Substituent groups, the same Substituent may be introduced in each Substituent Group, or two or more kinds may be introduced in combination.

_{R 0} in the general formula (1) and the general formula (2) represents a hydrogen atom or a hydroxyl group. _{From the viewpoint of foaming property, R 0} in the general formula (1) and the general formula (2) is preferably a hydroxyl group.

_{R 1} in the general formula (1) is a linear or branched alkyl group having 3 to 30 carbon atoms. The number of carbon atoms of the alkyl group is 3 or more and 30 or less, but from the viewpoint of foaming property, it is preferably 25 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 12 or less. , More preferably 10 or less. Specifically, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, octadecyl group, isooctadecyl group, Examples thereof include an icosyl group and a triacontyl group.

_{R 1} in the general formula (2) is a linear or branched alkyl group having 3 or more and 30 or less carbon atoms. The number of carbon atoms of the alkyl group is 3 or more and 30 or less, but it is preferably 4 or more, more preferably 6 or more from the viewpoint of foaming property, and preferably from the viewpoint of foaming property, availability and reactivity improvement. Is 27 or less, more preferably 22 or less, still more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 12 or less. _{Specifically, the same as R 1} in the above-mentioned general formula (1) can be mentioned.

A in the general formula (2) is a linear or branched divalent saturated hydrocarbon group having 1 or more and 6 or less carbon atoms, and forms an oxyalkylene group with an adjacent oxygen atom. The carbon number of A is 1 or more and 6 or less, but is preferably 2 or more from the viewpoint of foamability, availability and cost, and preferably 4 or less, more preferably 3 or less from the same viewpoint. Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like are exemplified, and among them, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable.

N in the general formula (2) indicates the number of moles of alkylene oxide added. n is a number of 0 or more and 50 or less, but is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more from the viewpoint of foamability, availability, and cost, and is preferably 10 or more from the same viewpoint. It is 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less.

The combination of A and n in the general formula (2) is preferably a straight-chain or branched divalent saturated hydrocarbon group having 2 or more and 3 or less carbon atoms, and n is 0, from the viewpoint of foaming property. It is a combination of a number of 20 or more, more preferably A is a linear or branched divalent saturated hydrocarbon group having 2 or more and 3 or less carbon atoms, and n is a combination of 5 or more and 15 or less.

Specific examples of the substituent represented by the general formula (1) include a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and an isooctadecyl group. Group, icosyl group, propylhydroxyethyl group, butylhydroxyethyl group, pentylhydroxyethyl group, hexylhydroxyethyl group, heptylhydroxyethyl group, octylhydroxyethyl group, 2-ethylhexylhydroxyethyl group, nonylhydroxyethyl group, decylhydroxyethyl Examples thereof include a group, an undecyl hydroxyethyl group, a dodecyl hydroxyethyl group, a hexadecyl hydroxyethyl group, an octadecyl hydroxyethyl group, an isooctadecyl hydroxyethyl group, an icosyl hydroxyethyl group, a triacyl hydroxyethyl group and the like.

Specific examples of the substituent represented by the general formula (2) include, for example, 3-butoxy-2-hydroxy-propyl group, 3-hexitoxyethylene oxide-2-hydroxy-propyl group, 3-hexoxy-2-hydroxy. -Propyl group, 3-octoxyethylene oxide-2-hydroxy-propyl group, 3-octoxy-2-hydroxy-propyl group, 6-ethyl-3-hexitoxy-2-hydroxy-propyl group, 6-ethyl-3-hex Toxyethylene oxide-2-hydroxy-propyl group, 3-detoxyethylene oxide-2-hydroxy-propyl group, 3-detoxy-2-hydroxy-propyl group, 3-undetoxyethylene oxide-2-hydroxy-propyl group, 3-undetoxy -2-Hydroxy-propyl group, 3-dodetoxyethylene oxide-2-hydroxy-propyl group, 3-dodetoxy-2-hydroxy-propyl group, 3-hexadetoxyethylene oxide-2-hydroxy-propyl group, 3-hexadetoxy Examples thereof include a -2-hydroxy-propyl group, a 3-octadetoxyethylene oxide-2-hydroxy-propyl group, and a 3-octadetoxy-2-hydroxy-propyl group. The number of moles of alkylene oxide added may be 0 or more and 50 or less. For example, among the above-mentioned substituents having oxyalkylene groups such as ethylene oxide, substituents having 10, 12, 13, and 20 moles of addition are exemplified. Will be done.

(Introduction rate)
In the etherified cellulose fiber of the first aspect, the introduction rate of the substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2) with respect to 1 mol of the anhydrous glucose unit of cellulose is Although it cannot be unconditionally limited depending on the type of substituent, it is preferably 0.0001 mol or more, more preferably 0.0005 mol or more, still more preferably 0.0007 mol or more, and from the viewpoint of foaming property. It has a cellulose type I crystal structure, and from the viewpoint of foaming property, it is preferably 1.5 mol or less, more preferably 1.3 mol or less, still more preferably 1.0 mol or less, still more preferably 0.8 mol or less. , More preferably 0.6 mol or less, still more preferably 0.5 mol or less. Here, when both the substituent represented by the general formula (1) and the substituent represented by the general formula (2) are introduced, it is the total introduced molar ratio. In this specification, the introduction rate can be measured according to the method described in Examples described later, and may also be described as the introduction molar ratio or the modification rate.

As a more preferable embodiment (aspect 2) of the etherified cellulose fiber in the present invention, for example, one selected from a substituent represented by the following general formula (1) and a substituent represented by the following general formula (2). Alternatively, two or more kinds of substituents and a substituent represented by the following general formula (3) are independently bonded to the cellulose fiber via an ether bond, and have a cellulose type I crystal structure. Can be mentioned.
-CH ₂ -CH (R ₀ ) -R ₁ (1)
-CH _2- CH (R ₀ ) -CH _2- (OA) _n- O-R ₁ (2)
-CH ₂ -CH (R ₀ ) -R ₂ (3)
_{[In the formula, R 0} in the general formula (1) and the general formula (2) _{indicates a hydrogen atom or a hydroxyl group, and R 1} in the general formula (1) and the general formula (2) has 3 or more carbon atoms, respectively. The following linear or branched alkyl groups are shown, where n in the general formula (2) is a number of 0 or more and 50 or less, and A is a linear or branched divalent saturated hydrocarbon group having 1 or more and 6 or less carbon atoms. In the general formula (3), R ₀ represents a hydrogen atom or a hydroxyl group, and R ₂ represents an alkyl group having 1 or more and 2 or less carbon atoms. ]

Specific examples of the etherified cellulose fiber of the second aspect include those represented by the following general formula (5).

[In the formula, R is the same or different, hydrogen, (a) a substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2), or (b). ) Indicates a substituent represented by the general formula (3), and m is preferably an integer of 20 or more and 3000 or less, except that all R are hydrogen at the same time and the substituent (a) at the same time. And at the same time, it is a substituent (b)]

The etherified cellulose fibers represented by the general formula (5) have the same or different R, and are represented by hydrogen, (a) the substituent represented by the general formula (1), and the general formula (2). It represents a substituent selected from the substituents, or (b) a substituent represented by the general formula (3), and has a repeating structure of a cellulose unit into which the substituent has been introduced. As the number of repetitions of the repeating structure, m in the general formula (5) is preferably an integer of 20 or more and 3000 or less, and more preferably 100 or more and 2000 or less from the viewpoint of foaming property.

(Hydrocarbon group which may have a substituent)
The hydrocarbon group which may have a substituent in the etherified cellulose fiber of the second aspect is (a) the substituent represented by the general formula (1) and the substitution represented by the general formula (2). One or more substituents selected from the groups, and (b) the substituents represented by the above general formula (3), that is, the substituents of the group (a) and the group (b). Substituents are attached together and introduced alone or in any combination in each group. In addition, in the substituent of the group (a), even in the case of either the substituent represented by the general formula (1) or the substituent represented by the general formula (2), in each substituent. May be introduced in combination of two or more of the same substituent. In the substituents of the group (a), the substituents represented by the general formula (1) and the substituents represented by the general formula (2) may be introduced individually or in combination of two or more. ..

The general formula (1) and the general formula (2) are the same as those in the first aspect.

_{R 0} in the general formula (3) represents a hydrogen atom or a hydroxyl group, and a hydroxyl group is preferable from the viewpoint of foaming property.
_{R 2} in the general formula (3) is an alkyl group having 1 or more carbon atoms and 2 or less carbon atoms, and specifically, it is a methyl group or an ethyl group. Specific examples of the substituent represented by the general formula (3) include a propyl group, a butyl group, a 2-hydroxy-propyl group, a 2-hydroxy-butyl group and the like.

(Introduction rate)
In the etherified cellulose fiber of the second aspect, the introduction rate of the substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2) with respect to 1 mol of the anhydrous glucose unit of cellulose is Similar to the first aspect, the introduction rate of the substituent represented by the general formula (3) with respect to 1 mol of the anhydrous glucose unit of cellulose has a cellulose type I crystal structure, and is preferably from the viewpoint of foaming property. 1.5 mol or less, more preferably 1.0 mol or less, still more preferably 0.8 mol or less, preferably 0.01 mol or more, more preferably 0.02 mol or more, still more preferably 0.04 mol. That is all.

(Average fiber diameter)
The etherified cellulose fiber in the present invention is not particularly limited in average fiber diameter regardless of the type of substituent. For example, an embodiment in which the average fiber diameter is on the micro order and an embodiment in which the average fiber diameter is on the nano order are exemplified.

The etherified cellulose fiber of the micro-order embodiment is preferably 5 μm or more, more preferably 7 μm or more, still more preferably 10 μm or more, from the viewpoint of foamability, handleability, availability, and cost. Although the upper limit is not particularly set, it is preferably 100 μm or less, more preferably 70 μm or less, still more preferably 50 μm or less, still more preferably 40 μm or less, still more preferably 30 μm or less, from the viewpoint of foaming property and handleability. In this specification, the average fiber diameter of micro-order cellulose fibers can be measured according to the following method.

Specifically, for example, water obtained by stirring absolutely dried cellulose fibers in ion-exchanged water using a household mixer or the like to dissolve the fibers, and then further adding ion-exchanged water and stirring the fibers so as to be uniform. A method of analyzing a part of the dispersion liquid with "Kajaani Fiber Lab" manufactured by Mezzo Automation Co., Ltd. can be mentioned. By such a method, the fiber diameter having an average fiber diameter of micro order can be measured.

The etherified cellulose fiber of the nano-order embodiment is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 10 nm or more, still more preferably 20 nm or more from the viewpoint of foamability, handleability, availability, and cost. From the viewpoint of foaming property and handleability, it is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 120 nm or less. In this specification, the average fiber diameter of nano-order cellulose fibers can be measured according to the following method.

Specifically, the dispersion obtained when the micronization treatment was performed was observed with an optical microscope (“Digital Microscope VHX-1000” manufactured by KEYENCE CORPORATION) at a magnification of 300 to 1000 times, and the fiber 30 was observed. The nano-order fiber diameter can be measured by measuring the average value of the number or more. When observation with an optical microscope is difficult, an atomic force microscope (AFM, AFM) prepares a dispersion prepared by further adding a solvent to the dispersion and drops it on mica (mica) and dries it as an observation sample. It can be measured using a Nanoscope III Tapping mode AFM, manufactured by Digital instrument, and a probe using Point Probe (NCH) manufactured by Nanosensors). In general, the smallest unit of cellulose nanofibers prepared from higher plants is that 6 × 6 molecular chains are packed in a nearly square shape, so the height analyzed by AFM images should be regarded as the fiber width. Can be done.

(Crystallinity)
The crystallinity of the etherified cellulose fiber in the present invention is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more from the viewpoint of developing foaming property. Further, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, still more preferably 75% or less. In this specification, the crystallinity of cellulose is the cellulose type I crystallinity calculated from the diffraction intensity value by the X-ray diffraction method, and can be measured according to the method described in Examples described later. The cellulose type I is the crystal form of natural cellulose, and the cellulose type I crystallinity means the ratio of the amount of the crystal region to the whole cellulose. The presence or absence of the cellulose I-type crystal structure can be determined by the peak at 2θ = 22.6 ° in the X-ray diffraction measurement.

[Manufacturing method of etherified cellulose fiber]
In the etherified cellulose fiber of the present invention, as described above, a hydrocarbon group which may have a substituent is bonded to the surface of the cellulose fiber via an ether bond, but the introduction of the substituent is particularly limited. It can be carried out according to a known method.

Hereinafter, specific examples of the methods for producing the etherified cellulose fibers of Aspects 1 and 2 will be described.

(Method for Producing Ethereal Cellulose Fiber of Aspect 1)
As a specific example of the method for producing the etherified cellulose fiber of the first aspect, there is an embodiment in which a specific compound is reacted with a cellulosic raw material in the presence of a base.

(Cellulose-based raw material)
Cellulose-based raw materials are not particularly limited, and are wood-based (coniferous / broad-leaved trees), herbaceous (rice family, blue-green algae, legume family plant raw materials, palm family plant non-wood raw materials), pulps (cotton seeds). (Cotton linter pulp, etc. obtained from the fibers around the), papers (newsprint, cardboard, magazines, high-quality paper, etc.). Of these, woody and herbaceous are preferable from the viewpoint of availability and cost.

The shape of the cellulosic raw material is not particularly limited, but is preferably fibrous, powdery, spherical, chip-shaped, or flake-shaped from the viewpoint of handleability. Moreover, it may be a mixture of these.

In addition, the cellulosic raw material can be pretreated with at least one pretreatment selected from biochemical treatment, chemical treatment, and mechanical treatment from the viewpoint of handleability and the like. The biochemical treatment is not particularly limited in the drug to be used, and examples thereof include treatments using enzymes such as endoglucanase, exoglucanase, and beta-glucosidase. The chemical treatment is not particularly limited in the chemicals used, and examples thereof include acid treatment with hydrochloric acid and sulfuric acid, and oxidation treatment with hydrogen peroxide and ozone. The machine processing is not particularly limited in the machine used and the processing conditions. For example, a high-pressure compression roll mill, a roll mill such as a roll rotation mill, a ring roller mill, a roller race mill, or a vertical roller mill such as a ball race mill, Container drive medium mills such as rolling ball mills, vibrating ball mills, vibrating rod mills, vibrating tube mills, planetary ball mills or centrifugal fluidization mills, tower type crushers, stirring tank type mills, distribution tank type mills or general type mills Examples thereof include compact shear mills such as type mills, high-speed centrifugal roller mills and ong mills, grinders such as mortars, stone mills, mass colloiders, fret mills and edge runner mills, knife mills, pin mills and cutter mills.

In addition, during the above mechanical treatment, solvents such as water, ethanol, isopropyl alcohol, t-butyl alcohol, toluene and xylene, plasticizers such as phthalic acid, adipic acid and trimellitic acid, urea and alkali (earth) ) It is also possible to promote the shape change by mechanical treatment by adding an auxiliary agent such as a metal hydroxide or a hydrogen bond inhibitor such as an amine compound. By adding the shape change in this way, the handleability of the cellulosic raw material is improved, the introduction of the substituent is improved, and the physical properties of the obtained etherified cellulose fiber can be improved. The amount of the additive aid used varies depending on the additive aid used, the machine treatment method used, etc., but from the viewpoint of exhibiting the effect of promoting the shape change, it is usually 5 parts by mass or more with respect to 100 parts by mass of the raw material. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and usually 10,000 parts by mass or less, preferably 5000 parts by mass or less, from the viewpoint of exhibiting the effect of promoting shape change and economic efficiency. It is preferably 3000 parts by mass or less.

The average fiber diameter of the cellulosic raw material is not particularly limited, but is preferably 5 μm or more, more preferably 7 μm or more, still more preferably 10 μm or more, still more preferably 15 μm or more, from the viewpoint of handleability and cost. Although the upper limit is not particularly set, from the viewpoint of handleability, it is preferably 10,000 μm or less, more preferably 5,000 μm or less, still more preferably 1,000 μm or less, still more preferably 500 μm or less, still more preferably 100 μm or less. Is.

Further, from the viewpoint of reducing the number of manufacturing steps, a cellulosic raw material finely divided in advance may be used, and the average fiber diameter in that case is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoint of availability and cost. It is more preferably 3 nm or more, still more preferably 10 nm or more. The upper limit is not particularly set, but from the viewpoint of handleability, it is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, still more preferably 100 nm or less, still more preferably 80 nm or less.

The average fiber diameter of the cellulosic raw material can be measured in the same manner as the etherified cellulose fiber described above.

The composition of the cellulosic raw material is not particularly limited, but the cellulose content in the cellulosic raw material is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass from the viewpoint of obtaining cellulose fibers. From the viewpoint of availability, it is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less, still more preferably 90% by mass or less. Here, the cellulosic content in the cellulosic raw material is the cellulosic content in the residual component excluding water in the cellulosic raw material.

The water content in the cellulose-based raw material is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5, from the viewpoint of availability and cost. By mass% or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2.0% by mass or more, and from the viewpoint of handleability, preferably 50% by mass or less. It is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably an absolute dry treatment, that is, 10% by mass or less.

(base)
In this production mode, a base is mixed with the cellulosic raw material.

The base is not particularly limited, but from the viewpoint of advancing the etherification reaction, alkali metal hydroxide, alkaline earth metal hydroxide, 1-3 amine, quaternary ammonium salt, imidazole and its derivative, pyridine. One or more selected from the group consisting of and derivatives thereof and alkoxides is preferable.

Examples of the alkali metal hydroxide and alkaline earth metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide and the like.

The 1st to 3rd amines are primary amines, secondary amines, and tertiary amines, and specific examples thereof include ethylenediamine, diethylamine, proline, N, N, N', and N'-tetramethylethylenediamine. N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, tris (3-dimethylaminopropyl) amine, Examples thereof include N, N-dimethylcyclohexylamine and triethylamine.

Examples of the quaternary ammonium salt include tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium fluoride, tetraethylammonium bromide, and water. Examples thereof include tetramethylammonium oxide, tetramethylammonium chloride, tetramethylammonium fluoride, tetramethylammonium bromide and the like.

Examples of imidazole and its derivatives include 1-methylimidazole, 3-aminopropylimidazole, carbonyldiimidazole and the like.

Examples of pyridine and its derivatives include N, N-dimethyl-4-aminopyridine, picoline and the like.

Examples of the alkoxide include sodium methoxide, sodium ethoxide, potassium-t-butoxide and the like.

The amount of the base is preferably 0.01 equal or more, more preferably 0.05 equal or more, still more preferably 0.1, from the viewpoint of advancing the etherification reaction with respect to the anhydrous glucose unit of the cellulosic raw material. Equal amount or more, more preferably 0.2 equal amount or more, preferably 10 equal amount or less, more preferably 8 equal amount or less, still more preferably 5 equal amount or less, still more preferably 3 equal amount or less from the viewpoint of manufacturing cost. It is less than the amount.

The cellulosic raw material and the base may be mixed in the presence of a solvent. The solvent is not particularly limited, and for example, water, isopropanol, t-butanol, dimethylformamide, toluene, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, etc. Included are 1,4-dioxane, and mixtures thereof.

The temperature and time of the mixture of the cellulosic raw material and the base are not particularly limited as long as they can be mixed uniformly.

Next, a compound for introducing a hydrocarbon group which may have a substituent is added to the mixture of the cellulosic raw material and the base obtained above, and the cellulosic raw material is reacted with the compound. Such a compound includes one or more substituents selected from the substituents represented by the general formula (1) and the substituents represented by the general formula (2) when reacting with a cellulose-based raw material. Is not particularly limited as long as it can be bonded via an ether bond, and in the present invention, a compound having a reactive cyclic structural group may be used from the viewpoint of a reactive and non-halogen-containing compound. It is preferable to use a compound having an epoxy group. Each compound is illustrated below.

Examples of the compound to which the substituent represented by the general formula (1) can be bonded via an ether bond include an alkylene oxide compound represented by the following general formula (1A) and an alkyl represented by the general formula (1B). Halides are preferred. Such a compound may be prepared according to a known technique, or a commercially available product may be used. From the viewpoint of foaming property, the total carbon number of the compound is 3 or more, preferably 5 or more, more preferably 6 or more, further preferably 8 or more, still more preferably 12 or more, and the foaming property. From the viewpoint, it is 32 or less, preferably 27 or less, more preferably 22 or less, still more preferably 20 or less, still more preferably 18 or less, still more preferably 14 or less, still more preferably 12 or less.

[In the formula, R ₁ represents a linear or branched alkyl group having 3 to 30 carbon atoms. ]

X- (CH ₂ ) _2- R ₁ (1B)
[In the formula, R ₁ represents a linear or branched alkyl group having 3 to 30 carbon atoms, and X is a halogen atom selected from fluorine, chlorine, bromine, and iodine. ]

_{R 1} in the general formulas (1A) and (1B) is a linear or branched alkyl group having 3 to 30 carbon atoms. The number of carbon atoms of the alkyl group is 3 or more and 30 or less, but from the viewpoint of foaming property, it is preferably 4 or more, more preferably 6 or more, still more preferably 10 or more, and preferably from the viewpoint of foaming property. It is 25 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 12 or less, still more preferably 10 or less. Specifically, there can be mentioned those described in the section R ₁ in the substituent represented by the general formula (1).

Specific examples of the compound represented by the general formula (1A) include 1,2-epoxyhexane, 1,2-epoxydecane, and 1,2-epoxyoctadecane.
Specific examples of the compound represented by the general formula (1B) include 1-chloropentane, 1-chlorohexane, 1-chlorooctane, 1-chlorodecane, 1-chlorododecane, 1-chlorohexadecane, 1-chlorooctadecane, 1 -Bromopentane, 1-bromohexane, 1-bromooctane, 1-bromodecane, 1-bromododecane, 1-bromohexadecane, 1-bromooctadecane, 1-iodopentane, 1-iodohexane, 1-iodooctane, 1- Examples thereof include iododecane, 1-iododecane, 1-iodohexadecane, and 1-iodooctadecane.

As the compound to which the substituent represented by the general formula (2) can be bonded via an ether bond, for example, the glycidyl ether compound represented by the following general formula (2A) is preferable. Such a compound may be prepared according to a known technique, or a commercially available product may be used. The total carbon number of the compound is preferably 5 or more, more preferably 6 or more, still more preferably 10 or more, still more preferably 20 or more, and 100 or less from the viewpoint of foaming property. Is preferable, more preferably 75 or less, still more preferably 50 or less.

[In the formula, R ₁ is a linear or branched alkyl group having 3 to 30 carbon atoms, A is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and n is 0 or more. Indicates a number of 50 or less]

_{R 1} in the general formula (2A) is a linear or branched alkyl group having 3 to 30 carbon atoms. The number of carbon atoms of the alkyl group is 3 or more and 30 or less, but from the viewpoint of foaming property, it is preferably 4 or more, more preferably 6 or more, and from the viewpoint of foaming property, it is preferably 27 or less, more preferably. It is 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 12 or less. Specifically, there can be mentioned those described in the section R ₁ in the substituent represented by the general formula (2).

A in the general formula (2A) is a linear or branched divalent saturated hydrocarbon group having 1 or more and 6 or less carbon atoms, and forms an oxyalkylene group with an adjacent oxygen atom. The carbon number of A is 1 or more and 6 or less, but is preferably 2 or more from the viewpoint of availability and cost, and preferably 4 or less, more preferably 3 or less from the same viewpoint. Specifically, those described in the section A of the substituent represented by the general formula (2) are exemplified, and among them, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable.

N in the general formula (2A) indicates the number of moles of alkylene oxide added. n is a number of 0 or more and 50 or less, but is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more from the viewpoint of availability and cost, and preferably 40 or less, more preferably from the same viewpoint. It is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less.

Specific examples of the compound represented by the general formula (2A) include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, stearyl glycidyl ether, isostearyl glycidyl ether, and polyoxyalkylene alkyl ether.

The amount of the compound can be determined by the desired introduction rate of the substituent represented by the general formula (1) and / or the substituent represented by the general formula (2) in the obtained etherified cellulose fiber. From the viewpoint of reactivity, the amount is preferably 0.01 equal or more, more preferably 0.1 equal or more, still more preferably 0.3 equal or more, still more preferably 0.3 equal or more, relative to the anhydrous glucose unit of the cellulosic raw material. 0.5 equal or more, more preferably 1.0 equal or more, preferably 10 equal or less, more preferably 8 equal or less, still more preferably 6.5 equal or less, from the viewpoint of manufacturing cost. More preferably, it is 5 equal or less.

(Ether reaction)
The ether reaction between the compound and the cellulosic raw material can be carried out by mixing both in the presence of a solvent. The solvent is not particularly limited, and a solvent exemplified as being usable when the base is present can be used.

The amount of the solvent used is not unconditionally determined depending on the type of the cellulose-based raw material or the compound for introducing the hydrocarbon group which may have the substituent, but is based on 100 parts by mass of the cellulose-based raw material. From the viewpoint of reactivity, it is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, further preferably 75 parts by mass or more, further preferably 100 parts by mass or more, still more preferably 200 parts by mass or more, and it is productive. From the viewpoint, it is preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, further preferably 2,500 parts by mass or less, still more preferably 1,000 parts by mass or less, still more preferably 500 parts by mass or less. is there.

The mixing conditions are not particularly limited as long as the cellulosic raw material and the compound for introducing the hydrocarbon group which may have the above-mentioned substituent are uniformly mixed and the reaction can proceed sufficiently, and are continuous. The mixing process may or may not be performed. When a relatively large reaction vessel exceeding 1 L is used, stirring may be appropriately performed from the viewpoint of controlling the reaction temperature.

The reaction temperature is not unconditionally determined by the type of the compound for introducing the cellulose-based raw material or the hydrocarbon group which may have the above-mentioned substituent and the target introduction rate, but from the viewpoint of improving the reactivity. Therefore, it is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C. or higher, and from the viewpoint of suppressing thermal decomposition, preferably 120 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 ° C. or higher. It is as follows.

The reaction time is not unconditionally determined by the type of the compound for introducing the cellulose-based raw material or the hydrocarbon group which may have the above-mentioned substituent and the target introduction rate, but from the viewpoint of reactivity, it is determined. It is preferably 0.5 hours or more, more preferably 1 hour or more, more preferably 2 hours or more, more preferably 3 hours or more, more preferably 6 hours or more, still more preferably 10 hours or more, from the viewpoint of productivity. It is preferably 60 hours or less, more preferably 48 hours or less, still more preferably 36 hours or less.

Further, after the reaction, the etherified cellulose fiber is subjected to, for example, the same treatment as the pretreatment for the cellulosic raw material from the viewpoint of handleability, and is in the form of chips, flakes, or powder. It may be. Since the shape change is brought about by such treatment, when the obtained etherified cellulose fiber is added to water, the composition of the etherified cellulose fiber and water can be produced with lower energy.

Furthermore, the etherified cellulose fiber may be miniaturized by performing a known miniaturization treatment after the reaction. For example, it can be miniaturized by performing a treatment using a high-pressure homogenizer or the like in an organic solvent. Further, it is also possible to obtain the fine etherified cellulose fiber by carrying out the above-mentioned substituent introduction reaction using a cellulosic raw material that has been finely divided in advance, but from the viewpoint of foaming property, after the reaction of introducing the substituent. , It is preferable to carry out a known miniaturization treatment to miniaturize.

Specifically, for example, in the case of obtaining an etherified cellulose fiber having an average fiber diameter of 5 μm or more, mechanical treatment such as a container-driven medium mill or a medium stirring type mill can be performed. Further, when an etherified cellulose fiber having an average fiber diameter of 1 nm or more and 500 nm or less is obtained, a treatment using a grinder such as a mass colloider or a treatment using a high-pressure homogenizer or the like in an organic solvent can be performed.

After the reaction, post-treatment can be appropriately performed in order to remove unreacted compounds, bases and the like. As a method of the post-treatment, for example, an unreacted base can be neutralized with an acid (organic acid, inorganic acid, etc.), and then washed with an unreacted compound or a solvent in which the base dissolves. If desired, further drying (vacuum drying or the like) may be performed.

Thus, etherified cellulose fibers are obtained.

(Method for Producing Ethered Cellulose Fiber of Aspect 2)
As an example of such a production method, for example, in the presence of a base, the etherified cellulose fiber of the first aspect is reacted with a compound capable of binding a substituent represented by the general formula (3) via an ether bond. The method can be mentioned. In the present invention, regardless of the order of introduction of the substituents represented by the general formulas (1) and / or (2) and the introduction of the substituents represented by the general formula (3), the general formula ( As the introduction condition of the substituent represented by 3), the same conditions as in the first aspect can be adopted.

Examples of the compound to which the substituent represented by the general formula (3) can be bonded via an ether bond include an alkylene oxide compound represented by the following general formula (3A) and an alkyl represented by the general formula (3B). Halides are preferred. Such a compound may be prepared according to a known technique, or a commercially available product may be used. The total number of carbon atoms of the compound is 3 or more and 4 or less from the viewpoint of foaming property.

[In the formula, R ₂ represents an alkyl group having 1 or more carbon atoms and 2 or less carbon atoms. ]

X- (CH ₂ ) _2- R ₂ (3B)
[In the formula, R ₂ represents an alkyl group having 1 or more carbon atoms and 2 or less carbon atoms, and X is a halogen atom selected from fluorine, chlorine, bromine and iodine. ]

_{R 2} in the general formulas (3A) and (3B) is an alkyl group having 1 or more carbon atoms and 2 or less carbon atoms, and is a methyl group or an ethyl group.

Specific examples of the compound represented by the general formula (3A) include 1,2-epoxypropane and 1,2-epoxybutane.
Specific examples of the compound represented by the general formula (3B) include 1-chloropropane, 1-chlorobutane, 1-bromopropane, 1-bromobutane, 1-iodopropane, 1-iodobutane and the like.

The amount of the compound can be determined by the desired introduction rate of the substituent represented by the general formula (3) in the obtained cellulose fiber, but from the viewpoint of foaming property, the anhydrous glucose unit of the cellulosic raw material can be used. On the other hand, it is preferably 5.0 equal or less, and the lower limit is about 0.02 equal.

(water)
The water constituting the composition of the present invention is not particularly limited, but it is preferable that the amount of impurities is as small as possible. For example, tap water, industrial water, ion-exchanged water, distilled water, and ultrapure water are preferable waters.

[Composition]
The etherified cellulose fibers can be mixed with water to obtain the composition of the present invention. The present invention also provides a composition comprising etherified cellulose fibers and water.

The content of the etherified cellulose fiber in the composition of the present invention is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass, from the viewpoint of foaming property. The above is more preferably 0.1% by mass or more, and from the viewpoint of cost, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 1% by mass or less. is there.

From the viewpoint of cost, the content of water in the composition of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, still more preferably 50% by mass or more, and further. It is preferably 80% by mass or more, and from the viewpoint of foaming property, it is preferably 99.99% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.95% by mass or less, still more preferably 99.9% by mass. It is as follows.

The amount of etherified cellulose fibers in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, still more preferably 0.03 parts by mass or more, with respect to 100 parts by mass of water from the viewpoint of foaming property. Is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and from the viewpoint of containing etherified cellulose fibers, preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, still more preferably. It is 50 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

In the composition of the present invention, as other components other than the above, inorganic salts, organic salts, surfactants, oils, moisturizers, preservatives, organic fine particles, inorganic fine particles, dyes, deodorants, fragrances, organic solvents Such functional additives can be contained within a range that does not impair the effects of the present invention. The content of such a component may be appropriately contained as long as the effect of the present invention is not impaired, but for example, it is preferably 50% by mass or less, more preferably 40% by mass or less, and about 30% by mass in the composition. The following is more preferable.

The composition of the present invention exists and is provided, for example, as a dispersion of etherified cellulose fibers and water.

The composition of the present invention has a surprisingly high foaming effect. Therefore, the composition of the present invention is provided as a foaming agent composition. Further, the composition obtained by removing water from the composition of the present invention, that is, a hydrocarbon group which may have a substituent is bonded to the cellulose fiber via an ether bond, and has a cellulose type I crystal structure. Quality cellulose fibers may be used as a foaming agent.

Specifically, by utilizing such effects, skin treatment composition such as body shampoo, hand cleaner, shave lotion, facial cleanser, cleansing cream, lotion, beauty liquid, pack, ointment, and patch, shampoo. , Conditioner, rinse, rinse-in shampoo, hair styling agent, hair treatment agent, hair dye, hair treatment agent composition such as hair restorer, dishwashing detergent, toilet cleaner, tile cleaner, metal cleaner, Selected from the group consisting of hard surface treatment agent compositions such as bath cleaners and floor cleaners, and clothing treatment agent compositions such as laundry detergents, washing softeners, clothing pastes, and finishing agents. It can be used for one or more purposes.

(Manufacturing method of composition)
The composition of the present invention can be prepared by mixing the etherified cellulose fiber, water, and if necessary, a raw material containing various additives, according to each use, using a known stirrer.

The mixing ratio of the etherified cellulose fiber and water and the amount of various additives added may be set so as to satisfy the above ranges.

Hereinafter, the present invention will be specifically described with reference to Production Examples, Examples and Test Examples. It should be noted that this embodiment is merely an example of the present invention and does not mean any limitation. The part in the example is a mass part unless otherwise specified. The "normal pressure" indicates 101.3 kPa, and the "room temperature" indicates 25 ° C.

Production Example 1 (Production of polyoxyalkylene alkyl etherifying agent)
Melt 250 kg of polyoxyethylene (13) -n-alkyl (C12) ether (manufactured by Kao, Emargen 120, alkyl chain length; n-C12, molar average degree of polymerization of oxyethylene group; 13) in a 1000 L reaction vessel. Then, 3.8 kg of tetrabutylammonium bromide (manufactured by Koei Chemical Industry Co., Ltd.), 81 kg of epichlorohydrin (manufactured by Dow Chemical Co., Ltd.) and 83 kg of toluene were added, and the mixture was stirred and mixed. While maintaining the temperature in the tank at 50 ° C. and stirring, 130 kg of a 48 mass% sodium hydroxide aqueous solution (manufactured by Nankai Chemical Co., Inc.) was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred and aged for 6 hours while maintaining the temperature in the tank at 50 ° C. After completion of aging, the reaction mixture was washed with 250 kg of water 6 times to remove salts and alkalis, and then the organic phase was heated to 90 ° C. under reduced pressure (6.6 kPa) to remove residual epichlorohydrin, solvent and water. Distilled away. Under reduced pressure, 250 kg of steam was further blown to remove the low boiling point compound to obtain 240 kg of n-alkyl (C12) polyoxyethylene (13) glycidyl ether (hereinafter, also referred to as emalgen 120GE) having the structure of the following formula.

Example 1 <Preparation of aqueous dispersion 1 of etherified cellulose fiber>
First, prepared by adding 96 g of 6.4 mass% sodium hydroxide aqueous solution (prepared with sodium hydroxide granules manufactured by Wako Pure Chemical Industries, Ltd. and ion-exchanged water) to 45 g of absolutely dried cellulose powder (ARBOCEL BC200 manufactured by Rettenmeier), NaOH 0.55. Equal amount / 1 equal amount of anhydrous glucose unit (AGU: calculated assuming that all cellulose raw materials are composed of anhydrous glucose unit, the same applies hereinafter), and after mixing uniformly, 39 g of propylene oxide (Wako Pure Chemical Industries, Ltd.) (2.4 equal amount / AGU) manufactured by the same company was added, and after sealing, a standing reaction was carried out at 50 ° C. for 24 hours. After the reaction, neutralize with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), thoroughly wash with water / isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.) to remove impurities, and vacuum dry at 50 ° C. overnight. As a result, an etherified cellulose fiber having one kind of substituent was obtained.

Next, 96 g (0.55 equal amount of NaOH) of a 6.4 mass% aqueous sodium hydroxide solution was added to 45 g of the etherified cellulose fiber obtained above, mixed uniformly, and then 1,2-epoxy. 5.6 g (0.20 equal amount / AGU) of hexane was added, and after sealing, a standing reaction was carried out at 70 ° C. for 20 hours. After the reaction, neutralize with acetic acid, thoroughly wash with acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and water / isopropanol mixed solvent to remove impurities, and further vacuum dry at 50 ° C. overnight to obtain two types. An etherified cellulose fiber having a substituent was obtained.

1.2 g of the obtained etherified cellulose fiber having two kinds of substituents was put into 98.8 g of ion-exchanged water, and after stirring with a homogenizer (TK Robomix manufactured by Primix Corporation) at 3000 rpm for 30 minutes. , Fine etherified cellulose dispersion 1 (solid content) in which finely divided etherified cellulose fibers are dispersed in water by 10-pass treatment at 100 MPa with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., "NanoVeta L-ES"). A concentration of 1.2% by mass) was obtained.

Example 2 <Preparation of aqueous dispersion 2 of etherified cellulose fiber>
To 45 g of the etherified cellulose fiber having one kind of substituent obtained in Example 1, 96 g of a 6.4 mass% sodium hydroxide aqueous solution (NaOH 0.55 equal amount / AGU) was added and mixed uniformly. After that, 23 g (0.10 equal amount / AGU) of the polyoxyalkylene alkyl ether agent prepared in Production Example 1 was added, and after sealing, a standing reaction was carried out at 70 ° C. for 20 hours. After the reaction, neutralize with acetic acid, thoroughly wash with acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and water / isopropanol mixed solvent to remove impurities, and further vacuum dry at 50 ° C. overnight to obtain two types. An etherified cellulose fiber having a substituent was obtained.

1.4 g of the obtained etherified cellulose fiber having two kinds of substituents was put into 100 g of ion-exchanged water, and the same dispersion treatment as in Example 1 was carried out to obtain the finely divided etherified cellulose fiber in water. Fine etherified cellulose dispersion 1 (solid content concentration 1.4% by mass) dispersed in 1 was obtained.

The obtained fine etherified cellulose fiber dispersion was evaluated for the substituent introduction rate and the confirmation of the crystal structure (crystallinity) according to the methods of Test Examples 1 and 2 below. The results are shown in Table 1.

Test Example 1 (Substituent introduction rate (degree of substitution))
The content% (mass%) of the hydrophobic ether group contained in the obtained etherified cellulose fiber is determined by Analytical Chemistry, Vol. 51, No. The Zeisel method, which is known as a method for analyzing the average number of moles of alkoxy groups added to cellulose ether, described in 13, 2172 (1979), "15th Amendment of the Japanese Pharmacy (Hydroxypropyl Cellulose Analysis Method)", etc. Calculated according to. The procedure is shown below.

(I) 0.1 g of n-octadecane was added to a 200 mL volumetric flask, and the volumetric flask was adjusted to the marked line with hexane to prepare an internal standard solution.
(Ii) 100 mg of purified and dried etherified cellulose fiber and 100 mg of adipic acid were precisely weighed in a 10 mL vial, and 2 mL of hydrogen iodide was added and sealed.
(Iii) The mixture in the vial was heated with a block heater at 160 ° C. for 1 hour while stirring with a stirrer tip.
(Iv) After heating, 3 mL of the internal standard solution and 3 mL of diethyl ether were sequentially injected into the vial, and the mixture was stirred at room temperature for 1 minute.
(V) The upper layer (diethyl ether layer) of the mixture separated into two phases in the vial was analyzed by gas chromatography (manufactured by SHIMADZU, "GC2010Plus"). The analysis conditions were as follows.
Column: Agilent Technologies DB-5 (12 m, 0.2 mm x 0.33 μm)
Column temperature: 100 ° C → 10 ° C / min → 280 ° C (10 min Hold)
Injector temperature: 300 ° C, detector temperature: 300 ° C, driving amount: 1 μL

The content (% by mass) of the ether group in the etherified cellulose fiber was calculated from the detected amounts of the etherification reagent used, that is, propylene oxide, polyoxyalkylene alkyl etherifying agent and 1,2-epoxide hexane.
From the obtained ether group content, the molar substitution degree (MS) (molar amount of substituents per 1 mol of anhydrous glucose unit) was calculated using the following mathematical formula (1).

(Formula 1)
MS = (W1 / Mw) / ((100-W1) /162.14)
W1: Content of ether group in etherified cellulose fiber (mass%)
Mw: Molecular weight of the introduced etherification reagent (g / mol)

Test Example 2 (Confirmation of crystal structure)
The crystal structure of the etherified cellulose fiber was confirmed by measuring under the following conditions using "Rigaku RINT 2500VC X-RAY differential tometer" manufactured by Rigaku.
The measurement conditions were X-ray source: Cu / Kα-radiation, tube voltage: 40 kv, tube current: 120 mA, measurement range: diffraction angle 2θ = 5 to 45 °, and X-ray scan speed: 10 ° / min. The measurement sample was prepared by compressing pellets having an ^{area of 320 mm 2 × thickness of 1 mm.} Further, the crystallinity of the cellulose type I crystal structure was calculated by calculating the obtained X-ray diffraction intensity based on the following formula (A).

Cellulose type I crystallinity (%) = [(I22.6-I18.5) /I22.6] x 100 (A)
[In the formula, I22.6 is the diffraction intensity of the lattice plane (002 surface) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 is the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5 °). Show]

On the other hand, when the crystallinity obtained by the above formula (A) is 35% or less, from the viewpoint of improving the calculation accuracy, the description on P199-200 of the "Wood Science Experiment Manual" (edited by the Japan Wood Society) is followed. , It is preferable to calculate based on the following formula (B).
Therefore, when the crystallinity obtained by the above formula (A) is 35% or less, the value calculated based on the following formula (B) can be used as the crystallinity.
Cellulose type I crystallinity (%) = [Ac / (Ac + Aa)] x 100 (B)
[In the formula, Ac is a lattice plane (002 plane) (diffraction angle 2θ = 22.6 °), (011 plane) (diffraction angle 2θ = 15.1 °) and (0-11 plane) (diffraction angle 2θ =) in X-ray diffraction. The sum of the peak areas of 16.2 °), Aa, indicates the peak area of the amorphous part (diffraction angle 2θ = 18.5 °), and each peak area is obtained by fitting the obtained X-ray diffraction chart with a Gaussian function.]

The composition of the etherified cellulose fibers obtained in the above examples is shown in Table 1. Here, the aqueous dispersion 1 obtained in Example 1 is CNF-1, the aqueous dispersion 2 obtained in Example 2 is CNF-2, and the cellulose fiber (CNF) used in Comparative Example 1 as a comparison target. (BiNFi-s manufactured by Sugino Machine Limited) is described as CNF-RF.

Using the above CNF-1, CNF-2 and CNF-RF, the active ingredient was diluted with ion-exchanged water to 0.3% by mass to prepare each test solution. As Comparative Example 2, the test solution was prepared only with ion-exchanged water without adding cellulose fibers. Using these test solutions, foaming, skin coating, hair coating, hard surface coating and clothing coating were tested according to the evaluation criteria and evaluation methods shown below. The results are shown in Table 2.

Evaluation method <foaming test>
Put 20 g of the test solution in a 100 mL graduated cylinder with a lid and shake at a speed of 10 times / 10 seconds to measure the amount of foam immediately after standing (air phase and foam surface boundary scale-solution phase and foam surface boundary). It was measured.

<Skin application test>
Five professional panelists applied 0.5 mL of the test solution to their fingers, rinsed it with tap water, and then dried it. According to the evaluation criteria and evaluation method shown below, the feeling of smoothness after drying and the feeling of coating after drying were obtained. Evaluation was performed. Table 2 shows the average score of the evaluations of 5 people.
・ Smooth feeling after drying 5: Very smooth and does not feel sticky skin at all.
4: Smooth and almost non-sticky.
3: Normal (equivalent to Comparative Example 2).
2: I feel a clear stickiness without exposing it.
1: Very sticky (no silky feeling at all).
・ Coat feeling after drying 5: The coat feeling is strong, and you do not feel the dryness of your fingertips at all.
4: There is a feeling of coat, and the dryness of the fingertips is weak.
3: Normal (equivalent to Comparative Example 2).
2: There is no coat feeling, and the fingertips are very dry.
1: There is no coat feeling at all, and the dryness of the fingertips is very strong.

<Hair application test>
Five specialized panelists apply 0.1 mL of the test solution to the tress (Asian hair, about 15 cm, 1 g), rinse and dry (dryer), and use the evaluation criteria and evaluation method shown below to apply the hair at the time of application. The cohesiveness, the cohesiveness of the hair after drying, the combability after drying, and the glossiness of the hair after drying were evaluated. Table 2 shows the average score of the evaluations of 5 people.
・ Hair cohesion at the time of application or after drying 5: Hair cohesion is very good.
4: Hair is well organized.
3: Normal (equivalent to Comparative Example 2).
2: Hair is not well organized.
1: My hair doesn't come together at all.
・ Combability after drying 5: Very good combability.
4: Good combing.
3: Combing is normal (equivalent to Comparative Example 2).
2: Combing is bad.
1: Combing is very bad.
・ Glossy hair after drying 5: Strong luster.
4: There is a slight luster.
3: Normal (equivalent to Comparative Example 2).
2: Not very glossy.
1: There is no luster.

<Hard surface coating test>
0.1 mL of the test solution was uniformly applied to a slide glass (18 mm × 50 mm), rinsed with ion-exchanged water (100 mL), and dried using a dryer. Ion-exchanged water (0.02 mL) is dropped on the slide glass that has undergone the above treatment with a microsyringe, and 5 seconds after dropping with an optical microscope (“Digital Microscope VHX-1000” manufactured by Keyence, 25x magnification). After photographing the subsequent droplets, the contact angle was calculated using this machine. The larger the value (contact angle), the more hydrophobic the surface and the better the water repellency.

<Clothing application test>
Put 10 g of the test solution and 20 g of ion-exchanged water in a 50 mL glass sample bottle (Maruem Co., Ltd., No. 7), mix them uniformly, put a cotton cloth (5 cm x 5 cm), and vigorously 30 times / 10 seconds. It was shaken and the test solution was sufficiently immersed in a cotton cloth. After allowing to stand for 1 hour, the test solution was drained, washed with tap water (40 mL, 25 ° C.) three times, and then dried. Using these cotton cloths, the wrinkle suppression property after drying and the quick-drying property were evaluated.
Usability of cotton cloth after drying Five expert panelists evaluated the wrinkle suppression property after drying by the following evaluation criteria and evaluation method. Table 2 shows the average score of the evaluations of 5 people.
-Wrinkle suppression after drying 5: No wrinkles occur even if the fibers are squeezed strongly.
4: Wrinkles are less likely to occur even if the fibers are squeezed strongly.
3: When the fibers are squeezed strongly, wrinkles are generated, but when the fibers are squeezed weakly, wrinkles are not generated.
(Equivalent to Comparative Example 2)
2: Even if the fibers are squeezed weakly, slight wrinkles occur.
1: Even if the fibers are squeezed weakly, a large amount of wrinkles are generated.

Quick-drying After immersing 0.5 g of ion-exchanged water in the dried cotton cloth, it is dried with a dryer, and the drying rate is evaluated by measuring the water weight after 30 seconds, 60 seconds, and 90 seconds. did. It is shown that the quick-drying property is better when the water content is reduced in a short time.

The following was found from Table 2.
Regarding the foaming property, from Examples 1 and 2 and Comparative Example 1, the foaming property was not observed with the simple cellulose fiber, and the foaming property was clearly confirmed by using the etherified cellulose fiber.
With respect to skin application, hair application, hard surface application and clothing application, the mere cellulose fiber of Comparative Example 1 had the same effect as the standard water, but the etherified cellulose fiber of Examples 1 and 2 clearly showed. The effect was improved.

The composition containing the etherified cellulose fiber and water of the present invention can be suitably used for cleaning agents for skin, hair, hard surfaces, and clothing.

Claims (3)

A foaming agent comprising a modified cellulose fiber having a cellulose I-type crystal structure in which a hydrocarbon group which may have a substituent is bonded to the cellulose fiber via an ether bond. In the modified cellulose fiber, one or more substituents selected from the substituent represented by the following general formula (1) and the substituent represented by the following general formula (2) are cellulose via an ether bond. The foaming agent according to claim 1, which has a cellulose type I crystal structure bonded to fibers.
-CH ₂ -CH (R) ₀ ) -R ₁ (1)
-CH ₂ -CH (R) ₀ ) -CH ₂ -(OA) _n -OR ₁ (2)
[In the formula, R ₀ Indicates a hydrogen atom or a hydroxyl group, and R ₁ Independently indicate an alkyl group of a linear or branched chain having 3 or more and 30 or less carbon atoms, n indicates a number of 0 or more and 50 or less, and A is 2 of a linear or branched chain having 1 to 6 carbon atoms. It shows a saturated hydrocarbon group of valence. ] The modified cellulose fiber contains one or more substituents selected from the substituents represented by the following general formula (1) and the substituents represented by the following general formula (2), and the following general formula (3). The foaming agent according to claim 1, wherein the substituents represented by () each independently have a cellulose type I crystal structure bonded to a cellulose fiber via an ether bond.
-CH ₂ -CH (R) ₀ ) -R ₁ (1)
-CH ₂ -CH (R) ₀ ) -CH ₂ -(OA) _n -OR ₁ (2)
-CH ₂ -CH (R) ₀ ) -R ₂ (3)
[In the formula, R ₀ Indicates a hydrogen atom or a hydroxyl group, and R ₁ Independently indicate an alkyl group of a linear or branched chain having 3 or more and 30 or less carbon atoms, n indicates a number of 0 or more and 50 or less, and A is 2 of a linear or branched chain having 1 or more and 6 or less carbon atoms. Indicates a saturated hydrocarbon group of valence, R ₂ Indicates an alkyl group having 1 or more carbon atoms and 2 or less carbon atoms. ]