JP2018145334A - Etherified cellulose fiber and composition containing water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel composition having excellent foamability.SOLUTION: A composition contains an etherified cellulose fiber and water, and the etherified cellulose fiber is a modified cellulose fiber in which an optionally substituted hydrocarbon group is bound to a cellulose fiber through ether linkage, to form a cellulose I type crystal structure.SELECTED DRAWING: None

Description

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

  Conventionally, plastic materials derived from petroleum, which is a finite resource, have been widely used, but in recent years, technologies with less environmental impact have come to the spotlight. Various compositions using cellulose fibers have attracted attention.

  For example, Patent Document 1 discloses cellulose nanofibers obtained by defibration by high-pressure jetting.

JP2015-157796A

  The cellulose fiber itself hardly exhibits foaming properties in water, but it has been newly found that when a specific modified cellulose fiber is used, it unexpectedly exhibits foaming properties.

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the novel composition excellent in foaming property can be provided.

  According to the structure of this invention, foaming property is unexpectedly expressed. The reason for this is not clear, but the cellulose fiber according to the present invention has a functional group via an ether bond, so that it is presumed that the foaming property in the aqueous dispersion can be expressed by expressing the surface activity. .

  Furthermore, according to the configuration of the present invention, when applied to the skin, a smooth feeling and a coat feeling are exhibited, and when applied to the hair, cohesiveness, combing and gloss are exhibited and applied to a hard surface. In some cases, the effect of increasing the contact angle of water droplets is exhibited, and when applied to clothing, the effect of suppressing wrinkles and the effect of quick drying are exhibited. Although these reasons are not clear, they are estimated as follows.

  Cellulose fibers generally remain on the skin, hair and fibers, and film formation and coating effects are known. Using the composition using cellulose fibers according to the present invention, skin, hair, hard surface, When processing clothing (coating, washing, etc.) is performed, the residual amount increases due to the effect of the functional group, or the residual state such as remaining uniformly on the surface changes, or the effect of the functional group Thus, it is presumed that the effect can be obtained by improving the hydrophobicity of the cellulose fiber itself.

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

[Etherized cellulose fiber]
The etherified cellulose fiber in the present invention is 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 surface of the cellulose fiber via an ether bond. It is characterized by. In the present specification, “bonded via an ether bond” means a state in which the modifying group reacts with a hydroxyl group on the surface of the cellulose fiber to form an ether bond.

In the hydrocarbon group 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 alicyclic hydrocarbon group such as a cyclohexyl group can be mentioned, and from the viewpoint of foamability and economy, it is preferably a saturated or unsaturated linear or branched aliphatic hydrocarbon group, more preferably A saturated linear or branched aliphatic hydrocarbon group.
In the hydrocarbon group which may have a substituent in the present invention, examples of the substituent include a halogen atom, an oxyalkylene group such as an oxyethylene group, a hydroxyl group, and the like, from the viewpoint of foamability and economy. Preferably, they are an oxyethylene group and a hydroxyl group.

As a suitable aspect (aspect 1) of such an etherified cellulose fiber, for example, one kind selected from a substituent represented by the following general formula (1) and a substituent represented by the following general formula (2) or Two or more kinds of substituents are bonded to the cellulose fiber through an ether bond, and examples thereof have a cellulose I-type crystal structure.
—CH ₂ —CH (R ₀ ) —R ₁ (1)
—CH ₂ —CH (R ₀ ) —CH ₂ — (OA) _n —O—R ₁ (2)
[R ₀ in the formula, the general formula (1) and the general formula (2) represents a hydrogen atom or a hydroxyl group, the general formula (1) and R ₁ is 3 or more carbon atoms each independently of the general formula (2) 30 In the general formula (2), n represents a number of 0 or more and 50 or less, and A represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms. Show. ]

  As a specific example of the aspect 1, for example, an etherified cellulose fiber represented by the following general formula (4) is exemplified.

[Wherein, R is the same or different and represents hydrogen or a substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2); An integer of 3,000 or more is preferable, except that all R are hydrogen at the same time.]

  The etherified cellulose fiber represented by the general formula (4) has the same or different R, hydrogen, a substituent represented by the general formula (1) and / or a substitution represented by the general formula (2) It represents a group and has a repeating structure of a cellulose unit into which the substituent is introduced. As the repeating number 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 foamability.

(Hydrocarbon group which may have a substituent)
In the etherified cellulose fiber of aspect 1, one or more substituents selected from the substituents represented by the general formula (1) and the following general formula (2) are introduced alone or in any combination. Is done. In addition, even if it is a case where the substituent introduce | transduced is any one of the said substituent groups, in each substituent group, even if it is the same substituent, 2 or more types may be combined and introduced.

R ₀ in the general formulas (1) and (2) represents a hydrogen atom or a hydroxyl group. From the viewpoint of foamability, R ₀ in the general formulas (1) and (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 foamability, it is preferably 25 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and still more preferably 12 or less. 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 include icosyl group and 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, preferably 4 or more, more preferably 6 or more, from the viewpoint of foamability, preferably from the viewpoint of foamability, 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. A specific example is same as R ₁ in the general formula (1) described above.

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

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

  Specific examples of the substituent represented by the general formula (1) include, for example, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isooctadecyl group. Group, icosyl group, propylhydroxyethyl group, butylhydroxyethyl group, pentylhydroxyethyl group, hexylhydroxyethyl group, heptylhydroxyethyl group, octylhydroxyethyl group, 2-ethylhexylhydroxyethyl group, nonylhydroxyethyl group, decylhydroxyethyl Group, undecylhydroxyethyl group, dodecylhydroxyethyl group, hexadecylhydroxyethyl group, octadecylhydroxyethyl group, isooctadecylhydroxyethyl group, icosylhydroxyethyl group, triacon Le 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-hexoxyethylene 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-hexoxy-2-hydroxy-propyl group, 6-ethyl-3-hex Toxiethylene oxide-2-hydroxy-propyl group, 3-deoxyethylene oxide-2-hydroxy-propyl group, 3-deoxy-2-hydroxy-propyl group, 3-undeoxyethylene oxide-2-hydroxy-propyl group, 3-undetoxy 2-hydroxy-propyl group, 3-dodeoxyethyleneoxy Do-2-hydroxy-propyl group, 3-dodeoxy-2-hydroxy-propyl group, 3-hexadeoxyethylene oxide-2-hydroxy-propyl group, 3-hexadetox-2-hydroxy-propyl group, 3-octadetoxoxy Examples thereof include an ethylene oxide-2-hydroxy-propyl group and a 3-octadeoxy-2-hydroxy-propyl group. In addition, the addition mole number of alkylene oxide should just be 0 or more and 50 or less, for example, in the substituent which has oxyalkylene groups, such as an ethylene oxide mentioned above, the substituent whose addition mole number is 10, 12, 13, 20 mol is illustrated. Is done.

(Introduction rate)
In the etherified cellulose fiber of aspect 1, 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 anhydroglucose unit of cellulose is: The type of the substituent is not generally limited, but from the viewpoint of foaming properties, it is preferably 0.0001 mol or more, more preferably 0.0005 mol or more, still more preferably 0.0007 mol or more, From the viewpoint of foamability, it has a cellulose I-type crystal structure, and 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, it is 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 means the total introduction molar ratio. In the present specification, the introduction rate can be measured according to the method described in the examples described later, and may be described as the introduction molar ratio or the modification rate.

As a more preferred embodiment (embodiment 2) of the etherified cellulose fiber in the present invention, for example, one kind selected from a substituent represented by the following general formula (1) and a substituent represented by the following general formula (2) Or two or more kinds of substituents and the substituent represented by the following general formula (3) are each independently bonded to the cellulose fiber via an ether bond and have a cellulose I-type 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)
[R ₀ in the formula, the general formula (1) and the general formula (2) represents a hydrogen atom or a hydroxyl group, the general formula (1) and R ₁ is 3 or more carbon atoms each independently of the general formula (2) 30 The following linear or branched alkyl groups are shown, n in the general formula (2) is a number from 0 to 50, and A is a linear or branched divalent saturated hydrocarbon group having 1 to 6 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 to 2 carbon atoms. ]

  Specific examples of the etherified cellulose fiber of aspect 2 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 ) Represents a substituent represented by the general formula (3), m is preferably an integer of 20 or more and 3000 or less, provided that when all Rs are hydrogen at the same time, and when they are simultaneously the substituent (a), And except when it is a substituent (b) at the same time]

  The etherified cellulose fiber represented by the general formula (5) has the same or different R, and is represented by hydrogen, (a) a substituent represented by the general formula (1), and the general formula (2). A substituent selected from substituents, or (b) a substituent represented by the general formula (3), which has a repeating structure of a cellulose unit into which the substituent is introduced. As a repeating number 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 foamability.

(Hydrocarbon group which may have a substituent)
The hydrocarbon group which may have a substituent in the etherified cellulose fiber of Aspect 2 includes (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 group, and (b) the substituent represented by the general formula (3), that is, the substituent in the group (a) and the substituent in the group (b) The substituents are bonded together and introduced in each group alone or in any combination. In addition, in the substituent of (a) group, even if it is the case of either the substituent represented by General formula (1) or the substituent represented by General formula (2), in each substituent, May be introduced in combination of two or more of the same substituents. In the substituent group (a), the substituent represented by the general formula (1) and the substituent represented by the general formula (2) may be introduced singly or in combination of two or more. .

  About general formula (1) and general formula (2), it is the same as that of aspect 1.

R ₀ in the general formula (3) represents a hydrogen atom or a hydroxyl group, and a hydroxyl group is preferred from the viewpoint of foamability.
R ₂ in the general formula (3) is an alkyl group having 1 to ₂ carbon atoms, specifically 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, and a 2-hydroxy-butyl group.

(Introduction rate)
In the etherified cellulose fiber of aspect 2, 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 anhydroglucose unit of cellulose is: The introduction rate of the substituent represented by the general formula (3) with respect to 1 mol of anhydroglucose unit of cellulose is the same as in Embodiment 1, and has a cellulose I-type crystal structure, preferably from the viewpoint of foamability. 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's it.

(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 aspect in which the average fiber diameter is in the micro order and an aspect in which the average fiber diameter is in the nano order are exemplified.

  The etherified cellulose fiber in a micro-order mode is preferably 5 μm or more, more preferably 7 μm or more, and even more preferably 10 μm or more from the viewpoint of foamability, handleability, availability, and cost. The upper limit is not particularly set, but 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, and even more preferably 30 μm or less from the viewpoint of foaming properties and handling properties. In the present 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 the completely dried cellulose fiber in ion-exchanged water using a household mixer or the like to dissolve the fiber, and then adding ion-exchanged water and stirring uniformly. An example is a method in which a part of the dispersion is analyzed by “Kajaani Fiber Lab” manufactured by Metso Automation. By this method, a fiber diameter having an average fiber diameter of micro order can be measured.

  From the viewpoint of foamability, handleability, availability, and cost, the etherified cellulose fiber in the nano-order mode is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 10 nm or more, and further preferably 20 nm or more. In view of foamability 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, and even more preferably 120 nm or less. In the present specification, the average fiber diameter of nano-order cellulose fibers can be measured according to the following method.

  Specifically, the dispersion liquid obtained at the time of the micronization treatment was observed with an optical microscope (manufactured by Keyence Corporation, “Digital Microscope VHX-1000”) at a magnification of 300 to 1000 times, and fiber 30 By measuring an average value of at least the number of fibers, a nano-order fiber diameter can be measured. When observation with an optical microscope is difficult, a dispersion prepared by further adding a solvent to the dispersion is dropped on mica (mica) and dried, and an observation sample is used as an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital instrument, and probe using Nano Probes Point Probe (NCH) can be used. In general, the smallest unit of cellulose nanofibers prepared from higher plants is a 6 × 6 molecular chain packed in a nearly square shape, so the height analyzed by AFM images is regarded as the fiber width. Can do.

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

[Method for producing etherified cellulose fiber]
In the etherified cellulose fiber in 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. And can be carried out according to known methods.

  Hereinafter, a specific example of the method for producing the etherified cellulose fiber of Embodiment 1 and Embodiment 2 will be described.

(Method for producing etherified cellulose fiber of embodiment 1)
As a specific example of the method for producing the etherified cellulose fiber of aspect 1, there may be mentioned an aspect in which a specific compound is reacted with a cellulose-based raw material in the presence of a base.

(Cellulosic material)
Cellulosic raw materials are not particularly limited, and are woody (coniferous and broadleaf), herbaceous (grass, mallow, leguminous plant, palmaceous plant non-woody), pulp (cotton seeds) And cotton linter pulp obtained from the surrounding fibers) and papers (newspaper, cardboard, magazines, high-quality paper, etc.). Of these, woody and herbaceous are preferred from the viewpoints of availability and cost.

  The shape of the cellulosic raw material is not particularly limited, but is preferably a fiber, powder, sphere, chip, or flake from the viewpoint of handleability. Moreover, these mixtures may be sufficient.

  In addition, the cellulosic raw material can be subjected in advance to 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 to the drug used, and examples thereof include treatment using an enzyme such as endoglucanase, exoglucanase, or betaglucosidase. The chemical treatment is not particularly limited as to the chemical used, and examples thereof include acid treatment with hydrochloric acid and sulfuric acid, and oxidation treatment with hydrogen peroxide and ozone. As the mechanical treatment, there is no particular limitation on the machine to be used and the treatment conditions, for example, a high pressure compression roll mill, a roll mill such as a roll rotating mill, a vertical roller mill such as a ring roller mill, a roller race mill or a ball race mill, Rolling ball mill, vibrating ball mill, vibrating rod mill, vibrating tube mill, planetary ball mill, centrifugal fluidizing mill and other container driven medium mills, tower type grinder, stirring tank type mill, flow tank type mill or annular type mill, etc. Condensation shearing mills such as type mills, high-speed centrifugal roller mills and ong mills, mortars, millstones, mass colloiders, fret mills, edge runner mills and other grinding machines, knife mills, pin mills, cutter mills and the like.

  In the above mechanical treatment, water, ethanol, isopropyl alcohol, t-butyl alcohol, toluene, xylene and other solvents, phthalic acid-based, adipic acid-based, trimellitic acid-based plasticizers, urea and alkali (earth) ) It is possible to promote shape change by mechanical treatment by adding auxiliary agents such as metal hydroxides and hydrogen bond inhibitors such as amine compounds. By adding a shape change in this manner, the handling property of the cellulose-based raw material is improved, the introduction of substituents is improved, and the physical properties of the resulting etherified cellulose fiber can also be improved. The amount of the additive aid used varies depending on the additive aid used, the mechanical processing technique used, and the like, but from the viewpoint of expressing the effect of promoting shape change, usually 5 parts by mass or more with respect to 100 parts by mass of the raw material, Preferably, it is 10 parts by mass or more, more preferably 20 parts by mass or more, and from the viewpoint of developing the effect of promoting shape change and from the viewpoint of economy, it is usually 10000 parts by mass or less, preferably 5000 parts by mass or less. Preferably it is 3000 mass parts 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, and still more preferably 15 μm or more from the viewpoints of handleability and cost. In addition, the upper limit is not particularly set, but 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, and even more preferably 100 μm or less. It is.

  In addition, from the viewpoint of reducing the number of production steps, a cellulose material that has been refined 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. More preferably, it is 3 nm or more, More preferably, it is 10 nm or more. Moreover, although an upper limit in particular is not set, from a viewpoint of handleability, Preferably it is 500 nm or less, More preferably, it is 300 nm or less, More preferably, it is 200 nm or less, More preferably, it is 100 nm or less, More preferably, it is 80 nm or less.

  In addition, the average fiber diameter of a cellulosic raw material can be measured like the above-mentioned etherified cellulose fiber.

  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, and 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, and still more preferably 90% by mass or less. Here, the cellulose content in the cellulosic raw material is the cellulose content in the remaining components excluding moisture in the cellulosic raw material.

  The water content in the cellulosic material is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.5% from the viewpoint of availability and cost. % By mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, more preferably 2.0% by mass or more, and from the viewpoint of handling, preferably 50% by mass or less, more Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is what was absolutely dry-processed, ie, 10 mass% or less.

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

  Although there is no restriction | limiting in particular as a base, From a viewpoint of advancing etherification reaction, an alkali metal hydroxide, an alkaline-earth metal hydroxide, a 1-3 tertiary amine, a quaternary ammonium salt, imidazole and its derivative, pyridine And one or more selected from the group consisting of alkoxides and derivatives thereof.

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

  The primary to secondary amines are primary amines, secondary amines, and tertiary amines. Specific examples include ethylenediamine, diethylamine, proline, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, tris (3-dimethylaminopropyl) amine, N, N-dimethylcyclohexylamine, triethylamine and the like can be mentioned.

  Quaternary ammonium salts include tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium fluoride, tetraethylammonium bromide, water Examples thereof include tetramethylammonium oxide, tetramethylammonium chloride, tetramethylammonium fluoride, and tetramethylammonium bromide.

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

  Examples of pyridine and derivatives thereof include N, N-dimethyl-4-aminopyridine and picoline.

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

  The amount of the base is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, still more preferably 0.1 from the viewpoint of allowing the etherification reaction to proceed with respect to the anhydroglucose unit of the cellulosic raw material. Equal amount or more, more preferably 0.2 equivalent or more, and from the viewpoint of production cost, it is preferably 10 equivalents or less, more preferably 8 equivalents or less, still more preferably 5 equivalents or less, still more preferably 3 etc. Less than the amount.

  In addition, you may perform mixing of the said cellulose raw material and a base in presence of a solvent. The solvent is not particularly limited, and examples thereof include water, isopropanol, t-butanol, dimethylformamide, toluene, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, 1,4-dioxane, and mixtures thereof.

  The mixing of the cellulosic raw material and the base is not particularly limited as long as it can be uniformly mixed.

  Next, a compound for introducing a hydrocarbon group which may have a substituent is added to the cellulose-based raw material and base mixture obtained above, and the cellulose-based raw material is reacted with the compound. As such a compound, when reacting with the cellulose-based raw material, one or more substituents selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2) In the present invention, from the viewpoint of reactivity and non-halogen-containing compounds, a compound having a reactive cyclic structure group may be used. It is preferable to use a compound having an epoxy group. Below, each compound is illustrated.

  As a compound which can couple | bond the substituent represented by General formula (1) through an ether bond, the alkylene oxide compound shown by the following general formula (1A) and the alkyl shown by General formula (1B) are mentioned, for example. Halides are preferred. As such a compound, one prepared according to a known technique may be used, or a commercially available product may be used. The total carbon number of the compound is 3 or more from the viewpoint of foamability, preferably 5 or more, more preferably 6 or more, still more preferably 8 or more, still more preferably 12 or more. From the viewpoint, it is 32 or less, preferably 27 or less, more preferably 22 or less, further preferably 20 or less, still more preferably 18 or less, still more preferably 14 or less, and still more preferably 12 or less.

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

_{X- (CH 2) 2 -R 1} (1B)
[Wherein, R ₁ represents a linear or branched alkyl group having 3 to 30 carbon atoms, and X represents 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, preferably 4 or more, more preferably 6 or more, still more preferably 10 or more from the viewpoint of foamability, preferably from the viewpoint of foamability. 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. Specific examples include those described in the section of 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 include iododecane, 1-iodododecane, 1-iodohexadecane, and 1-iodooctadecane.

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

[Wherein, 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, preferably 4 or more, more preferably 6 or more from the viewpoint of foamability, and preferably 27 or less, more preferably from the viewpoint of foamability. It is 22 or less, more preferably 20 or less, more preferably 18 or less, more preferably 16 or less, and 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 to 6 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 from the viewpoint of availability and cost, it is preferably 2 or more, and from the same viewpoint, it is preferably 4 or less, more preferably 3 or less. Specific examples include those described in the section A in the substituent represented by the general formula (2), 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) represents the number of added moles of alkylene oxide. n is a number of 0 or more and 50 or less, but from the viewpoint of availability and cost, it is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and from the same viewpoint, preferably 40 or less. Preferably it is 30 or less, More preferably, it is 20 or less, More preferably, it is 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 a 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, it is preferably 0.01 equivalents or more, more preferably 0.1 equivalents or more, still more preferably 0.3 equivalents or more, and still more preferably, relative to the anhydroglucose unit of the cellulosic material. 0.5 equivalents or more, more preferably 1.0 equivalents or more, and from the viewpoint of production cost, preferably 10 equivalents or less, more preferably 8 equivalents or less, still more preferably 6.5 equivalents or less, More preferably, it is 5 equivalents or less.

(Ether reaction)
The ether reaction between the compound and the cellulose-based raw material can be carried out by mixing both in the presence of a solvent. There is no restriction | limiting in particular as a solvent, The solvent illustrated as being able to be used when making the said base exist can be used.

  The amount of the solvent used is not generally determined by the type of the compound for introducing the cellulose-based raw material or the hydrocarbon group which may have the substituent, but with respect to 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, more preferably 100 parts by mass or more, and further preferably 200 parts by mass or more. From a viewpoint, Preferably it is 10,000 mass parts or less, More preferably, it is 5,000 mass parts or less, More preferably, it is 2,500 mass parts or less, More preferably, it is 1,000 mass parts or less, More preferably, it is 500 mass parts or less. is there.

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

  The reaction temperature is not generally determined by the kind 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 the viewpoint of improving the reactivity From the viewpoint of suppressing thermal decomposition, it is preferably 120 ° C. or less, more preferably 110 ° C. or less, and still more preferably 100 ° C. It is as follows.

  The reaction time is not determined unconditionally depending on the type of the compound for introducing the cellulose-based raw material and the hydrocarbon group optionally having the substituent and the target introduction rate, but from the viewpoint of reactivity, 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. , Preferably 60 hours or less, more preferably 48 hours or less, and still more preferably 36 hours or less.

  In addition, from the viewpoint of handleability, the etherified cellulose fiber is subjected to the same treatment as the pretreatment performed on the cellulosic material, for example, in the form of chips, flakes, and powders. It may be. When the resulting etherified cellulose fiber is added to water due to the shape change caused by such treatment, a composition of etherified cellulose fiber and water can be produced with lower energy.

  Further, the etherified cellulose fiber may be refined by performing a known refinement 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. In addition, it is possible to obtain a fine etherified cellulose fiber by carrying out the above-described substituent introduction reaction using a cellulose-based raw material that has been refined in advance, but from the viewpoint of foamability, after the reaction of introducing the substituent. It is preferable to carry out a known miniaturization treatment for miniaturization.

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

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

  Thus, etherified cellulose fibers are obtained.

(Method for producing etherified cellulose fiber of embodiment 2)
As an example of such a production method, for example, in the presence of a base, the etherified cellulose fiber of Embodiment 1 is reacted with a compound capable of bonding a substituent represented by the general formula (3) via an ether bond. A method is mentioned. In the present invention, regardless of the order of introduction of the substituent represented by the general formula (1) and / or (2) and the introduction of the substituent represented by the general formula (3), the general formula ( The conditions for introducing the substituent represented by 3) can adopt the same conditions as in the first aspect.

  As a compound which can couple | bond the substituent represented by General formula (3) through an ether bond, the alkylene oxide compound shown by the following general formula (3A) and the alkyl shown by General formula (3B) are mentioned, for example. Halides are preferred. As such a compound, one prepared according to a known technique may be used, 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 foamability.

Wherein, R ₂ represents an alkyl group having 1 to 2 carbon atoms. ]

_{X- (CH 2) 2 -R 2} (3B)
[Wherein, R ₂ represents an alkyl group having 1 to ₂ carbon atoms, and X represents 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 to 2 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 a desired introduction rate of the substituent represented by the general formula (3) in the cellulose fiber to be obtained. On the other hand, it is preferably 5.0 equivalent or less, and the lower limit is about 0.02 equivalent.

(water)
Although the water which comprises the composition of this invention is not restrict | limited in particular, What has as few impurities as possible is preferable. For example, tap water, industrial water, ion exchange water, distilled water, and ultrapure water are preferable water.

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

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

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

  The amount of etherified cellulose fibers in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and further preferably 100 parts by mass of water from the viewpoint of foamability. 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. 50 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.

  The composition of the present invention includes inorganic salts, organic salts, surfactants, oils, moisturizers, preservatives, organic fine particles, inorganic fine particles, dyes, deodorants, fragrances, organic solvents as components other than the above. Etc. can be contained in the range which does not impair the effect of this invention. As such a component content ratio, it may be appropriately contained within a range where the effects of the present invention are not impaired. For example, the content is preferably 50% by mass or less, more preferably about 40% by mass or less, and more preferably about 30% by mass. The following is more preferable.

  The compositions of the present invention exist and are provided, for example, in a dispersion of etherified cellulose fibers and water.

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

  Specifically, using such effects, body shampoos, hand cleaners, shave lotions, facial cleansers, cleansing creams, skin lotions, cosmetics, packs, ointments, patches, and other skin treatment compositions, shampoos. Hair conditioner composition such as conditioner, rinse, rinse-in shampoo, hair styling agent, hair treatment agent, hair dye, hair restorer, dishwashing detergent, toilet cleaner, tile cleaner, metal cleaner, Selected from the group consisting of hard surface treatment compositions such as bath cleaning agents and floor cleaning agents, and garment treatment composition compositions such as garment detergents, laundry softeners, garment pastes and finishes. It can be used for one or more applications.

(Method for producing composition)
The composition of the present invention can be prepared by mixing the etherified cellulose fiber, water, and, if necessary, raw materials containing various additives using a known stirrer according to each application.

  What is necessary is just to set so that the mixing ratio of an etherified cellulose fiber and water and the addition amount of various additives may satisfy | fill the said range.

  Hereinafter, the present invention will be specifically described with reference to production examples, examples and test examples. Note that this example is merely illustrative of the present invention and is not meant to be limiting. The parts in the examples are parts by mass unless otherwise specified. “Normal pressure” indicates 101.3 kPa, and “room temperature” indicates 25 ° C.

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

Example 1 <Preparation of Aqueous Dispersion 1 of Etherified Cellulose Fiber>
First, 45 g of an absolutely dry cellulose powder (ARBOCEL BC200, manufactured by Rettenmeier) was added to 96 g of a 6.4 mass% aqueous sodium hydroxide solution (prepared with sodium hydroxide granules and ion-exchanged water manufactured by Wako Pure Chemical Industries, Ltd., NaOH 0.55). Equivalent / Anhydrous glucose unit 1 equivalent (AGU: Calculated on the assumption that all cellulose raw materials are composed of anhydroglucose units, the same applies hereinafter)) and after mixing uniformly, 39 g of propylene oxide (Wako Pure Chemical Industries, Ltd.) (Equivalent 2.4 equivalent / AGU) was added and sealed, followed by a stationary reaction at 50 ° C. for 24 hours. After the reaction, neutralize with acetic acid (manufactured by Wako Pure Chemical Industries), remove impurities by washing thoroughly with a mixed solvent of water / isopropanol (manufactured by Wako Pure Chemical Industries), and further vacuum dry at 50 ° C. overnight. Thus, an etherified cellulose fiber having one type of substituent was obtained.

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

  1.2 g of the etherified cellulose fiber having two kinds of substituents thus obtained was put into 98.8 g of ion-exchanged water, and stirred for 30 minutes at 3000 rpm with a homogenizer (Primics Co., Ltd., TK Robotics). The fine etherified cellulose dispersion 1 (solid content) in which the refined etherified cellulose fibers were dispersed in water by 10 passes at 100 MPa with a high-pressure homogenizer (“NanoVita L-ES” manufactured by Yoshida Kikai Co., Ltd.) 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 type of substituent obtained in Example 1, 96 g of a 6.4 mass% aqueous sodium hydroxide solution (0.55 equivalent of NaOH / AGU) was added and mixed uniformly. Thereafter, 23 g (0.10 equivalent / AGU) of the polyoxyalkylene alkyl etherifying agent prepared in Production Example 1 was added, and after sealing, a standing reaction was performed at 70 ° C. for 20 hours. After the reaction, neutralize with acetic acid, remove impurities by washing thoroughly with acetone (manufactured by Wako Pure Chemical Industries) and water / isopropanol mixed solvent, and further vacuum dry overnight at 50 ° C. 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 carrying out the same dispersion treatment as in Example 1, the refined etherified cellulose fiber is submerged in water. A finely etherified cellulose dispersion 1 (solid content concentration of 1.4% by mass) dispersed in was obtained.

  About the obtained fine etherified cellulose fiber dispersion, the substituent introduction rate and the confirmation (crystallinity) of the crystal structure were evaluated 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))
Content% (mass%) of the hydrophobic ether group contained in the obtained etherified cellulose fiber was measured by Analytical Chemistry, Vol. 51, no. 13, 2172 (1979), Zeisel method known as a technique for analyzing the average number of moles of an alkoxy group added to cellulose ether, as described in “Fifteenth revised Japanese pharmacopoeia (hydroxypropylcellulose analysis method)”, etc. It 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 volume was increased to the marked line with hexane to prepare an internal standard solution.
(Ii) 100 mg of etherified cellulose fibers and 100 mg of adipic acid that had been purified and dried were precisely weighed into a 10 mL vial, and 2 mL of hydroiodic acid 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 chip.
(Iv) After heating, 3 mL of the internal standard solution and 3 mL of diethyl ether were sequentially injected into the vial and 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: DB-5 manufactured by Agilent Technologies (12 m, 0.2 mm × 0.33 μm)
Column temperature: 100 ° C. → 10 ° C./min→280° C. (10 min Hold)
Injector temperature: 300 ° C., detector temperature: 300 ° C., implantation amount: 1 μL

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

(Formula 1)
MS = (W1 / Mw) / ((100−W1) /162.14)
W1: Ether group content (mass%) in etherified cellulose fiber
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 “RigakuRINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation.
The measurement conditions were X-ray source: Cu / Kα-radiation, tube voltage: 40 kv, tube current: 120 mA, measurement range: diffraction angle 2θ = 5-45 °, and X-ray scan speed: 10 ° / min. The measurement sample was prepared by compressing a pellet having an area of 320 mm ² × thickness of 1 mm. Further, the crystallinity of the cellulose I-type crystal structure was calculated based on the obtained X-ray diffraction intensity based on the following formula (A).

Cellulose type I crystallinity (%) = [(I22.6−I18.5) /I22.6] × 100 (A)
[Where I22.6 is the diffraction intensity of the grating plane (002) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °). Show

On the other hand, when the degree of crystallinity obtained by the above formula (A) is 35% or less, from the viewpoint of improving the calculation accuracy, in accordance with the description of P199-200 of the “Wood Science Experiment Manual” (edited by the Japan Wood Society). 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)] × 100 (B)
[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 = 16.2 °) sum of peak areas, 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.

  Table 1 shows the composition of the etherified cellulose fibers obtained in the above examples. 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. (Sufino Machine Co., Ltd., BiNFi-s) is described as CNF-RF.

  Using the above-mentioned CNF-1, CNF-2 and CNF-RF, the active ingredient was diluted with ion-exchanged water so that the active ingredient would be 0.3% by mass, and used as each test solution. As Comparative Example 2, a test solution was prepared by adding only ion-exchanged water without adding cellulose fiber. Using these test solutions, foaming, skin application, hair application, hard surface application and clothing application were tested according to the following evaluation criteria and evaluation methods. The results are shown in Table 2.

Evaluation method <Foaming test>
Put 20 g of the test solution into a 100 mL graduated cylinder, shake at a speed of 10 times / 10 seconds, and determine the amount of foam immediately after standing (scale between air phase and foam surface boundary-solution phase and foam surface boundary). It was measured.

<Skin application test>
Five expert panelists apply 0.5 mL of the test solution to their fingers, rinse with tap water, and then dry, and the dry feeling after drying and the feeling of coat after drying according to the evaluation criteria and methods shown below. Evaluation was performed. Table 2 shows the average score of five people.
-Dry feeling after drying 5: Very dry and no skin stickiness.
4: Smooth and almost non-sticky.
3: Normal (equivalent to Comparative Example 2).
2: The stickiness is clearly felt without being exposed.
1: Very sticky (no feeling of smoothness)
-Coat feeling after drying 5: The coat feeling is strong and the touch of the fingertips is not felt at all.
4: There is a feeling of a coat, and the softness of a fingertip is weak.
3: Normal (equivalent to Comparative Example 2).
2: There is no coat feeling and the fingertips are strong.
1: There is no coat feeling and the fingertip is very strong.

<Hair application test>
Five expert panelists apply 0.1 mL of the test solution to tress (Asian hair, approx. 15 cm, 1 g), rinse, and dry (dryer). Using the following evaluation criteria and evaluation method, Evaluation was made on the cohesiveness, the cohesiveness of the hair after drying, the combability after drying, and the glossiness of the hair after drying. Table 2 shows the average score of five people.
-Hair cohesion at the time of application or after drying 5: Hair cohesion is very good.
4: The hair is well-organized.
3: Normal (equivalent to Comparative Example 2).
2: The hair is not well organized.
1: Hair is not settled at all.
・ Combination after drying 5: The combing is very good.
4: Comb street is good.
3: Comb is normal (equivalent to Comparative Example 2).
2: Comb is bad.
1: Comb street is very bad.
-Hair gloss after drying 5: Strong gloss.
4: There is some glossiness.
3: Normal (equivalent to Comparative Example 2).
2: There is not much glossiness.
1: There is no glossiness.

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

<Clothing application test>
Put 10 g of test solution and 20 g of ion-exchanged water in a 50 mL glass sample bottle (manufactured by Maruemu Co., No. 7), and after mixing uniformly, put a cotton cloth (5 cm × 5 cm) and vigorously in 30 times / 10 seconds. Shake and fully immerse the test solution in cotton cloth. After standing 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, wrinkle suppression after drying and quick drying were evaluated.
Usability of cotton cloth after drying The wrinkle suppression after drying was evaluated by five professional panelists according to the following evaluation criteria and evaluation methods. Table 2 shows the average score of five people.
-Wrinkle suppression after drying 5: Even if the fiber is squeezed strongly, no wrinkle is generated.
4: Even if the fiber is squeezed strongly, wrinkles are unlikely to occur.
3: Wrinkles are generated when the fibers are squeezed strongly, but no wrinkles are generated when the fibers are squeezed weakly.
(Equivalent to Comparative Example 2)
2: Even if the fiber is squeezed weakly, slight wrinkles occur.
1: Even if the fiber is squeezed weakly, a large amount of wrinkles is generated.

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

Table 2 shows the following.
Regarding foamability, from Examples 1 and 2 and Comparative Example 1, no foamability was observed with simple cellulose fibers, and the foamability was clearly confirmed by using etherified cellulose fibers.
With regard to skin application, hair application, hard surface application and apparel application, the simple cellulose fiber of Comparative Example 1 was as effective as the reference water, but the etherified cellulose fiber of Examples 1 and 2 clearly The effect was improved.

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

Claims (6)

  A composition comprising etherified cellulose fiber and water, wherein the etherified cellulose fiber has a hydrocarbon group which may have a substituent bonded to the cellulose fiber via an ether bond, and cellulose I A composition, which is a modified cellulose fiber having a type crystal structure. The etherified cellulose fiber is a cellulose in which 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 via an ether bond. The composition according to claim 1, wherein the composition is a modified cellulose fiber bonded to a fiber and having 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)
[R ₀ in the formula, the general formula (1) and the general formula (2) represents a hydrogen atom or a hydroxyl group, the general formula (1) and R ₁ is 3 or more carbon atoms each independently of the general formula (2) 30 In the general formula (2), n represents a number of 0 or more and 50 or less, and A represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms. Show. ] 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), and the following general formula (3 2. The composition according to claim 1, wherein each of the substituents represented by (2) is independently bonded to cellulose fibers via an ether bond, and is a modified cellulose fiber having a cellulose I-type crystal structure.
—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)
[R ₀ in the formula, the general formula (1) and the general formula (2) represents a hydrogen atom or a hydroxyl group, the general formula (1) and R ₁ is 3 or more carbon atoms each independently of the general formula (2) 30 The following linear or branched alkyl groups are shown, n in the general formula (2) is a number from 0 to 50, and A is a linear or branched divalent saturated hydrocarbon group having 1 to 6 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 to 2 carbon atoms. ]   The composition according to any one of claims 1 to 3, which is a dispersion.   The composition according to any one of claims 1 to 4, which is a skin treatment composition, a hair treatment composition, a hard surface treatment composition, or a clothing treatment composition.   A foaming agent comprising a modified cellulose fiber having a cellulose I-type crystal structure, wherein a hydrocarbon group which may have a substituent is bonded to the cellulose fiber via an ether bond.