JP2017036217A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide cosmetics that use fine fibrous celluloses as thickener in a cosmetic formulation while fine fibrous celluloses are inhibited in its agglomeration and uniform.SOLUTION: The cosmetics comprise the following components (A) and (B): (A) fine fibrous celluloses with a fiber width of 1000 nm or less, having phosphoric acid-derived substituents of 0.1 mmol/g or more and 3.0 mmol/g or less; and (B) water-soluble polymers.SELECTED DRAWING: None

Description

  The present invention relates to a cosmetic comprising fine fibrous cellulose and a water-soluble polymer.

  Generally, cosmetics are adjusted to a viscosity according to the purpose and application, and various thickeners and gelling agents are used depending on the preparation. Specifically, water-soluble polymers such as carboxyvinyl polymer, xanthan gum, cellulose, guar gum, alginic acid, and polyacrylic acid are often used as the thickener and gelling agent. By using these appropriately for each application and changing the blending amount, blending components, etc., it is possible to prepare from a low-viscosity cosmetic such as a lotion thick to a solid gel state such as a hair tic.

  Carboxyvinyl polymers and salts thereof are frequently used in cosmetics because they can be gelled in a small amount and can be used in combination with emulsifiers. However, the gel structure produced by the carboxyvinyl polymer has problems such as the gel structure being easily broken in the presence of salt and being easily affected by pH. Further, when the blending amount of the thickener is increased in order to obtain a highly viscous composition, there is a problem that it becomes sticky at the time of application or distorts. Furthermore, there is known a technique (Patent Document 1) that uses a salt-resistant alkylated starch or an alkyl methacrylate / acrylic acid copolymer in combination, but such a method has a tendency that the gel hardness is hard and fragile. was there.

  It is known that fine fibrous cellulose is used as one component in a gel composition. For example, Patent Document 2 discloses a dry composition having good dispersibility and further improved stability by adding fine fibrous cellulose to a water-soluble polymer, a thickening gelling agent using the same, Liquid compositions and gel compositions are described. More specifically, Patent Document 2 describes a dry composition comprising 1 to 49% by mass of crystalline fine fibrous cellulose and 51 to 99% by mass of a water-soluble polymer using plant cell walls as raw materials. . Patent Document 2 describes that it is preferable to use carboxymethylcellulose sodium and dextrin as the water-soluble polymer. Patent Document 2 describes that the fiber width (minor axis) of the fine fiber is 2 nm to 60 μm, but the fine fibrous cellulose of Patent Document 2 includes a fiber width on the order of μm, It is not comprised only of the fiber which has a fiber width of nm order.

  Patent Document 3 is a gel composition using cellulose fibers, wherein the content of cellulose fibers is in the range of 0.3 to 5.0% by weight of the entire gel composition. A gel composition is described. The cellulose fiber in Patent Document 3 has a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm. The cellulose has an aldehyde group of 0.08 to 0.3 mmol / g and a carboxyl group of 0.6 to 2. 0.0 mmol / g. Patent Document 4 discloses a viscous aqueous composition containing cellulose fibers, a thickening accelerator (selected from nonionic thickening polysaccharides, acrylic polymers, cellulose derivatives having a weight average molecular weight of 120,000 or more), and water. Is described. The cellulose fiber in Patent Document 4 has a maximum fiber diameter of 1000 nm or less, a number average fiber diameter of 2 to 150 nm, and a ratio of 0.6 to 2.0 mmol / g of carboxyl groups in cellulose.

  Since dispersions composed of cellulose fibers described in Patent Document 3 and Patent Document 4 have high viscosity, it has been proposed to use these fine fibrous celluloses as thickeners for cosmetics and the like. Patent Document 5 describes that fine fibrous cellulose has a moisturizing action.

JP 2000-327516 A JP 2008-106178 A JP 2010-37348 A JP 2012-126788 A JP 2011-56456 A

  The fine fibrous cellulose described in Patent Document 2 and Patent Document 3 has a fiber width of 100 nm or less, and maintains a dispersed state by electrostatic repulsion between fibers. However, it is known that the fine fibrous cellulose is weak in electrostatic repulsion between fibers in the presence of an electrolyte such as a salt and causes a decrease in viscosity, aggregation, layer separation, and the like. When fine fibrous cellulose is intended for use as a thickener for cosmetics, cosmetic formulations often contain electrolytes such as salts, and the thickening of fine fibrous cellulose is not fully demonstrated in cosmetic formulations. There was a problem of causing aggregation or the like. On the other hand, when fine fibrous cellulose is not used as a thickener in a cosmetic formulation, and only a water-soluble polymer such as xanthan gum is used, there is a problem that the cosmetic becomes sticky. In view of the above background, there has been a demand for the development of a cosmetic material that has a good touch even in the coexistence of salt, powder, and the like, and realizes a sufficient thickening effect and formulation stability.

  An object of the present invention is to provide a uniform cosmetic by suppressing aggregation of fine fibrous cellulose while using fine fibrous cellulose as a thickener in a cosmetic formulation.

  In order to solve the above-described problems, the present inventors diligently studied the conditions under which fine fibrous cellulose maintains high dispersibility even during cosmetic formulation. As a result, the above-mentioned problem can be obtained by using fine fibrous cellulose having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less as a fine fibrous cellulose, and further incorporating a water-soluble polymer. It was found that cosmetics that solved this problem can be provided. The present invention has been completed based on the above findings.

That is, the present invention includes the following inventions.
(1) A cosmetic comprising the following components (A) and (B).
(A) Fine fibrous cellulose having a fiber width of 1000 nm or less and having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less;
(B) Water-soluble polymer:
(2) The cosmetic according to (1), wherein the component (B) contains a thickening polysaccharide.
(3) The cosmetic according to (2), wherein the component (B) contains the ionic thickening polysaccharide.
(4) Cosmetics as described in any one of (1)-(3) whose compounding quantity of the said component (A) is 0.01-2.0 mass% with respect to the whole cosmetics.
(5) Cosmetics as described in any one of (1)-(4) whose compounding quantity of the said component (B) is 0.03-1.0 mass% with respect to the whole cosmetics.
(6) As component (C), one or more selected from the group consisting of inorganic powder, organic powder, inorganic acid, organic acid, inorganic acid salt, organic acid salt, and anionic surfactant The cosmetic according to any one of (1) to (5), further contained.
(7) A cellulose-containing composition used for forming a cosmetic, comprising the following components (A) and (B).
(A) Fine fibrous cellulose having a fiber width of 1000 nm or less and having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less;
(B) Water-soluble polymer:

  A cosmetic comprising the fine fibrous cellulose of the present invention and a water-soluble polymer has good uniformity of the preparation, and has no stickiness of the preparation and good usability.

FIG. 1 shows the relationship between the amount of NaOH dripped with respect to a fiber raw material and electrical conductivity.

  Hereinafter, the present invention will be described in more detail. Note that the descriptions of materials, methods, and numerical ranges described in this specification are not intended to be limited to the materials, methods, and numerical ranges, and other materials, methods, and numerical ranges are not intended. It does not exclude the use of such as.

The cosmetic of the present invention contains the following components (A) and (B).
(A) Fine fibrous cellulose having a fiber width of 1000 nm or less and having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less;
(B) Water-soluble polymer:

<Fine fibrous cellulose>
Examples of cellulose raw materials include paper pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw, and bagasse, cellulose isolated from sea squirts and seaweed, etc., but are not particularly limited. . Among these, paper pulp is preferable in terms of availability, but is not particularly limited. Papermaking pulp includes hardwood kraft pulp and softwood kraft pulp. Examples of hardwood kraft pulp include bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), and oxygen bleached kraft pulp (LOKP). Examples of softwood kraft pulp include bleached kraft pulp (NBKP), unbleached kraft pulp (NUKP), and oxygen bleached kraft pulp (NOKP). Moreover, although deinking pulp made from chemical pulp, semi-chemical pulp, mechanical pulp, non-wood pulp, and waste paper is mentioned, it is not particularly limited. Examples of chemical pulp include sulfite pulp (SP) and soda pulp (AP). Semi-chemical pulp includes semi-chemical pulp (SCP), chemiground wood pulp (CGP), and the like. Examples of mechanical pulp include groundwood pulp (GP) and thermomechanical pulp (TMP, BCTMP). Non-wood pulp includes those made from cocoon, cocoon, hemp, kenaf and the like. Among these, kraft pulp, deinked pulp, and sulfite pulp are preferable because they are more easily available, but are not particularly limited. A cellulose raw material may be used individually by 1 type, and may be used in mixture of 2 or more types.

  The average fiber width of fine fibrous cellulose (sometimes simply referred to as fine fiber) is 1000 nm or less as observed with an electron microscope. The average fiber width is preferably 2 to 1000 nm, more preferably 2 to 100 nm, more preferably 2 to 50 nm, and further preferably 2 nm to 10 nm, but is not particularly limited. When the average fiber width of the fine fibrous cellulose is less than 2 nm, the physical properties (strength, rigidity, dimensional stability) as the fine fibrous cellulose are not expressed because the cellulose molecules are dissolved in water. Here, the fact that the fine fibrous cellulose has a type I crystal structure can be identified in a diffraction profile obtained from a wide-angle X-ray diffraction photograph using CuKα (λ = 1.5418Å) monochromatized with graphite. Specifically, it can be identified by having typical peaks at two positions near 2θ = 14-17 ° and 2θ = 22-23 °.

  Measurement of the fiber width of the cellulose fiber by electron microscope observation is performed as follows. An aqueous suspension of cellulose fibers having a concentration of 0.05 to 0.1% by mass is prepared, and the suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to obtain a sample for TEM observation. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, or 50000 times depending on the width of the constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.

(1) One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
(2) A straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.

  The width of the fiber that intersects with the straight line X and the straight line Y is visually read from the observation image that satisfies the above conditions. In this way, at least three sets of images of the surface portion that do not overlap each other are observed, and the width of the fiber intersecting with the straight lines X and Y is read for each image. Thus, at least 20 × 2 × 3 = 120 fiber widths are read. The average fiber width of cellulose fibers (sometimes simply referred to as “fiber width”) is an average value of the fiber widths read in this way.

  The fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.1 to 800 μm, and particularly preferably 0.1 to 600 μm. When the fiber length is less than 0.1 μm, the crystalline region of the fine fibrous cellulose is also destroyed, and the original physical properties cannot be exhibited. If it exceeds 1000 μm, the slurry viscosity of the fine fibers becomes very high and it becomes difficult to handle. The fiber length can be obtained by image analysis using TEM, SEM, or AFM.

  The ratio of the crystal part contained in the fine fibrous cellulose is not particularly limited in the present invention, but it is preferable to use cellulose having a crystallinity obtained by an X-ray diffraction method of 60% or more. The degree of crystallinity is preferably 65% or more, more preferably 70% or more. In this case, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion. The degree of crystallinity is obtained by measuring an X-ray diffraction profile and determining the crystallinity by a conventional method (Seagal et al., Textile Research Journal, 29, 786, 1959).

<Chemical treatment>
In the present invention, as the fine fibrous cellulose, a fine fibrous cellulose having a phosphate group obtained by subjecting a cellulose raw material to chemical treatment and defibration treatment can be used. Fine fibrous cellulose having a substituent such as a phosphoric acid group is preferable in that it can be made ultrafine due to the electrostatic repulsion effect. Further, the fine fibrous cellulose having a substituent does not aggregate in water due to the electrostatic repulsion effect and can be stable, but the effect is weakened in water containing salt, and it becomes difficult to stably disperse. Therefore, it is particularly suitable for applying the present invention to stabilize in water containing a salt and exhibit a thickening effect. The fine fibrous cellulose used in the present invention is particularly characterized by having a substituent derived from phosphoric acid as a substituent in the range of 0.1 mmol / g to 3.0 mmol / g. By using fine fibrous cellulose having such characteristics, a uniform preparation as a cosmetic can be obtained.

[Chemical processing in general]
The method of chemical treatment of the cellulose raw material is not particularly limited as long as it is a method capable of obtaining fine fibers. Examples include, but are not limited to, acid treatment, ozone treatment, TEMPO oxidation treatment, enzyme treatment, or treatment with a compound that can form a covalent bond with a functional group in cellulose or a fiber raw material. However, since the fine fibrous cellulose used in the present invention has a substituent derived from phosphoric acid, the chemical treatment is preferably carried out with a compound having a phosphoric acid group and / or a salt thereof.

Examples of acid treatment include Otto van den Berg; Jeffrey R. Capadona; Christoph Weder;
Although the method described in Biomacromolecules 2007, 8, 1353-1357. Can be mentioned, it is not specifically limited. Specifically, the cellulose fiber is hydrolyzed with sulfuric acid or hydrochloric acid. Those produced by acid treatment with a high concentration of 51 are almost decomposed in amorphous regions and become short fibers (also called cellulose nanocrystals), which are also included in fine fibrous cellulose.

  As an example of the ozone treatment, a method described in JP 2010-254726 A can be exemplified, but it is not particularly limited. Specifically, after the fiber is treated with ozone, it is dispersed in water, and the resulting aqueous suspension of the fiber is pulverized.

  Examples of TEMPO oxidation include the methods described in Saito T & al. Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 2006, 7 (6), 1687-91. There is no particular limitation. Specifically, the fiber is subjected to TEMPO oxidation treatment, and then dispersed in water, and the aqueous suspension of the obtained fiber is pulverized.

  As an example of the enzyme treatment, the method described in WO2013 / 176033 (all contents described in WO2013 / 176033 shall be cited in the present specification) can be mentioned, but is not particularly limited. . Specifically, the fiber raw material is treated with an enzyme at least under a condition that the ratio of the EG activity to the CBHI activity of the enzyme is 0.06 or more.

EG activity is measured and defined as follows.
A substrate solution of carboxymethylcellulose (CMCNa High viscosity; Cat No150561, MP Biomedicals, Lnc.) At a concentration of 1% (W / V) (concentration 100 mM, pH 5.0 containing acetic acid-sodium acetate buffer) is prepared. The enzyme for measurement was diluted in advance with a buffer solution (same as above) (dilution ratio is such that the absorbance of the enzyme solution shown below falls within a calibration curve obtained from the glucose standard solution below). Add 10 μl of the diluted enzyme solution to 90 μl of the substrate solution and react at 37 ° C. for 30 minutes.
In order to prepare a calibration curve, ion-exchanged water (blank) and glucose standard solution (4 standard solutions having different concentrations from at least 0.5 to 5.6 mM) were selected, and 100 μl each was prepared at 37 ° C., Keep warm for 30 minutes.

300 μl of DNS coloring solution (1.6% by weight NaOH, 1% by weight 3,5-dinitrosalicylic acid, 30% by weight tartaric acid was added to the enzyme-containing solution after the reaction, the calibration curve blank, and the glucose standard solution, respectively. Add potassium sodium) and boil for 5 minutes to develop color. Immediately after color development, cool with ice, add 2 ml of ion-exchanged water, and mix well. After standing for 30 minutes, the absorbance is measured within 1 hour.
Absorbance can be measured by dispensing 20 Oμl into a 96-well microwell plate (for example, 269620, manufactured by NUNC), and measuring the absorbance at 540 nm using a microplate reader (for example, infiniteM200, manufactured by TECAN).

A calibration curve is prepared using the absorbance and glucose concentration of each glucose standard solution obtained by subtracting the absorbance of the blank. The amount corresponding to glucose in the enzyme solution is calculated using the calibration curve after subtracting the blank absorbance from the absorbance of the enzyme solution. (If the absorbance of the enzyme solution does not fall within the calibration curve, use the buffer to dilute the enzyme. Measure again by changing the dilution ratio. EG activity can be obtained from the following formula by defining the amount of enzyme that produces a reducing sugar equivalent to 1 μmole of glucose per minute as 1 unit.
EG activity = Glucose equivalent of 1 ml of enzyme solution obtained by diluting with buffer (μmole) / 30 minutes x dilution factor
[Sakuzo Fukui, “Biochemical Experimental Method (Reducing Sugar Quantification Method) Second Edition”, Academic Publishing Center, p. 23-24 (1990)]

CBHI activity is measured and defined as follows.
Dispense 2 μl of 1.25 mM 4-Methylumberiferyl-cel1obioside (dissolved in acetic acid-sodium acetate buffer at a concentration of 125 mM, pH 5.0) into a 96-well microwell plate (for example, 269620, manufactured by NUNC). Add 4 μl of 100 mM Glucono-l, 5-Lactone. Furthermore, 4 μl of the enzyme solution for measurement diluted with the same buffer as above (dilution ratio should be within the calibration curve obtained from the following standard solution for the fluorescence emission degree of the enzyme solution below) is added, and the reaction is carried out at 37 ° C. for 30 minutes. Let Thereafter, 200 μl of 500 mM glycine-NaOH buffer (pH 10.5) is added to stop the reaction.

Dispense 40 μ1 of 4-Methyl-umberiferon standard solution (standard solution with different concentrations of 0 to 50 μM at least 4 points) as a standard solution for the calibration curve into the same 96-well microwell plate.
Warm for 30 minutes at ℃. Thereafter, 200 μl of 500 mM glycine-NaOH buffer (pH 10.5) is added.

Using a microplate reader (for example, F1uoroskan Ascent FL, manufactured by Thermo-Labsystems), the fluorescence intensity at 350 nm (excitation light: 460 nm) is measured. Calculate the amount of 4-Methy1-umberiferon produced in the enzyme solution using the calibration curve created from the data of the standard solution. (If the fluorescence emission of the enzyme solution does not fit the calibration curve, change the dilution rate and perform measurement again. ) CBHI activity can be determined from the following formula, assuming that the amount of enzyme that produces 1 μmol of 4-Methyl-umberiferon per minute is 1 unit.
CBHI activity = Amount of 4-Methyl-umberiferon in enzyme solution 1m1 after dilution (μmo1e) / 30 minutes x dilution factor

Examples of the treatment with a compound capable of forming a covalent bond with a functional group in cellulose or a fiber raw material include the following methods, but are not particularly limited.
Use of “at least one compound selected from oxo acids, polyoxo acids or salts thereof containing a phosphorus atom in the structure” described in International Publication WO2013 / 073652 (PCT / JP2012 / 079743) Method.

[Introduction of phosphate group]
In the present invention, the fine fibrous cellulose has a substituent derived from phosphoric acid such as a phosphate group (sometimes simply referred to as a phosphate group).
The phosphoric esterification will be described below.

(Phosphate group introduction process)
The phosphate group introduction step can be performed by reacting a phosphor raw material-containing compound or / and a salt thereof (hereinafter referred to as “compound A”) with a fiber raw material containing cellulose. This reaction may be performed in the presence of urea or / and a derivative thereof (hereinafter referred to as “compound B”), whereby a phosphate group can be introduced into the hydroxy group of the cellulose fiber. It is not particularly limited to this.

  The phosphate group introduction step necessarily includes a step of introducing a phosphate group into cellulose, and may include an alkali treatment step described later, a step of washing excess reagent, and the like as desired.

  As an example of a method for causing compound A to act on a fiber raw material in the presence of compound B, a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material can be mentioned. Another example is a method in which powders and aqueous solutions of Compound A and Compound B are added to the fiber raw material slurry. Among these, since the uniformity of the reaction is high, a method of adding an aqueous solution of Compound A and Compound B to a dry fiber material, or a powder or an aqueous solution of Compound A and Compound B to a wet fiber material The method is preferred, but not particularly limited. Compound A and compound B may be added simultaneously or separately. Moreover, you may add the compound A and the compound B first used for reaction as aqueous solution, and remove an excess chemical | medical solution by pressing. The form of the fiber raw material is preferably cotton or thin sheet, but is not particularly limited.

Compound A used in this embodiment is a compound having a phosphate group and / or a salt thereof.
Examples of the compound having a phosphate group include, but are not limited to, phosphoric acid, lithium salt of phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, ammonium salt of phosphoric acid, and the like. Examples of the lithium salt of phosphoric acid include lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate. Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate. Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate. Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.

  Among these, phosphoric acid, sodium salt of phosphoric acid, from the viewpoint of high efficiency of introducing phosphate groups, easy improvement of the defibrating efficiency in the following defibrating process, low cost, and industrial applicability Or a potassium salt of phosphoric acid or an ammonium salt of phosphoric acid. Although sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable, it is not particularly limited.

  Further, the compound A is preferably used as an aqueous solution because the uniformity of the reaction is enhanced and the efficiency of introducing a phosphate group is increased, but there is no particular limitation. The pH of the aqueous solution of Compound A is not particularly limited, but is preferably 7 or less because the efficiency of introduction of phosphoric acid groups is high, and more preferably 3 to 7 from the viewpoint of suppressing hydrolysis of pulp fibers. The pH may be adjusted by, for example, using a phosphoric acid group-containing compound in combination with acidity and alkalinity, and changing the amount ratio. Alternatively, the pH may be adjusted by adding an inorganic alkali or an organic alkali to a phosphoric acid group-containing compound that exhibits acidity.

  The amount of compound A added to the fiber raw material is not particularly limited, but when the amount of compound A added is converted to a phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material is preferably 0.5 to 100% by weight, and 1 to 50% by weight. % Is more preferable, and 2 to 30% by mass is most preferable. If the addition amount of the phosphorus atom with respect to a fiber raw material is the range of 0.5-100 mass%, the yield of a fine fibrous cellulose can be improved more. When the amount of phosphorus atoms added to the fiber raw material exceeds 100% by mass, the effect of improving the yield reaches a peak and the cost of the compound A to be used increases, which is not preferable. On the other hand, if the amount of phosphorus atoms added to the fiber raw material is lower than 0.5% by mass, a sufficient yield cannot be obtained, which is not preferable.

  Examples of the compound B used in this embodiment include urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, benzoleinurea, and hydantoin, but are not particularly limited. Among these, urea is preferable because it is easy to handle at low cost and easily forms a hydrogen bond with a fiber raw material having a hydroxyl group.

Compound B is preferably used as an aqueous solution like Compound A, but is not particularly limited. Moreover, it is preferable to use an aqueous solution in which both compound A and compound B are dissolved because the uniformity of the reaction is increased, but there is no particular limitation.
The amount of compound B added to the fiber raw material is preferably 1 to 300% by mass, but is not particularly limited.

  In addition to Compound A and Compound B, amides or amines may be included in the reaction system. Examples of amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like. Examples of amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine, and the like. Among these, triethylamine is known to work as a good reaction catalyst.

(Introduction amount of substituent derived from phosphoric acid)
The introduction amount of the phosphate-derived substituent is 0.1 mmol / g or more and 3.0 mmol / g or less, and preferably 0.14 mmol / g or more and 2.5 mmol / g or less, per 1 g (mass) of fine fibrous cellulose. 0.2 mmol / g or more and 2.0 mmol / g or less is more preferable. More preferably, it is 0.2 mmol / g or more and 1.8 mmol / g or less, Especially preferably, it is 0.4 mmol / g or more and 1.8 mmol / g or less, Most preferably, it is 0.6 mmol / g or more and 1.8 mmol / g. It is as follows. If the introduction amount of the phosphate-derived substituent is less than 0.1 mmol / g, it is difficult to refine the fiber raw material, and the stability of the fine fibrous cellulose is poor. When the introduction amount of the substituent derived from phosphoric acid exceeds 3.0 mmol / g, sufficient viscosity cannot be obtained.

  The amount of the phosphate-derived substituent introduced into the fiber material can be measured by a conductivity titration method. Specifically, by performing the defibration process step, after treating the resulting fine fibrous cellulose-containing slurry with an ion exchange resin, by determining the change in electrical conductivity while adding an aqueous sodium hydroxide solution, The amount introduced can be measured.

  In conductivity titration, when alkali is added, the curve shown in FIG. 1 is given. Initially, the electrical conductivity rapidly decreases (hereinafter referred to as “first region”). Thereafter, the conductivity starts to increase slightly (hereinafter referred to as “second region”). Thereafter, the conductivity increment increases (hereinafter referred to as “third region”). That is, three areas appear. Among these, the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration, and the amount of alkali required in the second region is the amount of weakly acidic groups in the slurry used for titration. Will be equal. When the phosphoric acid group undergoes condensation, apparently weakly acidic groups are lost, and the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region. On the other hand, the amount of strongly acidic groups coincides with the amount of phosphorus atoms regardless of the presence or absence of condensation, so that the amount of phosphate groups introduced (or the amount of phosphate groups) or the amount of substituent introduced (or the amount of substituents) is simply When said, it represents the amount of strongly acidic group.

(Alkali treatment)
When manufacturing a phosphorylated fine fiber, an alkali treatment can be performed between the phosphate group introduction step and the defibration treatment step described later. Although it does not specifically limit as a method of an alkali treatment, For example, the method of immersing a phosphate group introduction | transduction fiber in an alkaline solution is mentioned.
The alkali compound contained in the alkali solution is not particularly limited, but may be an inorganic alkali compound or an organic alkali compound. The solvent in the alkaline solution may be either water or an organic solvent, and is not particularly limited. The solvent is preferably a polar solvent (polar organic solvent such as water or alcohol), and more preferably an aqueous solvent containing at least water.
Moreover, among alkaline solutions, since versatility is high, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution is especially preferable, However It does not specifically limit.

Although the temperature of the alkali solution in an alkali treatment process is not specifically limited, 5-80 degreeC is preferable and 10-60 degreeC is more preferable.
Although the immersion time in the alkaline solution in the alkali treatment step is not particularly limited, it is preferably 5 to 30 minutes, and more preferably 10 to 20 minutes.
Although the usage-amount of the alkaline solution in an alkali treatment is not specifically limited, It is preferable that it is 100-100000 mass% with respect to the absolute dry mass of phosphoric acid introduction | transduction fiber, and it is more preferable that it is 1000-10000 mass%.

  In order to reduce the amount of alkaline solution used in the alkali treatment step, the phosphate group-introduced fiber may be washed with water or an organic solvent before the alkali treatment step. After the alkali treatment, in order to improve the handleability, it is preferable to wash the alkali-treated phosphate group-introduced fiber with water or an organic solvent before the defibrating treatment step, but there is no particular limitation.

<Defibration processing>
The fine fibers obtained above can be defibrated in the defibrating process. In the defibrating process, the fiber is usually defibrated using a defibrating apparatus to obtain a fine fiber-containing slurry, but the processing apparatus and the processing method are not particularly limited.
As the defibrating apparatus, a high-speed defibrator, a grinder (stone mill type pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, a high-pressure collision type pulverizer, a ball mill, a bead mill, or the like can be used. Alternatively, as a defibrating apparatus, a device for wet grinding such as a disk type refiner, a conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater should be used. You can also. The defibrating apparatus is not limited to the above.

  Preferable defibrating methods include, but are not limited to, a high-speed defibrator, a high-pressure homogenizer, and an ultrahigh-pressure homogenizer that are less affected by the grinding media and less worried about contamination.

  In the defibrating process, it is preferable to dilute the fiber raw material with water and an organic solvent alone or in combination to form a slurry, but there is no particular limitation. As the dispersion medium, in addition to water, a polar organic solvent can be used. Preferable polar organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like, but are not particularly limited. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol. Examples of ketones include acetone and methyl ethyl ketone (MEK). Examples of ethers include diethyl ether and tetrahydrofuran (THF). The dispersion medium may be one type or two or more types. Further, the dispersion medium may contain a solid content other than the fiber raw material, such as urea having hydrogen bonding property.

  It is preferable that the compounding quantity of the fine fibrous cellulose which is a component (A) is 0.01-2.0 mass% with respect to the whole cosmetics.

<Water-soluble polymer>
In the cosmetic of the present invention, a water-soluble polymer is blended in order to stably disperse the fine fibrous cellulose. It is considered that the water-soluble polymer prevents the aggregation of fine fibrous cellulose and stabilizes the dispersion by steric hindrance due to the swelling action in the liquid.

  Examples of the water-soluble polymer include carboxyvinyl polymer, alkyl methacrylate / acrylic acid copolymer, thickening polysaccharide and the like, preferably thickening polysaccharide, more preferably ionic thickening polysaccharide. The thickening polysaccharide used in the present invention is not particularly limited as long as it is a thickening polysaccharide. Xanthan gum, carrageenan, guar gum, locust bean gum, quince seed, agar, methylcellulose, hydroxyethylcellulose, hydroxypropyl Examples include methyl cellulose stearoxy ether and carboxymethyl cellulose. Only 1 type may be used for a water-soluble polymer, and 2 or more types may be mixed and used for it. The blending amount of the water-soluble polymer in the entire cosmetic is preferably 0.03 to 1.0% by mass.

[Other ingredients]
In addition to the components (A) and (B) described above, the cosmetic composition of the present invention includes, as other components (C), inorganic powders, organic powders, inorganic acids, organic acids, inorganic acid salts, organic acids. One or more selected from the group consisting of a salt and an anionic surfactant can be further included.

  Examples of inorganic powders include metal oxide, metal sulfate, talc, mica, kaolin, sericite, various mica, silicic acid and silicate compounds, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, etc. It is done. Furthermore, examples of the inorganic powder include montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, silicon nitride, boron nitride, and a silica compound.

Examples of the metal oxide include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, and magnesium oxide.
Examples of the metal sulfate include barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, and magnesium carbonate.
Examples of mica include muscovite, synthetic mica, phlogopite, red mica, biotite, lithia mica, and the like.

Examples of silicic acid and silicic acid compounds include silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate and the like.
Specific examples of the above-described inorganic powder are merely examples, and are not limited thereto.
One kind of inorganic powder may be used alone, or two or more kinds may be used in combination.
The blending amount of the inorganic powder in the entire cosmetic is not particularly limited, but generally 1.0 to 30.0% by mass is preferable.

Examples of the organic powder include the following.
Polyamide powder, polyacrylic acid / acrylic acid ester powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder.
Tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose powder, silk powder, nylon powder such as 12 nylon and 6 nylon.
Crosslinked silicone fine powder having a structure obtained by crosslinking dimethylpolysiloxane, crosslinked spherical polymethylsilsesquioxane fine powder, fine powder obtained by coating the surface of crosslinked spherical organopolysiloxane rubber with polymethylsilsesquioxane particles etc.
Hydrophobized silica, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin.
Specific examples of the organic powder described above are merely examples, and are not limited thereto.
One kind of organic powder may be used alone, or two or more kinds may be used in combination.
Although the compounding quantity of the organic powder in the whole cosmetics is not specifically limited, Generally 1.0-10.0 mass% is preferable.

Examples of the inorganic acid and inorganic acid salt include edetic acid and its salt, sodium chloride, potassium chloride, potassium hydroxide, sodium hydroxide, phosphoric acid and its salt, and the like.
Although the compounding quantity of the inorganic acid and inorganic acid salt in the whole cosmetics is not specifically limited, Generally 0.01-10.0 mass% is preferable.

  Examples of the organic acid and organic acid salt include citric acid, kojic acid, malic acid, triethanolamine, diisopropanolamine, glycolic acid, dipotassium glycyrrhizinate, tranexamic acid, and the like. The blending amount of the organic acid and the organic acid salt in the entire cosmetic is not particularly limited, but generally 0.01 to 1.0% by mass is preferable, and more preferably, the dipotassium glycyrrhizinate is 0.05 to 0.00%. 30 mass% and a chelating agent are 0.05-0.50 mass%.

Specific examples of the anionic surfactant include the following.
The following fatty acid soaps. Sodium stearate, potassium stearate, triethanolamine stearate, sodium palmitate, potassium palmitate, triethanolamine palmitate, sodium laurate, potassium laurate, triethanolamine laurate and the like.
Alkyl ether carboxylic acids and salts thereof, condensates of amino acids and fatty acids, alkane sulfonates, alkene sulfonates, sulfonates of fatty acid esters, sulfonates of fatty acid amides, formalin condensation sulfonates, alkyl sulfates salt.
Secondary higher alcohol sulfates, alkyl and allyl ether sulfates, sulfate esters of fatty acid esters, sulfate esters of fatty acid alkylolamide, sulfate esters such as funnel oil, alkyl phosphates, ether phosphates .
Alkyl allyl ether phosphate, amide phosphate, N-acyl lactate, N-acyl sarcosine salt, N-acyl amino acid type activator and the like.

  Although the compounding quantity of the anionic surfactant in the whole cosmetics is not particularly limited, it is generally 0.01 to 10.0% by mass, more preferably 0.05 to 3.0% by mass. .

<Manufacturing method of cosmetics>
The manufacturing method of the cosmetics of this invention can be suitably selected according to the kind etc. of component to be used, and is not specifically limited. When the water-soluble component and the oil-soluble component are used, the cosmetic of the present invention can be produced by mixing the water phase and the oil phase. For example, an aqueous phase containing a water-soluble component is prepared, each component in the aqueous phase is heated and dissolved, and then uniformly dispersed and mixed with an oil phase (including an oil-soluble component) adjusted to an appropriate temperature. By emulsifying with a mixer or the like, the cosmetic of the present invention can be produced.

<Cosmetic form>
Specifically, the cosmetics of the present invention include skin cosmetics, makeup cosmetics, hair cosmetics, UV protective cosmetics, and cleaning agents such as hand cleaners, pre-shave lotions, after-shave lotions, fragrances and the like. A dentifrice, an ointment, a patch, etc. are mentioned. Examples of skin cosmetics include skin lotion, milky lotion (whitening milky lotion, etc.), cream, cosmetic liquid, pack, foundation, sunscreen cosmetics, suntan cosmetics, and various lotions. Examples of the cream include cold cream, burnishing cream, massage cream, emollient cream, cleansing cream, moisture cream, and hand cream. Examples of makeup cosmetics include makeup bases, foundations, eye shadows, and cheeks. Examples of hair cosmetics include shampoos, rinses, hair conditioners, rinse-in shampoos, hair styling agents (hair foams, gel-like hair styling agents, etc.), hair treatment agents, hair waxes, hair dyes and the like. Examples of the hair treatment agent include hair cream, treatment lotion, and hair milk. Further, the hair cosmetic may be a lotion type hair restorer or hair nourishing agent. The specific examples of the cosmetics described above are merely examples, and are not particularly limited thereto.

Furthermore, an additive can be blended in the cosmetic of the present invention in accordance with the type of the target cosmetic within a range that does not impair the effects of the present invention. Examples of the additive include, but are not limited to, the following.
Hydrocarbon oils such as liquid paraffin and petrolatum, vegetable oils and fats, waxes, synthetic ester oils, silicone oil phase components.
Higher alcohols, lower alcohols, fatty acids, ultraviolet absorbers, inorganic / organic pigments, coloring materials, various surfactants, polyhydric alcohols, saccharides, polymer compounds, physiologically active ingredients, transdermal absorption promoters, solvents, Antioxidants, pH adjusters, fragrances, etc. Examples of the various surfactants include nonionic surfactants, cationic surfactants, and amphoteric surfactants.

Furthermore, according to this invention, it is a cellulose containing composition used in order to form cosmetics, Comprising: The cellulose containing composition containing the following component (A) and (B) is provided.
(A) Fine fibrous cellulose having a fiber width of 1000 nm or less and having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less;
(B) Water-soluble polymer:
Details of components (A) and (B) are as described herein above.

  The following examples illustrate the invention, but the scope of the invention is not limited by the examples. A compounding quantity represents the mass%.

[Example 1]
<Manufacture of fine fibrous cellulose>
(Production Example 1) Production of fine fibrous cellulose 1 A phosphorylation reagent was prepared by dissolving 100 g of urea, 55.3 g of sodium dihydrogen phosphate dihydrate, and 41.3 g of disodium hydrogen phosphate in 109 g of water. .
The dried softwood bleached kraft pulp paper was processed with a cutter mill and a pin mill to form cotton-like fibers. 100 g of this cotton-like fiber was taken in absolute dry mass, and the phosphorylating reagent was sprayed evenly with a spray, and then kneaded by hand to obtain a chemical-impregnated pulp.
The obtained chemical-impregnated pulp was heat-treated for 80 minutes in a blower dryer with a damper heated to 140 ° C. to obtain phosphorylated pulp.

100 g of the obtained phosphorylated pulp was collected by pulp mass, poured with 10 L of ion exchange water, stirred and dispersed uniformly, and then subjected to filtration and dehydration to obtain a dehydrated sheet twice. Next, the obtained dehydrated sheet was diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added little by little while stirring to obtain a pulp slurry having a pH of 12 to 13. Thereafter, the pulp slurry was dehydrated to obtain a dehydrated sheet, and then 10 L of ion exchange water was added. The step of stirring and dispersing uniformly, followed by filtration and dehydration to obtain a dehydrated sheet was repeated twice. An infrared absorption spectrum of the obtained dehydrated sheet was measured by FT-IR. As a result, absorption based on phosphate groups was observed at 1320 to 1290 cm ⁻¹ , confirming the addition of phosphate groups. Therefore, the obtained dehydrated sheet (phosphoric acid oxoacid-introduced cellulose) was one in which a part of the hydroxy group of cellulose was substituted with a functional group of the following structural formula (1).

In the formula, a, b, m, and n are natural numbers (where a = b × m). At least one of α1, α2,..., αn and α ′ is O−, and the rest is either R or OR. R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group, respectively. One of a hydrogen group, an aromatic group, and a derivative group thereof. β is a monovalent or higher cation composed of an organic substance or an inorganic substance.

Ion exchange water was added to the obtained phosphorylated cellulose to prepare a 2% by mass slurry. This slurry is defibrated (M-Technic Co., CLEAMIX-11S).
Was used for defibration for 180 minutes under conditions of 6900 rotations / minute to obtain a cellulose suspension.
By X-ray diffraction, the cellulose maintained cellulose I type crystals. This cellulose suspension was further passed once at a pressure of 245 MPa with a wet atomizer (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain cellulose fibers 1. By X-ray diffraction, the cellulose maintained cellulose I type crystals.

(Production Example 2) Production of fine fibrous cellulose 2 Cellulose fibers were produced in the same manner as in Production Example 1 except that it was passed 10 times at a pressure of 245 MPa with a wet atomizer ("Ultimizer" manufactured by Sugino Machine). 2 was obtained. By X-ray diffraction, the cellulose maintained cellulose I type crystals.

(Production Example 3) Production of fine fibrous cellulose 3 The phosphorylated pulp obtained in Production Example 1 was impregnated with a phosphorylating reagent again, and heat treated for 80 minutes in a blower dryer with a damper heated to 140 ° C. Cellulose fibers 3 were obtained in the same manner as in Production Example 1 except that the phosphorylation reaction was performed twice. By X-ray diffraction, the cellulose maintained cellulose I type crystals.

(Production Example 4) Production of fine fibrous cellulose 4 The phosphorylated pulp obtained in Production Example 1 was impregnated again with a phosphorylating reagent, and heat treated for 50 minutes in a blower dryer with a damper heated to 140 ° C. Cellulose fibers 4 were obtained in the same manner as in Production Example 1 except that the phosphorylation reaction was performed twice. By X-ray diffraction, the cellulose maintained cellulose I type crystals.

(Production Example 5) Production of fine fibrous cellulose 5 Cellulose fibers were prepared in the same manner as in Production Example 1 except that 5.5 g of disodium hydrogen phosphate dihydrate and 4.1 g of disodium hydrogen phosphate were used. 5 was obtained. By X-ray diffraction, the cellulose maintained cellulose I type crystals.

(Measurement of phosphate group introduction amount (substituent amount))
The difference between the introduction amount of the strong acid group and the weak acid group derived from the phosphate group is a measure of the condensation of the phosphate group. The smaller this value, the smaller the condensation of phosphate groups, and the more highly fine fibrous cellulose-containing slurry is obtained. The introduction amount of the strongly acidic group and the weakly acidic group derived from the phosphoric acid group is obtained by diluting the fine fibrous cellulose-containing slurry after the defibration treatment as it is with a solid content concentration of 0.2% by mass with ion-exchanged water. Measured by treatment with ion exchange resin and titration with alkali.
In the treatment with an ion exchange resin, 1/10 by volume of a strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) is added to a slurry containing 0.2% by mass of fine fibrous cellulose and shaken for 1 hour. Processed. Thereafter, the mixture was poured onto a mesh having an opening of 90 μm to separate the resin and the slurry. In the titration using an alkali, the change in the value of electrical conductivity exhibited by the slurry was measured while adding a 0.1 N sodium hydroxide aqueous solution to the fine fibrous cellulose-containing slurry after ion exchange.
That is, by dividing the alkali amount (mmol) required in the first region of the curve shown in FIG. 1 by the solid content (g) in the slurry to be titrated, the amount of strongly acidic groups introduced (mmol / g) did. Further, the alkali amount (mmol) required in the second region of the curve shown in FIG. 1 is divided by the solid content (g) in the slurry to be titrated, and the amount of weak acidic groups introduced (mmol / g) did.

(Production Example 6) Production of fine fibrous cellulose 6 Undried softwood bleached kraft pulp equivalent to a dry mass of 200 g, TEMPO 2.5 g, and sodium bromide 25 g were dispersed in 1500 ml of water. Then, 13 mass% sodium hypochlorite aqueous solution was added so that the quantity of sodium hypochlorite might be set to 5.0 mmol with respect to 1.0 g of pulp, and reaction was started. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10 to 11, and the reaction was terminated when no change in pH was observed.
Thereafter, the pulp slurry was dehydrated to obtain a dehydrated sheet, and then 10 L of ion exchange water was added. Next, the step of stirring and dispersing uniformly and then dewatering by filtration to obtain a dehydrated sheet was repeated twice. An infrared absorption spectrum of the obtained dehydrated sheet was measured by FT-IR. As a result, absorption based on a carboxyl group was observed at 1730 cm ⁻¹ , confirming the addition of a carboxyl group. Using this dehydrated sheet (TEMPO oxidized cellulose), fine fibrous cellulose was prepared.

  Ion-exchanged water was added to the TEMPO-oxidized cellulose to which the carboxyl group obtained above was added to prepare a 2% by mass slurry. The slurry was defibrated for 180 minutes at 6900 rpm using a defibrating apparatus (Cleamix-11S, manufactured by M Technique Co., Ltd.) to obtain a cellulose suspension. By X-ray diffraction, the cellulose maintained cellulose I type crystals. This cellulose suspension was further passed 10 times at a pressure of 245 MPa with a wet atomizer (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain cellulose fibers 6. By X-ray diffraction, the cellulose maintained cellulose I type crystals.

[Example 2] Measurement of viscosity and crystallinity Viscosity of cellulose fibers 1 to 6 was measured by the following method.
Water was added to the cellulose fibers 1 to 6 to adjust the concentration of each cellulose fiber to 0.4% by mass. The suspension of cellulose fibers 1 to 6 was allowed to stand for 24 hours, and then the viscosity was measured at 25 ° C. at 3 rpm (3 minutes) using a B-type viscometer (BLOOKFIELD, analog viscometer T-LVT). . The results are shown in Table 1.

The fiber width of the cellulose fibers 1-6 was measured by the following method.
The supernatant liquid of the defibrated pulp slurry was diluted with water to a concentration of 0.01 to 0.1% by mass and dropped onto a hydrophilic carbon grid membrane. After drying, it was stained with uranyl acetate and observed with a transmission electron microscope (JEOL-2000EX, manufactured by JEOL Ltd.). In Production Examples 1 to 4 and Production Example 6, it was confirmed that the fine fibrous cellulose had a width of about 4 nm. In Production Example 5, fine fibrous cellulose fibers having a fiber width of about 4 nm could not be observed. The defibrated pulp slurry of Production Example 5 was diluted with water to a concentration of 0.01 to 0.1% by mass and dropped onto a slide glass. When covered with a cover glass and observed with a digital microscope (Hirox, KH-7700), coarse fibers of 10 μm or more were observed.

  About the crystallinity degree of the cellulose fibers 1-6, it measured using the X-ray-diffraction apparatus and calculated | required from the following formula. The “crystallization index” in the formula below is also referred to as “crystallinity”.

Cellulose type I crystallization index (%) = [(I22.6−I18.5) /I22.6] × 100 (1)
[I22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 is the diffraction of the amorphous portion (diffraction angle 2θ = 18.5 °). (Indicates strength)
0.45 ≦ αω (m · rad / sec) (2)
[Α represents a half amplitude (m), and ω represents an angular velocity (rad / sec). ].

  As shown in Table 1, the suspensions of cellulose fibers 1 to 4 had a sufficient viscosity. Cellulose fiber 5 is not sufficiently phosphorylated, only coarse fibers with a fiber width of 10 μm or more are observed even after defibration, and fine fibers with a fiber width of 1000 nm or less are hardly seen and do not exhibit sufficient viscosity. It was.

[Example 3]
<Evaluation of cosmetics>
Tables 2 and 3 show the results of preparing each cosmetic shown in Tables 2 and 3 below and examining the formulation stability and the feel in use (presence or absence of stickiness). In Tables 2 and 3, “To100” indicates an amount that becomes 100 in total. The evaluation was performed according to the following criteria.

(1) Preparation Method of Cosmetics Each component in the aqueous phase was heated and dissolved, and then uniformly dispersed, mixed with an oil phase adjusted to 80 ° C., and emulsified with a homomixer (5000 rpm, 5 minutes).

(2) Evaluation of formulation stability The prepared cosmetics were allowed to stand at 45 ° C for 1 month to evaluate the formulation stability. The evaluation criteria are as follows.
A: No separation of oil or water is observed, glossy formulation B: No separation of oil or water is observed, gloss is present, but rough formulation C: No separation of oil or water is observed 、 Glossy formulation D: Oil or water separation is clearly recognized or poorly dispersed

(3) Evaluation of stickiness after use An actual use test was conducted by 10 professional panels. The evaluation criteria are as follows.
A: Eight or more panelists recognize that there is no stickiness after use.
B: 6 or more and less than 8 panelists recognize that there is no stickiness after use.
C: 3 or more and less than 6 panelists recognize that there is no stickiness after use.
D: Less than 3 panelists recognize that there is no stickiness after use.

From Table 2, preparations containing fine cellulose fibers having ionic substituents and water-soluble polymers of Invention products 1 to 5 have a uniform gloss, no stickiness of the preparation, and excellent use feeling It was a thing.
On the other hand, the preparations containing no water-soluble polymer of Comparative products 1 and 2 had no texture and agglomerates that were thought to be derived from fine cellulose fibers could be visually confirmed and had a rough texture.
Comparative products 3 and 4 could not prepare a uniform preparation.
Since the comparative product 5 does not contain fine cellulose fibers, it was a sticky preparation.

  From Table 3, the blends of fine cellulose fibers and water-soluble polymers in the ratio of invention products 6 to 13 have a uniform gloss, no stickiness of the preparation, and excellent usability. It was.

  Although the application example which mix | blended (A) fine fibrous cellulose and (B) water-soluble polymer of this invention is given to the following, this invention is not limited by these. In Examples 4 to 10, all were confirmed by the method of Example 3 to have excellent formulation stability and a non-sticky feel.

[Example 4] Thorough lotion (A) Cellulose fiber 4 0.50 (mass%)
Hydroxyethyl cellulose 0.05
Glycerin 7.00
1,3-butylene glycol 5.00
Preservative appropriate amount Purified water Remaining amount (B) Dipotassium glycyrrhizinate 0.10
Purified water 10.00
Preparation method: A is heated to 80 ° C., and then stirred and cooled to 40 ° C. B is added while A is being stirred. Further, stirring and cooling are continued, and the preparation is completed at room temperature.

[Example 5] Gel serum (A) Cellulose fiber 3 0.30 (% by mass)
Xanthan gum 0.05
Glycerin 3.00
1,3-butylene glycol 7.00
Preservative Suitable amount Purified water Remaining amount (B) Arginine 0.05
Purified water 5.00
(C) Dipotassium glycyrrhizinate 0.10
Sodium hyaluronate (1% aqueous solution) 3.00
Purified water 5.00
Preparation method: A is heated to 80 ° C., and then stirred and cooled to 40 ° C. B and C are added to the place where A is being stirred. Further, stirring and cooling are continued, and the preparation is completed at room temperature.

[Example 6] Gel emulsion (A) Cellulose fiber 2 1.00 (mass%)
Guar gum 0.10
Glycerin 8.00
1,3-butylene glycol 5.00
Arginine 0.70
Preservative Appropriate amount Purified water Remaining amount (B) Jojoba oil 3.00
Squalane 5.00
Cetyl phosphate 1.40
Stearyl alcohol 2.00
Preparation method: A and B are heated to 80 ° C. and uniformly dissolved. Add A to B and stir to emulsify. The preparation is completed after stirring and cooling to room temperature.

[Example 7] Foundation (A) Cellulose fiber 3 0.70 (mass%)
Carboxymethylcellulose 0.10
Stearoyl methyl taurine sodium 0.50
1,3-butylene glycol 5.00
Preservative Suitable amount Purified water Remaining amount (B) Pigmented titanium oxide 7.00
Iron oxide (yellow) 0.70
Iron oxide (red) 0.20
Iron oxide (black) 0.10
(C) NIKKOL Nikomulus 41 2.50
Glyceryl stearate 1.00
Cetostearyl alcohol 1.00
Ethylhexyl methoxycinnamate 8.00
Dimethicone (6cs) 3.00
Cyclopentasiloxane 5.00
Preparation method: B is previously mixed in a disperser and uniformly dispersed. A and C are heated to 80 ° C. and uniformly dissolved. B is added to A, and C is added and emulsified while A is being stirred with a homomixer. The preparation is completed after stirring and cooling to room temperature.
* NIKKOL Nicolulus 41: behenyl alcohol, polyglyceryl-10 pentastearate, sodium stearoyl lactate

[Example 8] Sunscreen lotion (A) Cellulose fiber 4 0.05 (mass%)
Guar gum 0.03
Glycerin 5.00
Preservative appropriate amount Purified water remaining amount (B) CM3K40T4J 35.00
CM3K50XZ4J 25.00
X-21-5250L 3.00
Cyclopentasiloxane 15.00
(Vinyl Dimethicone / Methicon Silsesquioxane) Cross Polymer 2.00
Preparation method: B is stirred at room temperature and uniformly dispersed. A is added to the place where B is being stirred, and the preparation is completed after stirring.
* CM3K40T4J: PEG-10 dimethicone, fine particle titanium oxide, cyclopentasiloxane, methicone, alumina CM3K50XZ4J: PEG-10 dimethicone, methicone, fine particle zinc oxide, cyclopentasiloxane X-21-5250L: trimethylsiloxysilicate, dimethicone

[Example 9] Sunscreen gel (A) Cellulose fiber 3 1.00 (mass%)
Xanthan gum 0.50
Nylon-12 2.00
1,3-butylene glycol 5.00
Preservative Suitable amount Purified water Remaining amount (B) PEG-10 Dimethicone 0.50
CM3K40T4J 25.00
CM3K50XZ4J 15.00
Preparation method: A is heated to 80 ° C. and uniformly dissolved, and then stirred and cooled to room temperature. B is added to the place where A is being stirred with a homomixer and emulsified to complete the preparation.
* CM3K40T4J: PEG-10 dimethicone, fine particle titanium oxide, cyclopentasiloxane, methicone, alumina CM3K50XZ4J: PEG-10 dimethicone, methicone, fine particle zinc oxide, cyclopentasiloxane

[Example 10] Sunscreen milk (A) Cellulose fiber 3 0.30 (mass%)
Xanthan gum 0.05
Stearoyl methyl taurine sodium 0.50
1,3-butylene glycol 5.00
Preservative appropriate amount Purified water remaining amount (B) PEG-60 hydrogenated castor oil 0.50
Polysorbate 60 0.70
Sorbitan stearate 1.50
IOP50XZ4J 25.00
IOPP40VMJ 25.00
Ethylhexyl methoxycinnamate 8.00
Diethylaminohydroxybenzoyl hexyl benzoate 3.00
Preparation method: A and B are heated to 80 ° C. and uniformly dissolved. B is added and emulsified while A is being stirred with a homomixer. The preparation is completed after stirring and cooling to room temperature.
* IOP50XZ4J: ethylhexyl palmitate, fine particle zinc oxide, methicone, polyhydroxystearic acid IOPP40VMJ: ethylhexyl palmitate, fine particle titanium oxide, alumina, methicone, polyhydroxystearic acid

[Example 11] Hair mist (A) Cellulose fiber 1 0.70 (mass%)
Hydroxypropyl methylcellulose stearoxy ether 0.20
Preservative Suitable amount Purified water Remaining amount (B) Ethylhexyl methoxycinnamate 0.50
1,3-butylene glycol 3.00
PPG-6 decyltetradeces-30 1.00
(C) Panthenol 0.70
Ethanol 10.00
Preparation method: A is heated to 80 ° C. and uniformly dissolved, and then stirred and cooled to room temperature. B and C are respectively added to the place where A is being stirred, and after uniform dissolution, the preparation is completed.

[Example 12] Hair cream (A) Cellulose fiber 2 0.50 (mass%)
Xanthan gum 0.10
Arginine 0.70
Preservative appropriate amount Purified water Remaining amount (B) Hydrogenated lecithin 1.00
Polyglyceryl myristate-10 1.00
Cetanol 1.50
Triethylhexanoin 8.00
Cyclopentasiloxane 5.00
High polymerization dimethicone 3.00
Ethyl hexyl methoxycinnamate 1.50
Preparation method: A and B are heated to 80 ° C. and uniformly dissolved. B is added to the place where A is being stirred and emulsified, and then cooled to room temperature with stirring to complete the preparation.

  The present invention can provide a cosmetic having a good feel at the time of application and good formulation stability.

Claims (7)

A cosmetic comprising the following components (A) and (B).
(A) Fine fibrous cellulose having a fiber width of 1000 nm or less and having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less;
(B) Water-soluble polymer: The cosmetic according to claim 1, wherein the component (B) contains a thickening polysaccharide. The cosmetic according to claim 2, wherein the component (B) contains the ionic thickening polysaccharide. The cosmetics according to any one of claims 1 to 3, wherein a blending amount of the component (A) is 0.01 to 2.0 mass% with respect to the whole cosmetics. Cosmetics as described in any one of Claims 1-4 whose compounding quantity of the said component (B) is 0.03-1.0 mass% with respect to the whole cosmetics. Component (C) further contains one or more selected from the group consisting of inorganic powder, organic powder, inorganic acid, organic acid, inorganic acid salt, organic acid salt, and anionic surfactant. Cosmetics as described in any one of Claims 1-5. A cellulose-containing composition used to form a cosmetic,
A cellulose-containing composition comprising the following components (A) and (B).
(A) Fine fibrous cellulose having a fiber width of 1000 nm or less and having a substituent derived from phosphoric acid of 0.1 mmol / g or more and 3.0 mmol / g or less;
(B) Water-soluble polymer:

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