JP6866190B2 - Composition containing etherified cellulose fiber and surfactant - Google Patents

Description

The present invention relates to a composition containing an etherified cellulose fiber and a surfactant, and a foam sustaining agent composed of the etherified cellulose fiber. 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 foam. Regarding sustainers.

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, biomass is naturally present in large quantities. 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

Although the cellulose fibers themselves have little effect on foam persistence, we have newly found that the combined use of certain modified cellulose fibers with surfactants unexpectedly improves foam persistence.

The present invention relates to a novel composition having excellent foam durability.

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

According to the configuration of the present invention, the foam persistence is unexpectedly exhibited. Although the reason is not clear, the cellulose fiber according to the present invention exhibits surface activity by having a functional group via an ether bond, and the cellulose fiber alone or the interaction between the cellulose fiber and a surfactant causes the surface activity. It is presumed that the foam film formed by the surfactant used in combination was stabilized, and as a result, the durability of the foam was improved.

Further, according to the configuration of the present invention, when applied to the skin, a coat feeling after drying is exhibited, and when applied to hair, smoothness during rinsing, finger passage during towel drying, and after drying. A glossy feeling is exhibited. The reasons for these are not clear, but are presumed as follows.

Generally, it is known that cellulose fibers remain on skin, hair, and fibers to form a film and have a coating effect. However, treatment of skin, hair, etc. using the composition using cellulose fibers according to the present invention ( When coating, washing, etc.) is performed, the residual amount of the cellulose fibers increases due to the synergistic effect of the cellulose fibers having a functional group and the surfactant, or the adsorption state such that the cellulose fibers remain uniformly on the surface occurs. It is presumed that the above-mentioned effect can be obtained by changing or improving the hydrophobicity of the residual cellulose fiber or the complex of the cellulose fiber and the surfactant.

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

[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 is bonded to the surface of the cellulose fiber 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.

Among the hydrocarbon groups which may have a substituent in the present invention, the hydrocarbon group includes 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 alicyclic hydrocarbon groups such as cyclohexyl groups, which are preferably saturated or unsaturated linear or branched aliphatic hydrocarbon groups from the viewpoint of foam sustainability 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 foam sustainability and economy. , Preferably an oxyethylene group and a hydroxyl group.

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 bubble persistence.

(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 any 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 foam persistence, 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 foam persistence, 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 to 30 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 foam durability, and preferably from the viewpoint of improving foam durability, availability and reactivity. 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 foam durability, 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 foam durability, availability, and cost, and preferably 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 foam persistence. 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 an oxyalkylene group such as ethylene oxide, the number of moles of addition is 10, 12, 13, and 20 mol. 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 foam persistence. It has a cellulose type I crystal structure, and from the viewpoint of foam persistence, 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 straight 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 bubble persistence.

(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 (a) group and the (b) group. 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 substituent of the group (a), the substituent represented by the general formula (1) and the substituent 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 foam persistence.
_{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 foam persistence. 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 foam durability, 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 foam durability 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 foam durability, handleability, availability, and cost. From the viewpoint of foam durability 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 it is difficult to observe with an optical microscope, 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 foam persistence. 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 and the like. Examples thereof include compact shear mills such as type mills, high-speed centrifugal roller mills and ong mills, grinders such as mortars, millstones, mascoroiders, 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). Halide is preferred. Such a compound may be prepared according to a known technique, or a commercially available product may be used. From the viewpoint of foam persistence, the total carbon number of the compound is 3 or more, preferably 5 or more, more preferably 6 or more, still more preferably 8 or more, still more preferably 12 or more, and the foam persistence is high. 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 foam persistence, it is preferably 4 or more, more preferably 6 or more, still more preferably 10 or more, and from the viewpoint of foam persistence, it is preferable. 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 foam persistence. 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 alkyl group has 3 or more and 30 or less carbon atoms, but is preferably 4 or more, more preferably 6 or more, and preferably 27 or less, more preferably 27 or less, from the viewpoint of foam persistence. 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 having a hydrocarbon group which may have the substituent, but is reactive with 100 parts by mass of the cellulose-based raw material. From the viewpoint, 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 from the viewpoint of productivity. It is preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, still more 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.

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 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 is changed by such treatment, when the obtained etherified cellulose fiber is added to the surfactant, the composition of the etherified cellulose fiber and the surfactant 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 foam persistence, 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). Halide is preferred. 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 3 or more and 4 or less from the viewpoint of foam persistence.

[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 cellulosic fiber, but from the viewpoint of foam persistence, 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.

(Surfactant)
The composition of the present invention further contains one or more surfactants.
Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
When used as a cleaning agent for shampoos, anionic surfactants, nonionic surfactants, and amphoteric surfactants are preferable, and when used as rinses, conditioners, treatments, hair styling agents, etc., nonionic surfactants are preferred. Ionic surfactants and cationic surfactants are preferable.

As the anionic surfactant, those of a sulfate ester salt, a sulfonate, a carboxylate salt, a phosphate ester salt and an amino acid salt salt are preferable. Specific examples of the sulfate ester include alkyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl phenyl ether sulfate, and the like. Chain alkylbenzene sulfonate, sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinate alkyl ester salt, alkane sulfonate, acyl acetylate, acyl methyl taurate and the like can be mentioned, and examples of the carboxylate include higher fatty acid salts. Examples include polyoxyalkylene alkyl ether acetate, examples of phosphate ester salts include alkyl phosphates, polyoxyalkylene alkyl ether phosphates, and the like, and examples of amino acid salts include acyl glutamate, alanine derivatives, and N. -Glycine derivatives such as coconut oil fatty acid acylglycine potassium, arginine derivatives and the like can be mentioned.
Among these, alkyl sulfates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkenyl from the viewpoints of obtaining finger passage after drying of hair treated with the composition of the present invention, a good coating feeling, and a cohesive feeling. Ether sulfate, higher fatty acid salt, polyoxyethylene alkyl ether acetate, sulfosuccinic acid alkyl ester salt, and acyl glutamate are preferable, and polyoxyethylene alkyl ether sulfate represented by the following general formula (6) or (7) is particularly preferable. Salts or alkyl sulphates are preferred.
{R ^{3 −} O (CH ₂ CH ₂ O) _r SO ₃ } _t M (6)
{R ^4- OSO ₃ } _t M (7)
(In the formula, R ³ represents an alkyl group or an alkenyl group ^{having 10 to 18 carbon atoms, R 4} represents an alkyl group having 10 to 18 carbon atoms, and M represents an alkali metal, an alkaline earth metal, ammonium, or an alkanolamine. Indicates a salt or a basic amino acid, r indicates the average number of moles of ethyleneoxy groups added, and is 1 to 5. t is the same number as the valence of M.)

Nonionic surfactants include polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene sorbit fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, and poly. Examples include polyalkylene glycol types such as oxyalkylene (hardened) castor oil, polyhydric alcohol types such as monoalkylene glycol alkyl ethers, sucrose fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, and alkyl glycosides, and fatty acid alkanolamides. Be done.
Among the polyalkylene glycol types, the polyoxyalkylene alkyl ether and the polyoxyalkylene fatty acid ester are included in the polyalkylene glycol type from the viewpoint of obtaining the finger-passability after drying of the hair treated with the composition of the present invention, a good coating feeling, and a cohesive feeling. Polyoxyalkylene sorbitan fatty acid ester and polyoxyalkylene cured castor oil are preferable, and among polyhydric alcohol types, alkyl glycolicides are preferable.
Examples of the polyoxyalkylene alkyl ether include polyoxyethylene alkyl ethers and polyoxypropylene alkyl ethers from the viewpoint of obtaining finger passage after drying of hair treated with the composition of the present invention, a good coating feeling, and a cohesive feeling. Polyoxyethylene / polyoxypropylene alkyl ethers are preferable, and those having an alkyl group having 12 or more and 14 or less carbon atoms are preferable.

As the polyoxyalkylene fatty acid ester, those in which the oxyalkylene group is an oxyethylene group and the fatty acid is a fatty acid having 8 to 20 carbon atoms are preferable.
As the polyoxyalkylene sorbitan fatty acid ester, those in which the oxyalkylene group is an oxyethylene group and the fatty acid is a fatty acid having 8 to 20 carbon atoms are preferable.
As the polyoxyalkylene-cured castor oil, those in which the oxyalkylene group is an oxyethylene group are preferable.
The fatty acid alkanolamide may be either a monoalkanolamide or a dialkanolamide, but one having a hydroxyalkyl group having 2 to 3 carbon atoms is preferable. Specific examples of fatty acid alkanolamides include oleate diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, coconut oil fatty acid monoethanolamide, and laurin. Examples thereof include acid monoisopropanolamide, lauric acid monoethanolamide, palm kernel oil fatty acid methylethanolamide, and coconut oil fatty acid methylethanolamide.
As the alkyl glycoside, a polysaccharide having an alkyl chain having 8 to 18 carbon atoms via a glycosidic bond and having a degree of polymerization of 1 to 20 is preferable, and the degree of polymerization is more preferably 1 to 10 and particularly preferably 1 to 5. As the sugar constituting the polysaccharide, glucose and galactose are preferable, and glucose is more preferable. Specific examples include alkyl glucosides.

Examples of cationic surfactants are quaternary ammonium salts, pyridinium salts, or tertiary amines having a hydrocarbon group having 12 to 28 carbon atoms, which may be partitioned by an amide group, an ester group or an ether group. Examples of mineral acid or organic acid salt. Specifically, monolong-chain alkyltrimethylammonium chloride such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, and octadesyloxypropyltrimethylammonium chloride, distearyldimethylammonium chloride, and diisotetradecyldimethylchloride Dilong-chain alkyldimethylammonium chloride such as ammonium, and mono-long-chain alkyldimethylamine salts such as stearylamide propyldimethylamine, stearyldimethylamine, behenyldimethylamine, octadecyloxypropyldimethylamine hydrochloride, citric acid or lactate Can be mentioned.
Among these, mono-long-chain alkyltrimethylammonium chloride and mono-long-chain alkyldimethylamine salts are used from the viewpoint of obtaining finger-passability after drying of hair treated with the composition of the present invention, a good coat feeling, and a cohesive feeling. Is preferable.

Examples of amphoteric surfactants include betaine-based surfactants and amine oxide-type surfactants. Among these, imidazoline betaine, alkyldimethylaminoacetate betaine, fatty acid amide propyl betaine, from the viewpoint of obtaining finger-passability after drying, a good coat feeling, and a cohesive feeling of the hair treated with the composition of the present invention. Betaine-based surfactants such as sulfobetaine and amine oxide-type surfactants such as alkyldimethylamine oxide are more preferable, and alkylcarboxymethylhydroxyethyl imidazolium betaine, fatty acid amide propyl betaine, alkylhydroxysulfobetaine, alkylsulfobetaine, etc. Further preferred are sulfobetaines such as fatty acid amide propyl hydroxysulfobetaine and fatty acid amide propyl sulfobetaine, alkyldimethylaminoacetic acid betaines, and alkyldimethylamine oxides.
The fatty acid amide propyl betaine and alkyl hydroxysulfobetaine are preferably those having an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, particularly lauric acid amide propyl betaine, palm kernel oil fatty acid amide propyl betaine, and coconut oil fatty acid. Amidopropyl betaine, lauryl hydroxysulfobetaine, lauryl sulfobetaine, coconut oil fatty acid amide propyl hydroxy sulfobetaine, coconut oil fatty acid amide propyl sulfobetaine and the like are preferable.
The alkyldimethylamine oxide preferably has an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and particularly preferably lauryldimethylamine oxide and myristyldimethylamine oxide.

Surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether acetates, sulfosuccinic acid alkyl ester salts, acyl glutamates, higher fatty acid salts, polyoxyalkylene alkyl ethers, polyoxyethylene curing. One or more surfactants selected from the group consisting of castor oil, fatty acid alkanolamide, alkylglycoside, alkylhydroxysulfobetaine, fatty acid amide propyl betaine, alkyldimethylaminoacetic acid betaine, alkylamine oxide, alkyltrimethylammonium salt and alkyldimethylamine salt. It preferably contains an activator.

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

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 foam persistence. The above is more preferably 0.1% by mass or more, and from the viewpoint of cost, 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. More preferably, it is 0.7% by mass or less.

The content of the surfactant in the composition of the present invention is preferably 0.1 from the viewpoint of improving the finger-passability, coat feeling, and cohesiveness after drying of the hair treated with the composition and reducing the stickiness. It is 0% by mass or more and 80% by mass or less, more preferably 0.2% by mass or more and 50% by mass or less, and further preferably 0.3% by mass or more and 20% by mass or less. When the hair cosmetic is a shampoo, the content of the surfactant is more preferably 5% by mass or more and 30% by mass or less, and further preferably 8% by mass or more and 20% by mass or less from the same viewpoint. When the hair cosmetic is a rinse, conditioner, treatment or hair styling agent, the hair makeup is treated from the viewpoint of improving the finger passage, coat feeling and cohesiveness after drying of the hair treated with the composition and reducing the stickiness. The content in the material is more preferably 0.5% by mass or more and 10% by mass or less, and further preferably 1% by mass or more and 5% by mass or less.

In the composition of the present invention, the ratio of the etherified cellulose fiber to the surfactant is determined from the viewpoint of obtaining finger passage after drying of the hair treated with the composition of the present invention, a good coating feeling, and a cohesive feeling. The mass ratio of [etherified cellulose fiber / surfactant] is preferably 0.001 to 10, more preferably 0.003 to 2, still more preferably 0.005 to 1, and particularly preferably 0.01 to 0. It is 3. When the composition of the present invention is a shampoo, the etherified cellulose fiber and the surfactant are used from the viewpoint of improving the finger passage, coating feeling and cohesiveness after drying of the shampoo-treated hair and reducing the stickiness. The ratio (mass ratio of [etherified cellulose fiber / surfactant]) is preferably 0.001 to 3.0, more preferably 0.005 to 0.1, and particularly preferably 0.02 to 0.05. When the composition of the present invention is a rinse, conditioner, treatment or hair styling agent, from the viewpoint of improving the finger passage, coat feeling and cohesiveness after drying of the hair treated with such a composition, and reducing the stickiness. , The ratio of the etherified cellulose fiber to the surfactant (mass ratio of [etherified cellulose fiber / surfactant]) is preferably 0.005 to 1, more preferably 0.01 to 0.5, and 0.03. ~ 0.3 is particularly preferable.

(water)
The composition of the present invention may further contain water. The water 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.

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, from the viewpoint of foam durability and cost. % Or more, more preferably 80% by mass or more, and from the viewpoint of foam persistence, preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 95% by mass. % Or less.

The composition of the present invention has functionality as other components other than the above, such as inorganic salts, organic salts, oils, moisturizers, preservatives, organic fine particles, inorganic fine particles, dyes, deodorants, fragrances, and organic solvents. 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 about 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, for example, as a dispersion of an etherified cellulose fiber and a surfactant, and more preferably as a dispersion of an etherified cellulose fiber, a surfactant and water, and is provided.

The composition of the present invention has an unexpected effect of improving the durability of foam. Therefore, the composition of the present invention is provided as a foam-sustaining agent composition. Further, the composition obtained by removing the surfactant 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 to form a cellulose type I crystal structure. The modified cellulose fiber having may be used as a foam lasting agent.

Specifically, by utilizing this effect, a skin treatment composition such as body shampoo, hand cleaner, shave lotion, facial cleanser, cleansing cream, lotion, beauty liquid, pack, ointment, toothpaste, and patch. , Hair shampoo, hair conditioner, rinse, rinse-in shampoo, hair styling agent, hair treatment agent, hair dye, hair treatment agent composition such as hair restorer, dishwashing detergent, bath detergent, toilet cleaner, metal cleaning It can be used for one or more applications selected from the group consisting of agents, detergents for hard surfaces such as floor cleaners, and detergents for clothing.

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

The mixing ratio of the etherified cellulose fiber and the surfactant and the amount of water and 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 a 6.4 mass% sodium hydroxide aqueous solution (prepared with sodium hydroxide granules and ion-exchanged water manufactured by Wako Pure Chemical Industries, Ltd.) 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 volume / 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 Junyaku Co., Ltd.), thoroughly wash with water / isopropanol (manufactured by Wako Junyaku Co., 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% sodium hydroxide aqueous 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, wash thoroughly with acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and water / isopropanol mixed solvent to remove impurities, and 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% aqueous sodium hydroxide 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, wash thoroughly with acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and water / isopropanol mixed solvent to remove impurities, and vacuum dry at 50 ° C. overnight to obtain two types. An etherified cellulose fiber having a substituent was obtained.

By putting 1.4 g of the obtained etherified cellulose fiber having two kinds of substituents into 100 g of ion-exchanged water and performing the same dispersion treatment as in Example 1, the finely divided etherified cellulose fiber is put into water. A fine etherified cellulose dispersion 2 (solid content concentration 1.4% by mass) dispersed in the above 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 (substitution degree))
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 revised Japanese Pharmacopoeia (section of analysis method for hydroxypropyl cellulose)" and the like. 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 (12m, 0.2mm x 0.33μm)
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 etherifying reagents used, that is, propylene oxide, polyoxyalkylene alkyl etherifying agent and 1,2-epoxyhexane.
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 sample for measurement 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 compositions shown in Table 2 were prepared and used as test solutions. Using these test solutions, foam persistence, skin cleansing test and hair cleansing test were performed according to the following evaluation criteria and evaluation methods.

<Foam persistence test>
Foam persistence was measured by the following two methods.
(1) Shaking method 20 g of the measurement solution obtained by diluting each test solution by 20 times by weight with ion-exchanged water is placed in a 100 mL graduated cylinder with a lid, and shaken at a speed of 10 times / 10 seconds. It was allowed to stand for 1 minute. The amount of bubbles (scale of the boundary between the air phase and the bubble surface-the boundary between the solution phase and the bubble surface) (mL) after standing was measured and used as the sustainability of the bubbles. It is shown that the larger the amount of foam, the better the durability of foam.

(2) Torres method Using a tress, the persistence of foam was measured by whipping while sharing.
(Preparation for tress)
After washing the hair bundle (bleached Asian hair, about 20 cm, 20 g) with the plain shampoo shown below, the plain rinse shown below was applied, and then rinsed with tap water to obtain an evaluation tress.

(Composition of plain shampoo)
(Ingredient) (%)
Polyoxyethylene Lauryl Ether Sulfate Na 11.3
(42.0% as Emar E-27C (manufactured by Kao Corporation, effective content 27% by weight))
Coconut oil fatty acid N-methylethanolamide 3.0
(Aminone C-11S (manufactured by Kao Corporation))
Citric acid 0.2
Methylparaben 0.3
Purified water balance total 100.0

(Composition of plain rinse)
(Ingredient) (%)
Octadesyloxypropyl trimethylammonium chloride 3.0
(6.7% as Kotamin E-80K (manufactured by Kao Corporation, effective content 45% by weight))
Stearyl alcohol (Calcol 8098 (manufactured by Kao Corporation)) 6.0
Methylparaben 0.3
Purified water balance total 100.0

(Manufacturing of plain shampoo)
Each component was placed in a beaker, heated to 80 ° C., mixed, and after confirming that it was uniformly dissolved, cooled to obtain a plain shampoo.

(Manufacturing of plain rinse)
Octadesyloxypropyl trimethylammonium chloride and stearyl alcohol were placed in a beaker (A) and heated to 80 ° C. to melt them. Purified water and methylparaben were placed in another beaker (B) and heated to 80 ° C. with stirring to confirm that they were uniformly dissolved. Then, while stirring the beaker (B) at 80 ° C., the mixed solution in the beaker (A) was added, emulsified for 30 minutes, heating was stopped, and the mixture was cooled to room temperature to obtain a plain rinse.

(Evaluation method)
Add 0.5 mL of the test solution to the evaluation tress obtained by the above method, whisk 30 times while sharing the hair, and put the remaining foam without defoaming into a glass graduated cylinder with a diameter of 5 cm. , The volume of bubbles was measured. This operation was repeated 3 times, and the average value (rounded to the nearest whole number) was taken as the amount of bubbles (mL). It is shown that the larger the amount of foam, the better the durability of foam.

<Skin application test>
Five professional panelists took 1.0 mL of the test solution and washed their fingers. The coat feeling after drying was evaluated by the evaluation criteria and the evaluation method shown below.
・ Coat feeling after drying 5: Strong coat feeling, no dryness of fingertips 4: Coat feeling, weak dryness of fingertips 3: Normal (same as Comparative Example 2)
2: No coat feeling, strong fingertip dryness 1: No coat feeling, very strong fingertip dryness

<Hair application test>
Five specialized panelists perform a washing test of whipping, rinsing, towel drying, and drying in the same way as the foam persistence test (tress method), and the evaluation criteria and evaluation method shown below are used to smooth the hair during rinsing. Then, the finger passage during towel drying and the glossiness after drying were evaluated.
・ Smoothness of hair when rinsing 5: Very smooth hair, easy to hand comb without squeaky feeling or entanglement of hair 4: Smooth hair, hand combing without problems 3: Hair Smoothness is normal (equivalent to Comparative Example 2)
2: The hair is inferior in smoothness, and the fingers are entangled when combing the hands, making it difficult to comb the hands. 1: The hair is not smooth, the squeaky feeling is strong, and the fingers are entangled violently, so the hand combing is very difficult. Difficulty Hand combing means passing your finger through the tress like a comb when rinsing.
・ Finger passage after towel drying 5: Very good finger passage 4: Good finger passage 3: Normal finger passage (equivalent to Comparative Example 2)
2: Poor finger passage 1: Very poor finger passage / glossy hair after drying 5: Strong glossiness 4: Slightly glossy 3: Normal (same as Comparative Example 2)
2: Not very glossy 1: No glossiness at all

* 1: Made by Kao Corporation, Product name: Emar 270S (70% active ingredient)
* 2: Made by Kao Corporation, Product name: Anhitor 55AB (active ingredient 30%)

The following was found from Table 2.
Regarding the sustainability of foam, from Examples 1 and 2 and Comparative Examples 1 and 2, the sustainability of foam is rather lowered with simple cellulose fibers, while the etherified cellulose fibers of Examples 1 and 2 are used to clearly foam. It was confirmed that the sustainability of
Regarding the skin application and the hair application, each evaluation item was slightly improved or rather decreased in the simple cellulose fiber of Comparative Example 1, but in the etherified cellulose fiber of Examples 1 and 2, each evaluation item was clear. It was confirmed that the improvement was achieved.

Prescription example 1
Hair shampoos 1 to 4 having the following composition are prepared by a conventional method.

* 1: Made by Kao Corporation, Product name: Emar 270J (70% active ingredient)
* 2: Made by Kao Corporation, Product name: Emar 30NS
* 3: Made by Kao Corporation, Product name: Kao Akipo RLM-45NV (active ingredient 24%)
* 6: Made by Kao Corporation, Product name: Anhitor 55AB (active ingredient 30%)
* 8: Made by Kawaken Fine Chemical Co., Ltd., Product name: Amizol CME
* 11: Made by Kao Corporation, Product name: Poise C-150L
* 12: Made by Rhodia, Product name: Jaguar C-13S
* 14: Made by Toray Dow Corning, trade name: BY22-050 (active ingredient: 50%)

Prescription example 2
Hair conditioners 1 to 4 having the following composition are prepared by a conventional method.

* 2: Made by Toho Chemical Industry Co., Ltd., Product name: Katinal DC-80 (80% active ingredient)
* 3: Made by Toho Chemical Industry Co., Ltd., Product name: Katinal MPAS (80% active ingredient)
* 4: Made by Kao Corporation, Product name: Kotamin D86P (75% active ingredient)
* 5: Made by Kao Corporation, Product name: Calcor 6098
* 6: Made by Kao Corporation, Product name: Calcor 8098
* 8: Made by Kao Corporation, Product name: Concentrated glycerin for cosmetics
* 9: Made by Nippon Seiro Co., Ltd., Product name: Paraffin wax 125
* 11: Made by Toray Dow Corning, trade name: BY22-060 (active ingredient: 60%)
* 12: Made by Toray Dow Corning, trade name: PMX-1503 (active ingredient: 12%)
* 13: Made by Toray Dow Corning, trade name: BY22-079 (active ingredient: 14%)

Prescription example 3
Body shampoos 1 to 4 having the following composition are prepared by a conventional method.

* 1: Made by Kao Corporation, Product name: Emar 270J (70% active ingredient)
* 5: Made by Ajinomoto Co., Inc., Product name: Amilite GCK-11
* 7: Made by Kao Corporation, Product name: Anhitor 55AB (active ingredient 30%)
* 8: Made by Kao Corporation, Product name: Anhitor 20Y-B (active ingredient 40%)
* 10: Made by Kao Corporation, Product name: Lunac L-98
* 11: Made by Kao Corporation, Product name: Lunac MY-98
* 12: Made by Kao Corporation, Product name: Poise C-60H
* 15: Made by Kao Corporation, Product name: Concentrated glycerin for cosmetics

Prescription example 4
Facial cleansers 1 to 3 having the following compositions are prepared by a conventional method.

* 1: Made by Kao Corporation, Product name: Emar 270J (70% active ingredient)
* 2: Made by Kao Corporation, Product name: Lunac L-98
* 3: Made by Kao Corporation, Product name: Lunac MY-98
* 7: Made by Kao Corporation, Product name: Anhitor 20HD (active ingredient 30%)
* 9: Made by Kao Corporation, Product name: My Doll 12 (40% active ingredient)
* 12: Made by Asahi Glass Co., Ltd., Product name: Dipropylene glycol DPG-FC
* 15: Made by Kao Corporation, Product name: Concentrated glycerin for cosmetics

Prescription example 5
Cream 1 having the following composition is prepared by a conventional method.

* 1: Made by Kao Corporation, Product name: Exepearl IS-CE
* 2: Made by Kao Corporation, Product name: Penetol GE-IS
* 3: Made by Nikko Chemicals Co., Ltd., Product name: Nikkor HCO-10
* 7: Made by Shin-Etsu Chemical Co., Ltd., Product name: Silicone KF-96A (2cs)
* 9: Made by Kao Corporation, Product name: Exepearl IPP
* 10: Made by Kao Corporation, Product name: Coconard MT
* 11: Made by Kao Corporation, Product name: Concentrated glycerin for cosmetics

Prescription example 6
Toothpaste 1-2 having the following composition is prepared by a conventional method.

* 1: Made by Mitsubishi Shoji Food Tech Co., Ltd., Product name: Sorbitol # 650
* 2: Made by Daicel Co., Ltd., Product name: CMC Daicel <1350>
* 4: Made by Nippon Paper Industries, Ltd., Product name: Saccharin sodium (powder)
* 9: Made by Ashland Specialty Ingredients, trade name: PVP K-30
* 10: Made by Toho Chemical Industry Co., Ltd., Product name: Kohakuru L-300 (active ingredient 30%)
* 11: Made by Kao Corporation, Product name: Local law glycerin

Prescription example 7
Clothing detergents 1 to 3 having the following composition are prepared by a conventional method.

* 1: Made by Kao Corporation, Product name: Emar 270S (70% active ingredient)
* 2: Made by Kao Corporation, Product name: Lunac L-98
* 3: Made by Kao Corporation, Product name: Emargen 108
* 6: Made by Nippon Shokubai Co., Ltd., Product name: Softanol H
* 7: Made by Nippon Emulsifier Co., Ltd., Product name: New Call 2303-Y
* 9: Made by Kao Corporation, Product name: Lunac L-98

Prescription example 8
Dishwashing detergents 1 to 4 having the following composition are prepared by a conventional method.

* 1: Made by Kao Corporation, Product name: Emar 327 (active ingredient 27%)
* 3: Made by Kao Corporation, Product name: Emar 30NS
* 4: Made by Kao Corporation, Product name: Emargen 108
* 5: Made by Kao Corporation, Product name: Anhitor 20N

Prescription example 9
Detergents 1 and 2 for hard surfaces (baths) having the following composition are prepared by a conventional method.

* 2: Made by Kao Corporation, Product name: Neoperex F-65 (active ingredient 65%)
* 3: Made by Kao Corporation, Product name: Lunac L-98
* 4: Made by Kao Corporation, Product name: Emargen 106
* 5: Made by Tokyo Chemical Industry Co., Ltd., Product name: 1-ethoxy-2-propanol
* 7: Made by Kao Corporation, Product name: Anhitor 55AB

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

Claims (5)

A composition containing etherified cellulose fibers and a surfactant.
The etherified cellulose fiber has 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) via an ether bond. A composition which is a modified cellulose fiber which is bound to a cellulose fiber and has 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. ] A composition containing etherified cellulose fibers and a surfactant.
The etherified cellulose fiber contains 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), and the following general formula ( substituent represented by 3) are each independently, are bonded to the cellulose fibers via an ether bond, a modified cellulose fiber having a cellulose I type crystal structure, set Narubutsu.
-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 straight 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. ] The composition according to claim 1 or 2 , which is a dispersion. The composition according to any one of claims 1 to 3 , which is a skin treatment agent composition, a hair treatment agent composition, a hard surface treatment agent composition, or a clothing treatment agent composition. A foam persistent agent consisting of modified cellulose fibers,
A foam-sustaining agent, wherein the modified cellulose fiber is (A) and / or (B) below.
(A): 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 added to the cellulose fiber via an ether bond. A modified cellulose fiber that is bonded and has 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. ]
(B): 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), and the following general formula (3). A modified cellulose fiber having a cellulose type I crystal structure in which the represented substituents are independently bonded to the cellulose fiber via an ether bond.
-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 straight 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. ]