JP6861539B2 - Composition containing etherified cellulose fiber and oily component - Google Patents

Description

The present invention relates to a composition containing an etherified cellulose fiber and an oily component, and a thickener composed of the etherified cellulose fiber. More specifically, the present invention relates to a composition which is a dispersion, a composition preferably used as a skin treatment agent composition, a hair treatment agent composition, a clothing treatment agent composition, and the like, and a thickener.

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

The present inventors have newly found that when a specific modified cellulose fiber is used in combination with an oily component, the viscosity is unexpectedly reduced.

The present invention relates to a novel composition having excellent viscosity reduction.

The present invention relates to the following [1] to [2].
[1] A composition containing an etherified cellulose fiber and an oily component, 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 thickening 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 viscosity reduction.

According to the configuration of the present invention, the viscosity is unexpectedly reduced. Although the reason is not clear, it is presumed that the cellulose fiber according to the present invention has a functional group via an ether bond, so that the surface activity is exhibited, so that the oil-based component dispersion can exhibit deviscosity. ..

Further, according to the configuration of the present invention, when applied to the skin, a silky feeling and a coat feeling are exhibited, when applied to hair, a cohesiveness, a slippery feeling and a coat feeling are exhibited, and when applied to clothing. Has a silky feel, a coat feel, water repellency and a quick-drying effect. 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 the cellulose fibers according to the present invention can be used for skin, hair, clothing, and the like. When treatment (coating, washing, etc.) is performed, the residual amount increases due to the effect of the functional group, the residual state such as remaining uniformly on the surface changes, or the cellulose fiber is affected by the effect of the functional group. It is presumed that the above effect can be obtained by improving the hydrophobicity of itself.

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

[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 viscosity reduction and economy, and more preferably saturated. It is a linear or branched aliphatic hydrocarbon group of.
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 devitrification and economic efficiency, It is 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 viscosity reduction.

(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 Substituents, even if it is the same Substituent in each Substituent Group, 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 reducing viscosity, 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 viscosity reduction, 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. Even more preferably, it is 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 viscosity reduction, and preferably 27 from the viewpoint of viscosity reduction, availability and reactivity improvement. Below, it is 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 viscosity reduction, 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 viscosity reduction, availability, and cost, and preferably 40 or more from the same viewpoint. Below, it is 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 or more, from the viewpoint of viscosity reduction. It is a combination of numbers of 20 or less, 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 the 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 substituents having the number of moles of 10, 12, 13, and 20 moles 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 the 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 cellulose from the viewpoint of reducing viscosity. It has an I-type crystal structure, and from the viewpoint of reducing viscosity, 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, and further. It is preferably 0.6 mol or less, 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 viscosity reduction.

(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 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 viscosity reduction.
_{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 1 from the viewpoint of devitrification. .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 or more. Is.

(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 aspect 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 viscosity reduction, 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 viscosity reduction 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 viscosity reduction, handleability, availability, and cost. From the viewpoint of viscosity reduction 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 reduced viscosity. 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 Ethered 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 family, 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, woodfree 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 equivalent or more, more preferably 0.05 equivalent 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. Equivalent or more, more preferably 0.2 equivalent or more, preferably 10 equivalents or less, more preferably 8 equivalents or less, still more preferably 5 equivalents or less, still more preferably 3 equivalents, 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. 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 from the viewpoint of viscosity reduction, and from the viewpoint of viscosity reduction. , 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 viscosity reduction, it is preferably 4 or more, more preferably 6 or more, still more preferably 10 or more, and preferably 25 or less from the viewpoint of viscosity reduction. , 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 preferably 100 or less from the viewpoint of viscosity reduction. , 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 viscosity reduction, it is preferably 4 or more, more preferably 6 or more, and from the viewpoint of viscosity reduction, it is preferably 27 or less, more preferably 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 is changed by such treatment, when the obtained etherified cellulose fiber is added to the oily component, the composition of the etherified cellulose fiber and the oily component 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 introduction reaction of the substituent using a cellulosic raw material which has been finely divided in advance, but from the viewpoint of reducing the viscosity, 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 number of carbon atoms of the compound is 3 or more and 4 or less from the viewpoint of viscosity reduction.

[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 reducing viscosity, it is relative to the anhydrous glucose unit of the cellulosic raw material. The amount is preferably 5.0 equivalents or less, and the lower limit is about 0.02 equivalents.

(Oil component)
As the oily component used in the present invention, any poorly water-soluble or water-insoluble oily component having a solubility in 100 g of water at 20 ° C. of 0 g or more and 1 g or less can be used.

Examples of the oily component having a dissolution amount of 0 g or more and 1 g or less in 100 g of water at 20 ° C. include ester oil, silicone oil, ether oil, hydrocarbon oil, higher alcohols, glycerides, sterols, fluorine-based oils, and hydroxyl groups. Examples thereof include carboxylic acids having a hydrocarbon group having 17 to 23 carbon atoms which may be substituted with. Of these, one or more selected from ester oils, silicone oils, ether oils, hydrocarbon oils, higher alcohols, and carboxylic acids having a hydrocarbon group having 17 to 23 carbon atoms which may be substituted with hydroxyl groups. Ester oil, silicone oil, ether oil, hydrocarbon oil, or higher alcohol is more preferable, and ester oil, silicone oil, hydrocarbon oil, or higher alcohol is even more preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The ester oil is used from the viewpoint of imparting a good cohesive feeling to the hair after treatment and drying when the composition of the present invention is applied to the hair, and from the viewpoint of imparting a silky feeling to the skin when applied to the body. Ester oils represented by the following general formulas (6) or (7) and hydrophobic carboxylic acid esters of dipentaerythritol are preferable.
R ^1- COO-R ² (6)
(In the formula, R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. R ² is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms. )

In the general formula (6), ^{the carbon number of R 1} is preferably 10 to 20, more preferably 12 to 18, from the viewpoint of the cohesiveness of the hair. From the same viewpoint, ^{the carbon number of R 2} is preferably 1 to 20, more preferably 1 to 18. The R ^2, propyleneoxy group, or a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms which may be interrupted by a phenyl group is more preferable.

(In the formula, R ³ , R ⁴ and R ⁵ are independent hydrogen atoms or groups represented by the general formula (8), and not all of them are hydrogen atoms at the same time.)

(In the formula, R ⁶ is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms which may be substituted with a hydroxyl group.)
In the general formula (8), the ^{number of carbon atoms of R 6} is preferably 8 to 20, more preferably 8 to 18, still more preferably 14 to 18, still more preferably 16 to 18, from the viewpoint of the cohesiveness of the hair.

Specific examples of the esteric acid represented by the general formula (6) or (7) include sunflower oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, camellia oil, kyonin oil, almond oil, and wheat germ oil. , Theobroma Grange Florum Seed Oil, Grape Seed Oil, Babas Oil, Johova Oil, Macademia Nut Oil, Yucha Oil, Shea Fat Oil, Totsubaki Seed Oil, Meadowfoam Oil, Mitsurou, Lanolin, Reduced Lanolin, Lanolin Fatty Acid Octyldodecyl, Caprylyl Eikocenate , 2-ethylhexarate myristyl, 2-ethylhexarate cetyl, 2-ethylhexanoate stearyl, octyl octanate, lauryl octanoate, myristyl octanoate, isosetyl octanate, octyl propylheptylate, cetostearyl isononanoate, isononan Isononyl acid, isotridecyl isononanoate, methyl laurate, hexyl laurate, octyl laurate, isopropyl myristate, octyl myristate, myristyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyl palmitate, Cetyl palmitate, methyl oleate, oleyl oleate, decyl oleate, isobutyl oleate, methyl stearate, 2-ethylhexyl stearate, octyl stearate, isocetyl stearate, stearyl stearate, butyl stearate, isotridecyl stearate, Isopropyl isostearate, isosetyl isostearate, isostearyl isostearate, propylene glycol isostearate, 2-ethylhexyl hydroxystearate, oleyl erucate, 2-ethylhexyl succinate, polydose fatty acid sucrose, sucrose polybechenic acid, sucrose tetraisostearate, tribechenic acid Examples thereof include glyceryl and triisostearic acid. Other ester oils include, for example, diisopropyl dimerate, propanediol dicapric acid ester, diisopropyl adipate, diethoxyethyl succinate, hydroxyalkyl (C16-18) hydroxydimer linoleyl ether, pentaerythyl tetrastearate. And so on.

Among them, hojoba oil, from the viewpoint of imparting a good cohesive feeling to the treated and dried hair when the composition of the present invention is applied to the hair, and from the viewpoint of imparting a silky feeling to the skin when applied to the body. Glyceryl isostearate, sunflower oil, avocado oil, camellia oil, macadamia nut oil, shea butter oil, octyl laurate, octyl myristate, octyldodecyl myristate, isopropyl myristate, myristyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, Octyl palmitate, cetyl palmitate, methyl stearate, 2-ethylhexyl stearate, octyl stearate, isosetyl stearate, stearyl stearate, butyl stearate, or isotridecyl stearate are preferred, jojoba oil, glyceryl isostearate, myristic acid. Octyldodecyl, sunflower oil, avocado oil, camellia oil, macadamia nut oil, shea butter oil, octyl laurate, octyl myristate, myristyl myristate, isopropyl palmitate, octyl palmitate, cetyl palmitate, octyl stearate, isosetyl stearate, One or more selected from stearyl stearate, isostearyl stearate, and isostearyl isostearate are more preferable.

The hydrophobic carboxylic acid ester of dipentaerythritol refers to a compound obtained by dehydration condensation of dipentaerythritol and one or more hydrophobic carboxylic acids, where the hydrophobic carboxylic acid may have a hydroxyl group. A carboxylic acid having a good hydrocarbon group having 16 to 24 carbon atoms. Specific examples of the hydrophobic carboxylic acid include palmitic acid, stearic acid, oleic acid, isostearic acid, hydroxystearic acid, rosinic acid and the like. Of these, an ester composed of a mixed acid of hydroxystearic acid, stearic acid and rosin acid and dipentaerythritol is preferable from the viewpoint of availability.

The silicone oil is used from the viewpoint of imparting a good cohesive feeling to the hair after treatment and drying when the composition of the present invention is applied to the hair, and from the viewpoint of imparting a silky feeling to the skin when applied to the body. Dimethylpolysiloxane, dimethiconol (dimethylpolysiloxane with a hydroxyl group at the end), and amino-modified silicone (dimethylpolysiloxane with an amino group in the molecule), methylphenylpolysiloxane, polyether-modified silicone, glyceryl-modified silicone, amino derivative Silicone, fatty acid-modified polysiloxane, alcohol-modified silicone, aliphatic alcohol-modified polysiloxane, polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone, amino-modified siloxane-polyoxyalkylene block copolymer, etc. , Silicone wax, one or more selected from silicone elastomer is preferable.

The viscosity of the silicone oil determines the viewpoint and composition of imparting good finger passage and cohesiveness to the hair when the composition of the present invention is applied to the hair, and imparting a silky feeling to the skin when applied to the body. From the viewpoint of dispersibility during product preparation, 10 to 15,000,000 mm ² / s is preferable.

The ether oil was applied to the body from the viewpoint of improving the durability and rinsing property of the foam of the composition of the present invention, from the viewpoint of imparting a good cohesive feeling to the hair after treatment and drying when applied to the hair. From the viewpoint of imparting a silky feeling to the skin, the one represented by the following general formula (9) is preferable.
R ^7- O- (PO) r (EO) s-R ⁸ (9)
(In the formula, R ⁷ represents a linear or branched alkyl group or alkenyl group having 6 to 22 carbon ^{atoms. R 8} represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 16 carbon atoms. PO represents a propyleneoxy group, EO represents an ethyleneoxy group, the average number of added moles r of PO is 0.1 to 15, and the average number of added moles of EO is 0 to 10. When s is not 0, the addition form of PO and EO may be random or block, and the addition order of PO and EO does not matter.)

In the general formula (9), from the viewpoint of imparting a good cohesive feeling to the hair after treatment and drying when applied to the hair of the composition of the present invention, and from the viewpoint of imparting a silky feeling to the skin when applied to the body. , R ⁷ preferably has 6 to 20, more preferably 6 to 18, and even more preferably 8 to 18. R ⁸ is preferably a hydrogen atom or one having 1 to 12 carbon atoms, and more preferably a hydrogen atom or one having 1 to 8 carbon atoms. The average number of moles added r is preferably 1 to 15, more preferably 2 to 13.

Preferred specific examples of the ether oil include polyoxypropylene hexyl ether, polyoxypropylene octyl ether, polyoxypropylene decyl ether, and poly having an average number of moles of propyleneoxy groups added of 1 to 15, more preferably 2 to 10. Examples thereof include oxypropylene lauryl ether, dihexyl ether, dioctyl ether, didecyl ether, dilauryl ether, dimyristyl ether, disetyl ether, distearyl ether, diicosyl ether and dibehenyl ether.

Among them, from the viewpoint of improving the feel of the composition of the present invention, polyoxypropylene hexyl ether and polyoxypropylene octyl ether having an average addition molar number of 1 to 5, more preferably 2 to 4, and even more preferably 3. , Polyoxypropylene decyl ether, polyoxypropylene lauryl ether, dioctyl ether, didecyl ether, dilauryl ether are preferable, and the average number of moles of oxypropylene added is 1 to 5, more preferably 2 to 4, and even more preferably 3. One or more selected from polyoxypropylene octyl ether, polyoxypropylene decyl ether, and polyoxypropylene lauryl ether are more preferable.

The hydrocarbon oil has 20 or more carbon atoms from the viewpoint of improving the coat feeling of the composition of the present invention on the skin, hair or clothing, and imparting a good cohesive feeling to the hair after treatment and drying when applied to the hair. Saturated or unsaturated hydrocarbons are preferred.

Specific examples of the hydrocarbon oil include squalane, squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, cycloparaffin, polybutene, petrolatum, paraffin wax, microcrystallin wax, polyethylene wax, and selecin. From the viewpoint of imparting a good cohesive feeling to the hair when the cleaning agent composition of the present invention is applied to the hair, petrolatum, squalane, squalane, liquid paraffin, or paraffin wax is preferable, and petrolatum, squalane, liquid paraffin. , Or one or more selected from paraffin wax is more preferable.

The higher alcohol is used from the viewpoint of imparting a good cohesive feeling to the hair after treatment and drying when the composition of the present invention is applied to the hair, and from the viewpoint of imparting a silky feeling to the skin when applied to the body. An alcohol having a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms is preferable, an alcohol having 8 to 20 carbon atoms is more preferable, and the alkyl group or the alkenyl group has 8 to 20 carbon atoms, and more preferably 12 carbon atoms. It is of ~ 18.

Specific examples of the higher alcohol include hexyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, and 2-octyl. Dodecanol, icosyl alcohol, or behenyl alcohol can be mentioned.

Among them, lauryl alcohol, from the viewpoint of imparting a good cohesive feeling to the treated and dried hair when applied to the hair of the composition of the present invention, and from the viewpoint of imparting a silky feeling to the skin when applied to the body. Myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, or 2-octyldodecanol is preferable, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, or 2-octyldodecanol is more preferable, and myristyl alcohol, cetyl alcohol, stearyl alcohol. , Or one or more selected from 2-octyldodecanol is more preferred.

Examples of the sterols, such as cholesterol, cholesteryl isostearate, provitamin D _3, Kanbe sterol, stearyl grayed master Nord, stearyl bears sterol, 5-dihydro-cholesterol, alpha-spinasterol, Paris sterol, click Lyoner sterol, .gamma.-sitosterol, stearyl grayed mass tenor , Sargasterol, apenasterol, ergostanol, citosterol, corvisterol, chondrilasterol, polyferrasterol, halicronasterol, neosbongosterol, fucosterol, aptastanol, ergostazienol, ergosterol, 22-dihydroergosterol , Brush casterol, 24-methylene cholesterol, 5-dihydro ergosterol, dehydro ergosterol, fungisterol, chorestanol, coprostanol, dimosterol, 7-het cholesterol, latosterol, 22-dehydrocholesterol, β-citosterol, cholesterol Trien-3β-ol, coprostanol, cholestanol, ergosterols, 7-dehydrocholesterol, 24-dehydrocholestron-3β-ol, echillenin, equilin, estrone, 17β-estradiol, androsto-4-en-3β, Examples thereof include 17β-diol, dehydroebiandrosterone, cholesterol alkenyl succinate (Japanese Patent Laid-Open No. 5-294489) and the like. Of these, cholesterol, cholesteryl isostearate, and cholesteryl alkenyl succinate are particularly preferable.

As the fluorine-based oil, perfluoropolyether and fluorine-modified silicone, which are perfluoroorganic compounds that are liquid at room temperature, are preferable, and for example, perfluorodecalin, perfluoroadamantan, perfluorobutyltetrahydrofuran, perfluorooctane, and perfluoro Nonane, perfluoropentane, perfluorodecane, perfluorododecane, perfluoropolyether, fluorine-containing ether compound represented by the following general formula (10)

(In the formula, Rf represents a linear or branched perfluoro group having 1 to 20 carbon atoms, R ⁹ represents a linear or branched cycloalkyl group having 3 to 9 carbon atoms, and n is a number of 1 to 8. ), Etc. can be mentioned. Specific examples thereof include 1,3-dimethylbutyl {2- (perfluorooctyl) ethyl} represented by the following formula (11).

As the hydrocarbon group of the carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms in which the hydroxyl group may be substituted, a linear or branched alkyl group or alkenyl group is preferable.
Specific examples of the carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms in which the hydroxyl group may be substituted include stearic acid, oleic acid, isostearic acid, hydroxystearic acid, behenic acid, logonic acid and the like. .. Among them, stearic acid, from the viewpoint of imparting a good cohesive feeling to the hair after treatment and drying when the composition of the present invention is applied to the hair, and from the viewpoint of imparting a moist feeling to the skin when applied to the body. Oleic acid, isostearic acid, hydroxystearic acid, or behenic acid is preferable, and oleic acid or isostearic acid is more preferable.

The oily component used in the present invention gives a good cohesive feeling to the hair after treatment and drying when the composition of the present invention is applied to the hair, and gives a moist feeling to the skin when applied to the body. From the viewpoint, the solubility in 100 g of water at 20 ° C. is preferably 0 g or more and 1 g or less, the solubility in 100 g of water at 20 ° C. is preferably 0 g or more and 0.5 g or less, and the solubility in 100 g of water at 20 ° C. is 0 g or more and 0.1 g or less. Is more preferable.

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

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 or more, from the viewpoint of reducing viscosity. , 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, further. It is preferably 0.7% by mass or less.

From the viewpoint of cost, the content of the oily component 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. It is more preferably 80% by mass or more, preferably 99.99% by mass or less, more preferably 99.95% by mass or less, still more preferably 99.9% by mass or less from the viewpoint of devitrification.

The content of the oily component in the composition of the present invention is preferably 1.0% by mass or more and 99.9% by mass or less from the viewpoint of improving the silky feeling and the coating feeling after drying of the skin treated with the composition. , More preferably 10.0% by mass or more and 99.8% by mass or less, still more preferably 50.0% by mass or more and 99.7% by mass or less. When the skin treatment composition is lipstick, the content of the oily component in the composition is more preferably 20.0% by mass or more, 95.0% by mass or less, still more preferably 50. It is 0% by mass or more and 80.0% by mass or less. When the skin treatment composition is a bath salt, the content of the oily component in the composition is more preferably 10.0% by mass or more, 95.0% by mass or less, still more preferably 50, from the same viewpoint. It is 0.0% by mass or more and 90.0% by mass or less.

In the composition of the present invention, the ratio of the etherified cellulose fiber to the oily component is determined from the viewpoint of improving the dry and smooth feeling and the coat feeling of the skin treated with the composition of the present invention. Ingredients] by mass ratio, preferably 0.0001 to 0.10, more preferably 0.001 to 0.03, still more preferably 0.002 to 0.02, still more preferably 0.003 to 0.01. is there. When the composition of the present invention is a lipstick, the mass ratio is preferably 0.001 to 0.05, more preferably 0.003 to 0.02, still more preferably 0.005 to 0. It is 01. When the composition of the present invention is a bath agent, the mass ratio is preferably 0.0003 to 0.03, more preferably 0.001 to 0.01, still more preferably 0.003 to 0, from the same viewpoint. It is .008.

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, from the viewpoint of reducing viscosity with respect to 100 parts by mass of the oily component. 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, water, inorganic salts, organic salts, surfactants, moisturizers, preservatives, organic fine particles, inorganic fine particles, dyes, deodorants, fragrances, organic solvents, etc. The functional additive of the above can be contained within a range that does not impair the effects of the present invention. The content ratio of such a component may be appropriately contained as long as the effect of the present invention is not impaired. For example, when the other component is water, it is preferably 90% by mass or less in the composition, more preferably 70. It is about mass% or less, more preferably about 50% by mass or less. When the other component is other than water, it is preferably 50% by mass or less, more preferably about 40% by mass or less, and further preferably about 30% by mass or less in the composition.

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

The composition of the present invention has a surprisingly high viscosity-reducing effect. Therefore, the composition of the present invention is provided as a slimming agent composition. Further, the composition obtained by removing the oily component 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. The modified cellulose fiber may be used as a thickener.

Specifically, using this effect, skin treatments such as lipsticks, bathing agents, body shampoos, hand cleaners, shave lotions, facial cleansers, cleansing creams, lotions, beauty liquids, packs, ointments, and patches. Agent composition, shampoo, conditioner, rinse, rinse-in shampoo, hair styling agent, hair treatment agent, hair dye, hair treatment agent composition such as hair restorer, as well as clothing detergent, washing softener, clothing paste, It can be used for one or more uses selected from the group consisting of a garment treatment agent composition such as a finishing agent.

(Manufacturing method of composition)
The composition of the present invention can be prepared by mixing the etherified cellulose fiber, an oily component, 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 the oily component 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.

Example of production of a compound for introducing a substituent 1 Production of stearyl glycidyl ether In a 100 L reaction vessel, 10 kg of stearyl alcohol (manufactured by Kao, Calcol 8098), 0.36 kg of tetrabutylammonium bromide (manufactured by Koei Chemical Industry Co., Ltd.), epichlorohydrin. 7.5 kg (manufactured by Dow Chemical Co., Ltd.) and 10 kg of hexane were added and mixed in a nitrogen atmosphere. While maintaining the mixed solution at 50 ° C., 12 kg of a 48 mass% sodium hydroxide aqueous solution (manufactured by Nankai Chemical Co., Inc.) was added dropwise over 30 minutes. After completion of the dropping, the mixture was further aged at 50 ° C. for 4 hours, and then washed with 13 kg of water 8 times to remove salts and alkalis. Then, the temperature in the tank was raised to 90 ° C., hexane was distilled off from the upper layer, and under reduced pressure (6.6 kPa), steam was further blown to remove the low boiling point compound. After dehydration, 8.6 kg of white stearyl glycidyl ether was obtained by distillation under reduced pressure at a temperature in the tank of 250 ° C. and a pressure in the tank of 1.3 kPa.

Preparation Example 1 of Etherealized Cellulose Fiber <Preparation of Liquid Paraffin Dispersion of Ethereated Cellulose>
First, 30 g of bleached kraft pulp (NBKP) of absolutely dried coniferous tree and 30 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, 0.26 equal amount of NaOH / 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 80 g of methylisobutylketone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and mixed uniformly. After that, 6.4 g of propylene oxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.6 equal amount / AGU) 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, 120 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and 24 g of N, N-dimethyl-4-aminopyridine (manufactured by Wako Pure Chemical Industries, Ltd., DMAP, 1.6 equivalent / AGU) were added to 20 g of the obtained etherified cellulose fibers. Was added and mixed uniformly, then 414 g (6 equivalents / AGU) of stearyl glycidyl ether prepared in Production Example 1 was added, and after sealing, a standing reaction was carried out at 70 ° C. for 24 hours. After the reaction, neutralize with acetic acid, wash thoroughly with dimethylformamide (DMF) and water / isopropanol mixed solvent to remove impurities, and vacuum dry at 50 ° C. overnight to perform two types of substitution. An etherified cellulose fiber having a group was obtained.

5.0 g of the obtained etherified cellulose fiber having two kinds of substituents was put into 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and a homogenizer (manufactured by Primix Corporation, TK Robomix) was used at 3000 rpm for 30. After stirring for 1 minute, 8-pass treatment was performed at 100 MPa with a high-pressure homogenizer (“NanoVita L-ES” manufactured by Yoshida Machinery Co., Ltd.). 100 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained dispersion, and a 2-pass treatment was further carried out at 100 MPa using the high-pressure homogenizer. A fine etherified cellulose dispersion in which finely divided etherified cellulose fibers are dispersed in liquid paraffin by distilling off toluene in the dispersion liquid for a whole day and night under the condition of 80 ° C. and reduced pressure. (Solid content concentration 5.0% by mass) was obtained.

The obtained 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 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 (mass%) of the ether group in the etherified cellulose fiber was calculated from the detected amount of the etherification reagent used.
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 (% by 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.]

Evaluation method <viscosity>
100 mL of the test solution was put into a 120 mL standard bottle (manufactured by AS ONE Corporation, No. 11), sealed, and then allowed to stand in a constant temperature room adjusted to 25 ° C. for 5 hours. After that, the viscosity was measured using a B-type viscometer in the same constant temperature room, and the obtained measured viscosities are shown in Table 1 (using a TVB10 type viscometer manufactured by Toki Sangyo Co., Ltd., M2 rotor, measurement time 60 seconds). ). Further, the thixotropy index (TI) was calculated from the formula (measured viscosity at a rotation speed of 30 r / min) / (measured viscosity at a rotation speed of 6 r / min) and is shown in Table 1. The larger the TI value, the higher the thickening effect in the high shear region.

<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 1 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 1).
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 1).
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 smooth feeling of the hair after drying, and the coat feeling of the hair after drying were evaluated. Table 1 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 1).
2: Hair is not well organized.
1: My hair doesn't come together at all.
・ Smooth feeling of hair after drying 5: Hair is very smooth and smooth 4: Hair is smooth and smooth 3: Normal (equivalent to Comparative Example 1)
2: Hair is not smooth and lacks smoothness 1: Hair is not smooth at all and is not smooth (rather, it feels rough)
・ Coat feeling of hair after drying 5: Strong coat feeling, no pain at hair tips 4: Coat feeling, almost no pain at hair tips 3: Normal (same as Comparative Example 1)
2: No coat feeling, strong hair tip pain 1: No coat feeling, very strong hair tip pain (hair breakage occurs)

<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 silky feeling after drying, the coating feeling after drying, the water repellency, 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 1 shows the average score of the evaluations of 5 people.
・ Smooth feeling 5: Very smooth and no stickiness to the fingertips 4: Smooth and almost no stickiness 3: Normal (same as Comparative Example 1)
2: Feels clearly sticky without exposing it 1: Very sticky (does not feel smooth at all)
・ Coat feeling 5: Coat feeling is strong and no fiber damage (damage) is felt 4: Coat feeling and almost no fiber damage is felt 3: Normal (same as Comparative Example 1)
2: There is no coat feeling and the fiber is strongly damaged 1: There is no coat feeling at all and the fiber feels severely damaged

Water-repellent Ion-exchanged water (0.02 mL) is dropped on a cotton cloth after drying with a microsyringe, immediately after dropping with an optical microscope (Keyence, "Digital Microscope VHX-1000", magnification 25 times), and After photographing the droplets after 5 seconds, the contact angle was measured and calculated using this machine. The larger the value (contact angle), the more hydrophobic the surface and the better the water repellency.

Quick-drying After immersing 0.5 g of ion-exchanged water in the dried cotton cloth, dry it with a dryer, and evaluate the drying rate 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 composition of Example 1 containing the etherified cellulose fiber and the oily component has a lower viscosity than the composition of Comparative Example 1 containing only the oily component, and has a skin application test, a hair application test, a clothing treatment test, and clothing. All the results of the treatment test (quick-drying) were good.

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

Prescription example 2
Bath salt 1 having the following composition is prepared by a conventional method.

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

Claims (5)

A composition containing etherified cellulose fibers and oily components.
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 an etherified cellulose fiber represented by the following general formula (4), 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. ]

[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. Indicates an integer of 3000 or more, except when all Rs are hydrogen at the same time] A composition containing etherified cellulose fibers and oily components.
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 ( A composition which is an etherified cellulose fiber having a cellulose type I crystal structure in which the substituents represented by 3) are independently bonded to the cellulose fibers 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 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. ] A composition containing etherified cellulose fibers and oily components.
The etherified cellulose fiber is an etherified cellulose fiber having a cellulose type I crystal structure in which a hydrocarbon group which may have a substituent is bonded to the cellulose fiber via an ether bond.
Treatment agent composition for skin, treatment agent composition for hair or treatment agent composition for clothing. 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 bonded to the cellulose fiber via an ether bond. , A thickener comprising an etherified cellulose fiber represented by the following general formula (4), which 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. ]

[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. Indicates an integer of 3000 or more, except when all Rs are hydrogen at the same time] 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 substitutions represented by the following general formula (3). A thickener comprising an etherified cellulose fiber in which each group is independently bonded to a cellulose fiber via an ether bond 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 -OR ₁ (2)
-CH ₂ -CH (R) ₀ ) -R ₂ (3)
[In the formula, R in the general formula (1) and the general formula (2) ₀ Indicates a hydrogen atom or a hydroxyl group, and R in the general formula (1) and the general formula (2) ₁ Independently indicate a linear or branched alkyl group having 3 to 30 carbon atoms, n in the general formula (2) is a number of 0 to 50, and A is a linear or branched chain having 1 to 6 carbon atoms. Indicates a divalent saturated hydrocarbon group of the branched chain, and R in the general formula (3). ₀ Indicates a hydrogen atom or a hydroxyl group, and R ₂ Indicates an alkyl group having 1 or more carbon atoms and 2 or less carbon atoms. ]