JP2022032281A - Shaving agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a shaving agent composition having good physical properties such as coatability and more preferably capable of increasing transparency.
SOLUTION: The shaving agent contains at least one of a phosphorous acid-modified fine fiber and an unmodified fine fiber, the average fiber width of the fine fiber is 1 to 1000 nm, and the shaving agent can be discharged as a gel. It is a composition.
[Selection diagram] None

Description

The present invention relates to a shaving agent composition suitable for use as a non-foaming shaving agent such as, for example, a shaving gel.

Shaving agents used when shaving body hair such as beards and dead hair with a shaving shaving include solid or powder shaving soap using fatty acids such as soap, shaving cream, shaving gel, aerosol type shaving foam, and post-foaming shaving. There are gel foam etc.

As a proposal regarding such a shaving agent, for example, there is a problem that the gel-like ejected material has high transparency (see Patent Document 1). However, the issue of shaving agents is not only transparency, but rather transparency is a subordinate issue. For example, in the case of a non-foaming (mold) shaving agent such as a shaving gel, the viscosity of the gel itself is an important factor. As an example, Patent Document 2 proposes a non-foaming shaving agent composition in which a carboxyl vinyl polymer and a polysaccharide polymer are used in combination as a gelling agent and the viscosity of the composition is set in a specific range. is doing. In addition, the proposal exemplifies "cellulose-based polymer compounds such as sodium carboxymethyl cellulose (CMC), crystalline cellulose, and cellulose powder" as polysaccharide-based polymers.

However, the shaving agent has easy application to the skin (applicability), stress on the skin, difficulty in running off the discharge applied to the skin, slipperiness of the razor (slipperiness), and ease of washing off the shaving agent. There are various demands such as unshaving, and it is not possible to uniformly evaluate the performance of the shaving agent depending on the viscosity.

Japanese Unexamined Patent Publication No. 7-163861 Japanese Unexamined Patent Publication No. 9-132516

A main problem to be solved by the present invention is to provide a shaving agent composition which has good physical properties such as stress on the skin and can more preferably increase transparency.

The shaving agent is preferably soft to some extent in terms of ease of application and spreading on the skin, while it is preferably hard to some extent so that it does not run off after application, and the razor is easy to slip and wash off. In that respect, the required physical properties change, such as the fact that it is preferable to be soft to some extent. As a result of continuing various studies based on such analysis, I came up with the thixotropy property of cellulose fine fibers. However, the physical characteristics of the shaving agent were not sufficiently improved by simply using fine fibers. Therefore, I continued my research and came up with the means to solve the above problems shown below.

(Means according to claim 1)
Containing at least one of a phosphorous acid-modified fine fiber and an unmodified fine fiber,
The average fiber width of the fine fibers is 1 to 1000 nm, and the fine fibers can be discharged as a gel.
A shaving agent composition characterized by that.

(Means according to claim 2)
The ratio of the subphosphorus-modified fine fibers to the entire composition is 1 to 20% by mass.
The shaving agent composition according to claim 1.

(Means according to claim 3)
The amount of the phosphorous acid ester introduced exceeds 2.0 mmol / g.
The shaving agent composition according to claim 1 or 2.

(Means according to claim 4)
Contains oils and nonionic surfactants
The nonionic surfactant is HLB 10 or higher.
The shaving agent composition according to any one of claims 1 to 3.

(Means according to claim 5)
The gel has a viscosity of 1,000 to 30,000 cps.
The shaving agent composition according to any one of claims 1 to 4.

According to the present invention, a shaving agent composition having good physical properties such as stress on the skin is obtained.

Next, a mode for carrying out the invention will be described. The embodiment of the present invention is an example of the present invention. The scope of the present invention is not limited to the scope of the present embodiment.

The shaving agent composition of the present embodiment contains at least one of a phosphorous acid-modified fine fiber and an unmodified fine fiber, and the average fiber width of the fine fiber is 1 to 1000 nm, and the shaving agent composition can be discharged as a gel. In addition to the fine fibers, it usually contains a synthetic polymer such as a thickener for gelling, and if necessary, contains a moisturizing component, an oil agent, a surfactant, an alkaline agent, water and the like. However, the shaving agent composition of this embodiment is non-foaming and does not contain a foaming component such as a post-foaming agent or a compressed gas. Hereinafter, they will be described in order.

In the shaving agent composition of this embodiment, the discharged product discharged from a container such as a tube or a bottle is in the form of a gel, and the state as a gel is maintained as it is (non-foaming).

(Synthetic polymer)
The shaving agent composition of this embodiment contains a synthetic polymer. The inclusion of synthetic polymers improves the spread and stability of the composition during application. As the synthetic polymer, for example, those used in ordinary cosmetics, pharmaceuticals, etc. can be used. However, it is preferable to use it as a thickener for forming a composition such as a carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer (acrylic acid / alkyl methacrylate copolymer), and xanthan gum into a gel. The above thickeners can be used by selecting one type or two or more types.

(Alkaline agent)
In this embodiment, when a carboxyvinyl polymer or an alkyl-modified carboxyvinyl polymer (acrylic acid / alkyl methacrylate copolymer) is used, it is preferable to add an alkaline agent for gelation. As the alkaline agent, for example, an organic base such as an alkanolamine or a basic amino acid, or an inorganic base such as an alkali metal hydroxide can be used. Specifically, for example, alkanolamines such as triethanolamine and 2-amino-2-methyl-1-propanol, basic amino acids such as arginine, lysine and histidine, and alkali metal hydroxides such as sodium hydroxide. Potassium hydroxide or the like can be used. However, in this embodiment using phosphorous acid-modified fine fibers, it is preferable to use triethanolamine / sodium hydroxide, potassium hydroxide and the like.

(Moisturizing ingredient)
The shaving agent composition of this embodiment contains a moisturizing component composed of a polyhydric alcohol or the like. When the moisturizing component is contained, the shaving agent composition can be applied to the skin and after shaving with a razor, the skin can be prevented from drying out, and the skin can be kept in an appropriate moist state. Further, when the moisturizing component is contained, the viscosity and spread of the shaving agent composition are improved, and the composition can be uniformly applied to the skin.

Examples of the polyhydric alcohol as a moisturizing component include glycerin, ethylene glycol, polyethylene glycol (average molecular weight of 10,000 or less), propylene glycol, polypropylene glycol, isoprene glycol, propanediol, 1,3-butylene glycol, and dipre. Pyrene glycol, hexylene glycol, pentylene glycol, diglycerin, polyglycerin, trehalose, glucosyltrehalose, xylitol, fructose, raffinose, lactose, trimethylglycine, sorbitol, martitol, inositol, decanediol, lactose, phytantriol, 1 , 2-Hexanediol and the like can be selected and used by one or more.

(Oil)
The shaving agent composition of this embodiment contains an oil agent. As the oil agent, for example, those used in ordinary cosmetics, pharmaceuticals, etc. can be used. Specifically, for example, almond oil, apricot oil, avocado oil, grape seed oil, sesame oil, wheat germ oil, rice bran oil, corn oil, safflower oil, shea butter, hydrogenated rapeseed oil alcohol, soybean oil, honeybee oil. , Peanut oil, sunflower oil, cottonseed oil, horse oil, olive oil, jojoba oil, lanolin, sunflower oil, cacao oil, mink oil and other natural animal and vegetable oils; Synthetic ester oils such as octyldodecyl myristite, isopropyl myristate, isopropyl palmitate, neopentyl glycol dicaprate, isononyl isononanoate; silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane; higher alcohols such as cetanol and stearyl alcohol; One or more of them can be selected and used from intercellular lipids such as cholesterol and ceramide and similar compounds thereof. However, it is preferable to use natural animal and vegetable oils such as olive oil, jojoba oil and mink oil, and hydrocarbons such as squalane and liquid paraffin from the viewpoint that a good skin care effect can be easily obtained.

The blending ratio of the oil agent is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. If the blending ratio of the oil agent exceeds 10% by mass, it may lead to discomfort such as stickiness.

(Surfactant)
As the surfactant, for example, one or more can be selected and used from among anionic surfactants, amphoteric surfactants, nonionic surfactants and the like. However, in this embodiment where foamability is not a problem, it is preferable to use a nonionic surfactant. In particular, in this embodiment using phosphorous acid-modified fine fibers, the nonionic surfactant preferably has an HLB of 10 or more, more preferably 11 or more, and particularly preferably 12 or more. If the HLB is less than 10 in the form of using phosphorous acid-modified fine fibers, the surfactant itself may cause poor dispersion in the mixed solution.

Examples of the nonionic surfactant having an HLB of 10 or more include polyoxyethylene (hereinafter POE) (9) lauryl ether [HLB (hereinafter the same): 14.5] and POE (7) cetyl ether [11]. .5], POE alkyl ethers such as POE (20) stearyl ether [18.0], POE (7) oleyl ether [10.5], POE (20) behenyl ether [18.0], POE (10) POE / POP alkyl ethers such as polyoxypropylene (POP) (4) cetyl ether [10.5], POE (20) POP (6) decyltetradecyl ether, polyethylene glycol monolaurate (10EO) [12 .5], Polyethylene glycol fatty acid esters such as polyethylene glycol monostearate (10EO) [11.0], polyethylene glycol monooleate (10EO) [11.0], POE (20) Himashi POE castor oil such as oil [10.5], POE (30) hardened castor oil [11.0], hardened castor oil, monococonut oil fatty acid POE (20) sorbitan [16.9], monopalmitic acid POE (20). ) One or two of POE sorbitan fatty acid esters such as sorbitan [15.6], POE monostearate (20) sorbitan [14.9], POE monooleate (20) sorbitan [15.0], etc. More than seeds can be used in combination.

On the other hand, examples of the anionic surfactant include sulfonic acid salts such as α-olefin sulfonate, sulfosuccinate and α-sulfo fatty acid methyl ester salt; sodium polyoxyethylene lauryl ether sulfate and triethanol polyoxyethylene lauryl ether sulfate. Polyoxyethylene alkyl sulfates such as amines; N-acylamino acid salts such as lauroyl sarcosine sodium and lauroyl methyl alanine sodium; polyoxyethylene lauryl ether sodium phosphate, polyoxyethylene cetyl ether sodium phosphate, dipolyoxyethylene alkyl ethers Among polyoxyethylene alkyl ether phosphates such as phosphoric acid, tripolyoxyethylene alkyl ether phosphate, dipolyoxyethylene nonylphenyl ether phosphate, polyoxyethylene lauryl ether sodium phosphate, dipolyethylene lauryl ether sodium phosphate, etc. One type or two or more types can be selected and used.

As the amphoteric tenside, for example, one kind or two or more kinds can be selected and used from among alkyl betaine, alkyl amide betaine, alkyl sulfobetaine and the like.

Examples of the nonionic surfactant include polyoxyethylene hydrogenated castor oil; polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tetraoleate and other polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene. Polyoxyethylene glyceryl fatty acid ester such as glyceryl monoisostearate and polyoxyethylene glyceryl triisostearate, polyethylene glycol fatty acid ester such as polyethylene glycol monoisostearate, polyoxyethylene hexyl decyl ether, polyoxyethylene octyldodecyl ether, Polyoxyethylene addition type surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene nonylphenyl ether; polyglycerin Polyglycerin-type surfactants such as alkyl ethers and polyglycerin fatty acid esters; among silicone derivative surfactants such as polyoxyethylene methyl polysiloxane copolymers and poly (oxyethylene / oxypropylene) methyl polysiloxane copolymers. One type or two or more types can be selected and used.

The blending ratio of the surfactant is preferably 0.1 to 3% by mass, more preferably 0.2 to 1% by mass, from the viewpoint of solubilizing the oil agent.

(others)
Water is usually added to the shaving agent composition of this embodiment. The water may be tap water, distilled water, ion-exchanged water, purified water, or the like.

The mixing ratio of water is, for example, 50 to 95% by mass, preferably 55 to 890% by mass, and more preferably 60 to 85% by mass with respect to the entire composition.

In the shaving agent composition of this embodiment, components other than the fine fibers described later, for example, a moisturizer, a preservative, a pH adjuster, a viscosity regulator, an antioxidant, a refreshing agent, a bactericide, a fragrance, a pigment and the like are appropriately added. Can be blended. The fine fibers described in detail below also have a role as a viscosity modifier.

(Fine fiber)
The shaving agent composition of the present embodiment contains, as fine fibers, at least one of phosphorous acid-modified fine fibers, more preferably phosphorous acid-modified fine fibers and unmodified fine fibers. Since the viscosity of the shaving agent composition of this embodiment is improved by fine fibers having thixotropic properties, the shaving agent composition has good applicability to the skin, but after being applied, it runs off from the skin. Does not occur. Moreover, it is extremely easy to wash off. In addition, when at least one of the phosphorous acid-modified fine fibers and the unmodified fine fibers is used, the stress on the skin is small and the unshaved part is also small. However, considering the ease of application, it is preferable to use phosphorous acid-modified fine fibers rather than unmodified fine fibers. In particular, the phosphorous acid-modified fine fiber is also excellent in transparency, and is therefore suitable for expanding the use of the shaving agent composition.

The term "unmodified" in this embodiment assumes a case where the cellulose fiber is not chemically modified such as TEMPO oxidation, modification of phosphorus such as phosphoric acid and phosphorous acid with oxo acid, and carbamate modification. In this respect, when the cellulose raw material is chemically modified, the uniformity of the cellulose nanofibers obtained by the subsequent defibration is generally increased.

In the present invention, unmodified is defined as meaning that the hydroxyl group on the surface of the cellulose fiber is not modified.

On the other hand, in the phosphorous acid-modified fine fiber of this embodiment, a part or all of the hydroxy group (-OH group) of the cellulose fiber is modified with an ester of phosphorous acid. Preferably, a part or all of the hydroxy group is replaced with a functional group represented by the following structural formula (1) to introduce (modify, modify) the ester of phosphorous acid. Particularly preferably, a part of the hydroxy group of the cellulose fiber is replaced with a carbamate group, and carbamate (ester of carbamic acid) is also introduced.

In the structural formula (1), α is any of none, R, and NHR. R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched chain hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched chain hydrocarbon group. , Aromatic groups, and any of these inducing groups. β is a cation composed of an organic substance or an inorganic substance.

The ester of phosphoric acid is a compound in which a hydroxy group (hydroxyl group) (—OH) and an oxo group (= O) are bonded to a phosphorus atom, and the hydroxy group gives an acidic proton. Therefore, the ester of phosphorous acid has a high negative charge like the compound having a phosphoric acid group. Therefore, when the ester of phosphorous acid is introduced, the repulsion between the cellulose molecules becomes strong, and the defibration of the cellulose fibers becomes easy. In addition, the introduction of an ester of phosphorous acid improves the transparency and viscosity of the dispersion. Further, the phosphorous acid-modified fine fibers are also cellulose fine fibers, and the cellulose fine fibers have thixotropic properties. Therefore, as described above, inconveniences due to the improvement in viscosity (decrease in coatability, difficulty in washing off, etc.) do not occur.

In particular, when carbamate is introduced together with the ester of phosphorous acid, the transparency and viscosity are further improved. In this respect, when the transparency of the phosphorous acid-modified fine fibers is improved, the shaving agent composition containing the phosphorous acid-modified fine fibers can be provided in a desired color. Carbamate also has an amino group. Therefore, the introduction of carbamate will also have a positive charge. Therefore, it is considered that the introduction of carbamate also enhances the charge interaction between the ester of phosphorous acid and carbamate and improves the viscosity. When the viscosity of the phosphorous acid-modified fine fibers is improved, the viscosity of the shaving agent composition containing the phosphorous acid-modified fine fibers is also improved. As a result, the stability of the gel at the initial discharge (for example, the gel does not run off) can be achieved. Further, since the phosphorous acid-modified fine fibers have thixotropic properties, the gel at the time of ejection has stability but excellent applicability, and is also good for sliding a razor.

It should be noted that the carbamate is more easily introduced when the ester of phosphorous acid is introduced than when the compound having a phosphoric acid group is introduced at the same time. Further, when the ester of phosphorous acid is introduced, unlike the case where the compound having a phosphoric acid group is introduced, the yellowing of the obtained cellulose fine fibers is prevented (improvement of transparency). In this respect, the effect of preventing this yellowing change is not the effect obtained by introducing the oxoacid of phosphorus in general, but the effect obtained only by introducing the ester of phosphorous acid. Therefore, the concept of phosphorus oxoacids has no meaning in terms of preventing yellowing. Incidentally, the present inventors consider that the yellowing is likely to occur when a compound having a phosphate group is introduced because a double bond is likely to occur in cellulose due to the Maillard reaction or the reduction reaction. Since the compound having a phosphoric acid group has a larger number of hydrogens than the ester of phosphorous acid, the pH is lower. The lower the pH, the easier it is for the reaction between the amine and the sugar to occur, or the easier it is for the cellulose to be reduced. Therefore, when an attempt is made to introduce a compound having a phosphoric acid group, cellulose is easily decomposed to produce sugar during heating, or cellulose is easily reduced. As a result, the yellowing is more likely to occur when a compound having a phosphoric acid group is introduced.

The amount of phosphorous acid ester introduced is more than 2.0 mmоl, preferably 2.1 mmоl or more, and more preferably 2.2 mmоl or more per 1 g of cellulose fiber. If the introduced amount is less than 2.0 mmol, defibration of the cellulose fiber may not be easy (when denatured prior to defibration). In addition, the aqueous dispersion of cellulose fibers may become unstable. On the other hand, the amount of phosphorous acid ester introduced is preferably 3.39 mmol or less per 1 g of cellulose fiber. If the amount introduced exceeds 3.39 mmol, the cellulose fibers may dissolve in water.

The amount of phosphorous acid ester introduced is a value evaluated based on elemental analysis. For this elemental analysis, X-Max 50001 manufactured by HORIBA, Ltd. is used.

The amount of carbamate introduced is preferably 0.06 to 2.34 mmol, more preferably 0.15 to 1.28 mmol, and particularly preferably 0.39 to 1.02 mmol per 1 g of cellulose fine fibers. If the amount introduced is less than 0.06 mmol, the light transmittance and viscosity of the dispersion may not be sufficiently increased. On the other hand, if the introduced amount exceeds 2.34 mmol, the cellulose fibers may be dissolved in water. The method for calculating the amount of carbamate introduced is the Kjeldahl method.

In the above, the cases where the fine fibers are not denatured and the cases where they are denatured with phosphorous acid or carbamate have been described, but the cellulose fibers can also be denatured (esterified) by phosphorous acid in general. Esterification with a phosphorus oxo acid can be carried out, for example, by the method described in JP-A-2019-199671.

In the fine fiber esterified with phosphoric acid, a part of the hydroxy group of the cellulose fiber is preferably replaced with the functional group represented by the following structural formula (2). The amount of the functional group introduced in the structural formula (2) is more than 2.0 mmоl, preferably 2.1 mmоl or more, and more preferably 2.2 mmоl or more per 1 g of the cellulose fiber.

In the structural formula (2), a, b, m, and n are natural numbers.
At least one of A1, A2, ..., An and A'is O, and the rest is either R, OR, NHR, and none. R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched chain hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched chain hydrocarbon group. , Aromatic groups, and any of these inducing groups. α is a cation composed of an organic substance or an inorganic substance.

The esterification reaction with phosphoric acid proceeds by adding additives such as phosphoric acids and metal phosphates to the cellulose fibers and heating the fibers. Examples of additives include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, lithium dihydrogen phosphate, trilithium trilithium phosphate, and dihydrogen phosphate. Lithium, lithium pyrophosphate, lithium polyphosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium polyphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, triphosphate Potassium, potassium pyrophosphate, potassium polyphosphate, phosphite, sodium hydrogen phosphite, ammonium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, sodium phosphite, lithium phosphite, sub Examples thereof include phosphite compounds such as potassium phosphate, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, and pyrophosphoric acid. Each of these additives can be used alone or in combination of two or more.

The fiber width of the fine fibers (average diameter of single fibers) is preferably 1 to 1000 nm, more preferably 2 to 400 nm, and particularly preferably 3 to 100 nm. If the fiber width is less than 1 nm, the fiber may dissolve in water and lose its physical properties as cellulose fine fibers, such as viscosity, thixotropy, strength, rigidity, and dimensional stability. On the other hand, when the fiber width exceeds 1000 nm, it can no longer be said to be a cellulose fine fiber and is no different from a normal cellulose fiber, and for example, thixotropy may not be exhibited.

The fiber width of the fine fibers is measured using an electron microscope as follows.
First, 100 ml of an aqueous dispersion of fine fibers having a solid content concentration of 0.01 to 0.1% by mass is filtered through a membrane filter manufactured by Teflon (registered trademark), and the solvent is replaced once with 100 ml of ethanol and three times with 20 ml of t-butanol. do. Next, it is freeze-dried and coated with osmium to prepare a sample. This sample is observed by an electron microscope SEM image at a magnification of 5000 times, 10,000 times or 30,000 times depending on the width of the constituent fibers. In this observation, two diagonal lines are drawn on the observation image, and three straight lines passing through the intersections of the diagonal lines are arbitrarily drawn. Then, the width of a total of 100 fibers intersecting with these three straight lines is visually measured. The median diameter of this measured value is defined as the fiber width.

The average fiber length (length of the single fiber) of the fine fibers is preferably 1 to 5,000 μm, more preferably 2 to 4,000 μm, and particularly preferably 3 to 3,000 μm. If the average fiber length is less than 1 μm, the entanglement of the fibers may be weakened and the gel may lack cushioning properties. On the other hand, if the average fiber length exceeds 5,000 μm, the fibers may aggregate.

The average fiber length of the fine fibers can be arbitrarily adjusted by, for example, selection of pulp fibers, pretreatment, and micronization treatment.

The average fiber length of the fine fibers is measured visually by measuring the length of each fiber in the same manner as in the case of the average fiber diameter. The average fiber length is the medium length of the measured value.

The axial ratio (fiber length / fiber width) of the fine fibers is preferably 3 to 1,000,000, more preferably 6 to 340,000, and particularly preferably 10 to 340,000. If the axial ratio is less than 3, it can no longer be said to be fibrous. On the other hand, if the axial ratio exceeds 1,000,000, the viscosity of the composition (slurry) may become too high.

The fibrilization rate of the fine fibers is preferably 70% or more, more preferably 80% or more, and particularly preferably 95% or more. If the fibrillation rate exceeds 70%, the fineness of the fibers progresses and the feeling of foreign matter in the composition disappears, while if the fibrillation rate is lower than 70%, the risk of feeling foreign matter in the gel may increase.

The fibrillation rate means that fine fibers are dissociated in accordance with JIS-P-8220: 2012 "Pulp-Dissolution Method", and the obtained dissociated pulp is referred to as FiberLab. (Kajaani) means a value measured using.

The peak value in the pseudo particle size distribution curve of the fine fiber is preferably one peak. In the case of one peak, the fine fibers have high uniformity of fiber length and fiber diameter, and are excellent in drying property. Further, when the fiber diameter and the fiber length are highly uniform, the dispersibility is also excellent.

The peak value of the fine fibers is preferably 5 μm or more, more preferably 7 μm or more, and particularly preferably 9 μm or more. If the peak value is less than 5 μm, the miniaturization process needs to be performed for a long time, which leads to an increase in manufacturing cost.

The peak value of the fine fibers is preferably 60 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less. If the peak value exceeds 60 μm, the uniformity of the fiber diameter and the fiber length tends to be inferior.

The half width of the peak of the fine fiber is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 15 μm or less. If the half width of the peak exceeds 30 μm, the uniformity of the fiber is lacking.

The peak value of the fine fiber is measured according to ISO-13320 (2009). More specifically, a volume-based particle size distribution in an aqueous dispersion of fine fibers is investigated using a particle size distribution measuring device (a laser diffraction / scattering type particle size distribution measuring device manufactured by Seishin Enterprise Co., Ltd.). Then, the mode of the fine fiber is measured from this distribution. This mode is used as the peak value.

The crystallinity of the fine fibers is preferably 50 to 100%, more preferably 60 to 90%, and particularly preferably 65 to 85%. If the crystallinity is less than 50%, the viscosity of the discharged product may be insufficient.

The crystallinity can be adjusted by, for example, selection of pulp fibers, pretreatment, defibration and the like.

The crystallinity is a value measured by an X-ray diffraction method in accordance with the "general rule of X-ray diffraction analysis" of JIS-K0131 (1996). The fine fiber has an amorphous portion and a crystalline portion, and the crystallinity means the ratio of the crystalline portion to the entire fine fiber.

The light transmittance (solid content 0.2% solution) of the fine fibers is preferably 40.0% or more, more preferably 70.0% or more, and particularly preferably 90.0%. If the light transmittance is less than 40.0%, it may be considered that the transparency is insufficient.

The light transmittance of the fine fibers can be adjusted by, for example, selection of pulp fibers, pretreatment, defibration and the like.

The light transmittance of the fine fibers is a value obtained by measuring the transparency (transmittance of 350 to 880 nm light) of the dispersion liquid of 0.2% (w / v) fine fibers using a Spectrophotometer U-2910 (Hitachi, Ltd.). be.

When the concentration of the fine fibers is 1% by mass (w / w), the B-type viscosity of the dispersion is preferably 500 to 300,000 cps, more preferably 1,000 to 200,000 cps, and particularly preferably 10,000 cps. It is ~ 100,000 cps. If the B-type viscosity is less than 1000 cps, the stability (maintenance) of the discharged product over time may be inferior. On the other hand, if the B-type viscosity exceeds 200,000 cps, the viscosity may become too high and the fluidity of the discharged product such as gel may be insufficient (decrease in coatability).

The B-type viscosity (solid content concentration 1%) of the dispersion liquid containing fine fibers is a value measured in accordance with "Method for measuring liquid viscosity" of JIS-Z8803 (2011). The B-type viscosity is the resistance torque when the dispersion liquid is stirred, and the higher it is, the more energy is required for stirring.

The pulp viscosity of the fine fibers is preferably 2 cps or more, more preferably 4 cps or more. If the pulp viscosity of the fine fibers is less than 2 cps, it may be difficult to suppress the aggregation of the fine fibers.

The pulp viscosity of the fine fibers is a value measured according to TAPPI T 230.

The freeness of the fine fibers is preferably 500 ml or less, more preferably 300 ml or less, and particularly preferably 100 ml or less. If the freeness exceeds 500 ml, the viscosity improving effect may not be sufficiently obtained.

The freeness of the fine fiber is a value measured according to JIS P8121-2 (2012).

The water retention of the fine fibers is preferably 250 to 500%, more preferably 300 to 450%, and particularly preferably 300 to 400%. If the water retention rate is less than 250%, the fluidity and smoothness may be impaired. On the other hand, when the degree of water retention exceeds 500%, the drainage becomes worse. In this respect, the water retention degree of the fine fiber can be lowered by substituting the hydroxy group of the fiber with the carbamate group, and the dehydration property and the dryness can be improved.

The water retention level of the fine fibers can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration and the like.

The water retention of fine fibers is determined by JAPAN TAPPI No. It is a value measured according to 26 (2000).

The blending ratio of the fine fibers is preferably 1 to 20%, more preferably 5 to 20%, and particularly preferably 10 to 20% in terms of solid content with respect to the entire composition. If the blending ratio is less than 1%, the effect of containing the fine fibers may not be exhibited. On the other hand, if the blending ratio exceeds 20%, the viscosity may become too high.

(Manufacturing method of fine fibers)
In the production method of this embodiment, an additive (A) consisting of at least one of a phosphite and a phosphite metal salt is added to the cellulose fiber, preferably an additive (A) consisting of at least one of a urea and a urea derivative. The substance (B) is added and heated to introduce an ester of a phosphoric acid, preferably an ester of a phosphoric acid and a carbamate into the cellulose fiber. Further, after washing the cellulose fiber into which the phosphorous acid ester or the like is introduced, the fiber is defibrated to obtain a phosphorous acid-modified fine fiber. However, the introduction of phosphorous acid ester or carbamate may be performed after defibration (miniaturization). On the other hand, in the case of producing unmodified fine fibers, only the defibration and the like are performed without using the additive (A) and the additive (B). When introducing an ester of a phosphorus oxo acid, an additive such as a phosphorus oxo acid or a phosphorus oxo acid metal salt is added to the cellulose fiber as described above, and the fiber is deflated by heating. The method for defibrating unmodified fine fibers and phosphorous acid-modified fine fibers is the same as that for producing phosphorous acid-modified fine fibers. Therefore, the following examples are for producing phosphorous acid-modified fine fibers. explain.

(Cellulose fiber)
As the cellulose fiber used as a raw material, for example, plant-derived fiber (plant fiber), animal-derived fiber, microorganism-derived fiber and the like can be used. These fibers can be used alone or in combination, if desired. However, as the cellulose fiber, it is preferable to use a plant fiber, and it is more preferable to use a pulp fiber which is a kind of a plant fiber. When the cellulose fiber is a pulp fiber, it is easy to adjust the physical properties of the phosphorous acid-modified fine fiber.

As the plant fiber, for example, wood pulp made from broadleaf trees, coniferous trees, etc., non-wood pulp made from straw, bagasse, etc., recovered waste paper, used paper pulp made from waste paper, etc. (DIP), etc. shall be used. Can be done. These fibers can be used alone or in combination of two or more.

As the wood pulp, for example, chemical pulp such as broad-leaved kraft pulp (LKP) and softwood kraft pulp (NKP), mechanical pulp (TMP), used paper pulp (DIP) and the like can be used. These pulps can be used alone or in combination of two or more.

The hardwood kraft pulp (LKP) may be hardwood bleached kraft pulp, hardwood unbleached kraft pulp, or hardwood semi-bleached kraft pulp. The softwood kraft pulp (NKP) may be softwood bleached kraft pulp, unbleached softwood kraft pulp, or semi-bleached softwood kraft pulp. The used paper pulp (DIP) may be magazine used paper pulp (MDIP), newspaper used paper pulp (NDIP), stepped used paper pulp (WP), or other used paper pulp.

(Additive (A))
The additive (A) consists of at least one of a phosphorous acid and a metal phosphate salt. Examples of the additive (A) include phosphite, sodium hydrogen phosphite, ammonium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, sodium phosphite, lithium phosphite, and sub-phosphoric acid. Phosphoric acid compounds such as potassium phosphate, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, and pyrophosphoric acid can be used. These phosphorous acids or phosphorous acid metal salts can be used alone or in combination of two or more. However, it is preferable to use sodium hydrogenphosphite.

In adding the additive (A), the cellulose fibers may be in a dry state, a wet state, or a slurry state. Further, the additive (A) may be in a powder state or an aqueous solution state. However, since the reaction uniformity is high, it is preferable to add the additive (A) in the state of an aqueous solution to the cellulose fiber in the dry state.

The amount of the additive (A) added is preferably 1 to 10,000 g, more preferably 100 to 5,000 g, and particularly preferably 300 to 1,500 g with respect to 1 kg of the cellulose fiber. If the amount added is less than 1 g, the effect of adding the additive (A) may not be obtained. On the other hand, even if the addition amount exceeds 10,000 g, the effect of the addition of the additive (A) may reach a plateau.

(Additive (B))
The additive (B) consists of at least one of urea and a urea derivative. As the additive (B), for example, urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea and the like can be used. These ureas or urea derivatives can be used alone or in combination of two or more. However, it is preferable to use urea.

When the additive (B) is heated, it is decomposed into isocyanic acid and ammonia as shown in the following reaction formula (1). Isocyanic acid is very reactive and forms a carbamate group at the hydroxyl group of cellulose as shown in the following reaction formula (2).

NH ₂ -CO-NH ₂ → HN = C = O + NH ₃ ... (1)

Cell-OH + HN = C = O → Cell-CO-NH ₂ … (2)

The amount of the additive (B) added is preferably 0.01 to 100 mol, more preferably 0.2 to 20 mol, and particularly preferably 0.5 to 10 mol with respect to 1 mol of the additive (A). If the amount added is less than 0.01 mol, carbamate may not be sufficiently introduced into the cellulose fibers. On the other hand, even if the amount added exceeds 100 mol, the effect of adding urea may reach a plateau.

(heating)
The heating temperature at which the additive (A) and the cellulose fiber to which the additive (B) is added is heated is preferably 100 to 210 ° C, more preferably 100 to 200 ° C, and particularly preferably 100 to 180 ° C. When the heating temperature is 100 ° C. or higher, an ester of phosphorous acid can be introduced. However, if the heating temperature exceeds 210 ° C., the deterioration of cellulose progresses rapidly, which may cause coloring or a decrease in viscosity.

The pH at which the additive (A) and the cellulose fiber to which the additive (B) is added is heated is preferably 3 to 12, more preferably 4 to 11, and particularly preferably 6 to 9. The lower the pH, the easier it is to introduce phosphorous acid esters and carbamate. However, if the pH is less than 3, the deterioration of cellulose may progress rapidly.

It is preferable to heat the cellulose fiber to which the additive (A) and the additive (B) are added until the cellulose fiber is dried. Specifically, the cellulose fibers are dried until the moisture content is preferably 10% or less, more preferably 0.1% or less, and particularly preferably 0.001% or less. Of course, the cellulose fibers may be in an absolutely dry state without moisture.

The heating time of the additive (A) and the cellulose fiber to which the additive (B) is added is, for example, 1 to 1,440 minutes, preferably 10 to 180 minutes, and more preferably 30 to 120 minutes. If the heating time is too long, the introduction of phosphorous acid esters and carbamate may proceed too much. Further, if the heating time is too long, the cellulose fibers may turn yellow.

As a device for heating the cellulose fiber to which the additive (A) and the additive (B) are added, for example, a hot air dryer, a paper machine, a dry pulp machine and the like can be used.

(Preprocessing)
Prior to the introduction of the phosphorous acid ester or the like into the cellulose fiber and / or after the introduction of the phosphorous acid ester or the like, the cellulose fiber may be subjected to a defibering pretreatment such as beating, if necessary. can. By pretreating the pulp fiber prior to the defibration of the cellulose fiber, the number of defibration can be significantly reduced and the energy for defibration can be reduced.

The pretreatment of the cellulose fibers can be carried out by a physical method or a chemical method, preferably a physical method and a chemical method. The pretreatment by the physical method and the pretreatment by the chemical method can be performed simultaneously or separately.

As the pretreatment by the physical method, it is preferable to adopt tapping. When the cellulose fibers are beaten, the cellulose fibers are trimmed. Therefore, the entanglement of the cellulose fibers is prevented (prevention of aggregation). From this point of view, the beating is preferably carried out until the freeness of the cellulose fiber is 700 ml or less, more preferably 500 ml or less, and particularly preferably 300 ml or less.

The freeness of the cellulose fiber is a value measured according to JIS P8121-2 (2012). Further, the beating can be performed using, for example, a refiner, a beater, or the like.

Pretreatment by chemical method includes, for example, hydrolysis of polysaccharide with acid (acid treatment), hydrolysis of polysaccharide with enzyme (enzyme treatment), swelling of polysaccharide with alkali (alkali treatment), oxidation of polysaccharide with oxidizing agent (acid treatment). Oxidation treatment), reduction of polysaccharides with a reducing agent (reduction treatment), and the like can be exemplified. However, as the pretreatment by a chemical method, it is preferable to carry out an enzyme treatment, and in addition, it is more preferable to carry out one or more treatments selected from an acid treatment, an alkali treatment and an oxidation treatment. Hereinafter, the enzyme treatment and the alkali treatment will be described in order.

As the enzyme used for the enzyme treatment, it is preferable to use at least one of a cellulase-based enzyme and a hemicellulase-based enzyme, and it is more preferable to use both in combination. The use of these enzymes facilitates the defibration of cellulose fibers. The cellulase-based enzyme causes the decomposition of cellulose in the coexistence of water. In addition, hemicellulose-based enzymes induce the decomposition of hemicellulose in the presence of water.

Examples of the cellulase-based enzymes include Trichoderma (Filamentous fungus), Acremonium (Filamentous fungus), Aspergillus (Filamentous fungus), Fanerochaete (Phanerochaete), Tramethes (Tra). Genus Humicola, genus Humicola, genus Bacillus, genus Schizophyllum, genus Streptomyces, genus Pseudomonas, bacteria produced by Pseudomonas, etc. Enzymes can be used. These cellulase-based enzymes can be purchased as reagents or commercial products. Commercially available products include, for example, cellulosein T2 (manufactured by HPI), Meicerase (manufactured by Meiji Seika), Novozyme 188 (manufactured by Novozyme), Multifect CX10L (manufactured by Genencore), and cellulase-based enzyme GC220 (manufactured by Genecore). Manufactured by) and the like can be exemplified.

Further, as the cellulase-based enzyme, either EG (endoglucanase) or CBH (cellobiohydrolase) can be used. EG and CBH may be used alone or in combination. Further, it may be used in combination with a hemicellulase-based enzyme.

As the hemicellulase-based enzyme, for example, xylanase, which is an enzyme that decomposes xylan, mannase, which is an enzyme that decomposes mannan, and arabanase, which is an enzyme that decomposes araban, can be used. can. In addition, pectinase, which is an enzyme that decomposes pectin, can also be used.

Hemicellulose is a polysaccharide excluding pectins between the cellulose microfibrils of the plant cell wall. Hemicellulose is diverse and varies between wood types and cell wall layers. Glucomannan is the main component in the secondary walls of conifers, and 4-O-methylglucuronoxylan is the main component in the secondary walls of hardwoods. Therefore, when cellulose fine fibers are obtained from softwood bleached kraft pulp (NBKP), it is preferable to use mannase. Further, when cellulose fine fibers are obtained from hardwood bleached kraft pulp (LBKP), it is preferable to use xylanase.

The amount of the enzyme added to the cellulose fiber is determined by, for example, the type of the enzyme, the type of wood as a raw material (conifer or hardwood), the type of mechanical pulp, and the like. However, the amount of the enzyme added to the cellulose fibers is preferably 0.1 to 3% by mass, more preferably 0.3 to 2.5% by mass, and particularly preferably 0.5 to 2% by mass. If the amount of the enzyme added is less than 0.1% by mass, the effect of adding the enzyme may not be sufficiently obtained. On the other hand, if the amount of the enzyme added exceeds 3% by mass, cellulose may be saccharified and the yield of cellulose fine fibers may decrease. In addition, there is also a problem that the improvement of the effect corresponding to the increase in the addition amount cannot be recognized.

When a cellulase-based enzyme is used as the enzyme, the pH at the time of enzyme treatment is preferably in a weakly acidic region (pH = 3.0 to 6.9) from the viewpoint of the reactivity of the enzyme reaction. On the other hand, when a hemicellulase-based enzyme is used as the enzyme, the pH at the time of enzyme treatment is preferably in a weak alkaline region (pH = 7.1 to 10.0).

The temperature during the enzyme treatment is preferably 30 to 70 ° C, more preferably 35 to 65 ° C, and particularly preferably 40 to 60 ° C, regardless of whether the cellulase-based enzyme or the hemicellulase-based enzyme is used as the enzyme. .. When the temperature at the time of enzyme treatment is 30 ° C. or higher, the enzyme activity is less likely to decrease, and the treatment time can be prevented from being prolonged. On the other hand, if the temperature at the time of enzyme treatment is 70 ° C. or lower, inactivation of the enzyme can be prevented.

The time of the enzyme treatment is determined by, for example, the type of the enzyme, the temperature of the enzyme treatment, the pH at the time of the enzyme treatment, and the like. However, the general enzyme treatment time is 0.5 to 24 hours.

After the enzyme treatment, it is preferable to inactivate the enzyme. As a method for inactivating the enzyme, for example, there are a method of adding an alkaline aqueous solution (preferably pH 10 or higher, more preferably pH 11 or higher), a method of adding hot water at 80 to 100 ° C., and the like.

Next, the method of alkali treatment will be described.

As a method of alkaline treatment, for example, there is a method of immersing a cellulose fiber in which an ester of phosphorous acid or the like is introduced in an alkaline solution.

The alkaline compound contained in the alkaline solution may be an inorganic alkaline compound or an organic alkaline compound. Examples of the inorganic alkali compound include hydroxides of alkali metals or alkaline earth metals, carbonates of alkali metals or alkaline earth metals, and phosphates of alkali metals or alkaline earth metals. Further, as the hydroxide of the alkali metal, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like can be exemplified. Examples of the hydroxide of the alkaline earth metal include calcium hydroxide and the like. Examples of the alkali metal carbonate include lithium carbonate, lithium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like. Examples of the carbonate of the alkaline earth metal include calcium carbonate and the like. Examples of the alkali metal phosphate include lithium phosphate, potassium phosphate, trisodium phosphate, and disodium hydrogen phosphate. As the phosphate of the alkaline earth metal, for example, calcium phosphate, calcium hydrogen phosphate and the like can be exemplified.

Examples of the organic alkaline compound include ammonia, an aliphatic amine, an aromatic amine, an aliphatic ammonium, an aromatic ammonium, a heterocyclic compound and its hydroxide, a carbonate, and a phosphate. Specifically, for example, for example, ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, cyclohexylamine, aniline. , Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, pyridine, N, N-dimethyl-4-aminopyridine, ammonium carbonate, ammonium hydrogencarbonate, For example, diammonium hydrogen phosphate and the like can be exemplified.

The solvent of the alkaline solution may be either water or an organic solvent, but a polar solvent (a polar organic solvent such as water or alcohol) is preferable, and at least an aqueous solvent containing water is more preferable.

The pH of the alkaline solution at 25 ° C. is preferably 9 or more, more preferably 10 or more, and particularly preferably 11 to 14. When the pH is 9 or more, the yield of cellulose fine fibers is high. However, if the pH exceeds 14, the handleability of the alkaline solution deteriorates.

(Washing)
Cellulose fibers into which an ester of phosphorous acid or the like has been introduced are preferably washed prior to defibration. By cleaning the cellulose fibers, by-products and unreacted products can be washed away. Further, if this cleaning precedes the alkaline treatment in the pretreatment, the amount of the alkaline solution used in the alkaline treatment can be reduced.

The cellulose fibers can be washed using, for example, water, an organic solvent, or the like.

(Defibration)
Cellulose fibers into which an ester of phosphorous acid or the like has been introduced are defibrated (miniaturized) after washing. By this defibration, pulp fibers are microfibrillated into cellulose fine fibers (cellulose nanofibers and microfiber cellulose). The method of defibration is the same for unmodified fine fibers and phosphoric acid-modified fine fibers.

When defibrating the cellulose fibers, it is preferable to make the cellulose fibers into a slurry. The solid content concentration of this slurry is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1.0 to 5.0% by mass. If the solid content concentration is within the above range, defibration can be performed efficiently.

For defibration of cellulose fibers, for example, a high-pressure homogenizer, a homogenizer such as a high-pressure homogenizer, a high-speed rotary homogenizer, a grinder, a millstone friction machine such as a grinder, a conical refiner, a refiner such as a disc refiner, a uniaxial kneader, and many It can be carried out by selectively using one or more kinds of means from a shaft kneader, various bacteria and the like. However, it is preferable to defibrate the cellulose fibers by using a device / method for miniaturizing with a water stream, particularly a high-pressure water stream. According to this device / method, the dimensional uniformity and dispersion uniformity of the obtained cellulose fine fibers are very high. On the other hand, for example, when a grinder that grinds between rotating grindstones is used, it is difficult to uniformly refine the cellulose fibers, and in some cases, there is a possibility that undissolved fiber lumps may remain.

As a grinder used for defibrating cellulose fibers, for example, there is a mass colloider of Masuko Sangyo Co., Ltd. Further, as a device for miniaturizing with a high-pressure water flow, for example, Sugino Machine Limited's Starburst (registered trademark) and Yoshida Kikai Kogyo Co., Ltd.'s Nanovater (registered trademark) are available. Further, as a high-speed rotary homogenizer used for defibrating cellulose fibers, there is Clairemix-11S manufactured by M-Technique.

In addition, a method of defibrating cellulose fibers by a method of grinding between rotating grindstones and a method of refining with a high-pressure water flow, and a method of refining each obtained fiber with a high-pressure water flow when observed under a microscope. It has been found that the fibers obtained in 1) have a more uniform fiber width.

For defibration by high-pressure water flow, the dispersion liquid of cellulose fibers is pressurized to, for example, 30 MPa or more, preferably 100 MPa or more, more preferably 150 MPa or more, particularly preferably 220 MPa or more (high pressure conditions), and the pore diameter is 50 μm or more. It is preferable to use a method of ejecting the fiber from the nozzle of No. 1 and reducing the pressure so that the pressure difference is, for example, 30 MPa or more, preferably 80 MPa or more, more preferably 90 MPa or more (decompression condition). Pulp fibers are defibrated by the cleavage phenomenon caused by this pressure difference. When the pressure under the high pressure condition is low or when the pressure difference from the high pressure condition to the depressurized condition is small, the defibration efficiency decreases, and it becomes necessary to repeatedly defibrate (spout from the nozzle) in order to obtain the desired fiber diameter. ..

As a device for defibrating by a high-pressure water flow, it is preferable to use a high-pressure homogenizer. The high-pressure homogenizer refers to a homogenizer having the ability to eject a slurry of cellulose fibers at a pressure of, for example, 10 MPa or more, preferably 100 MPa or more. When the cellulose fibers are treated with a high-pressure homogenizer, collisions between the cellulose fibers, pressure difference, microcavitation and the like act, and the cellulose fibers are effectively defibrated. Therefore, the number of defibration treatments can be reduced, and the production efficiency of cellulose fine fibers can be improved.

As the high-pressure homogenizer, it is preferable to use one in which a slurry of cellulose fibers collides with each other in a straight line. Specifically, for example, a counter-collision type high-pressure homogenizer (microfluidizer / MICROFLUIDIZER®, wet jet mill). In this device, two upstream flow paths are formed so that the pressurized cellulose fiber slurries collide with each other at the confluence. Further, the cellulose fiber slurry collides with each other at the confluence, and the collided cellulose fiber slurry flows out from the downstream flow path. The downstream flow path is provided perpendicular to the upstream side flow path, and a T-shaped flow path is formed by the upstream side flow path and the downstream side flow path. When such a counter-collision type high-pressure homogenizer is used, the energy given by the high-pressure homogenizer is converted to the collision energy to the maximum, so that the cellulose fibers can be defibrated more efficiently.

In the defibration of the cellulose fiber, the average fiber width, the average fiber length, the water retention degree, the crystallization degree, the peak value of the pseudo particle size distribution, the pulp viscosity and the like of the obtained cellulose fine fiber (subphosphate-modified fine fiber) are described above. It is preferable to obtain a desired value or evaluation.

(Mixed composition)
The viscosity of the mixed composition (shaving agent composition) obtained by mixing each of the above components is preferably 1,000 to 30,000 cps, more preferably 1,500 to 25,000 cps, and particularly preferably 2,000 cps. It is ~ 20,000 cps. When the viscosity is below 1,000 cps, it is easier to apply the mixture to the skin, but it may be easier to feel skin stress when shaving with a razor. On the other hand, if the viscosity exceeds 30,000 cps, it may be difficult to apply to the skin and the usability may deteriorate.

The viscosity of the mixed composition is a value measured according to "Method for measuring viscosity of liquid" of JIS-Z8803 (2011).

Next, examples of the present invention will be described.
A shaving agent composition was prepared with the formulations shown in Table 1 and various tests were performed. The test results are shown in Table 2. The details of each test and the details of each raw material are as follows.

(Test method)
In this test, 10 men who usually shave with a T-shaped razor performed a 5-point evaluation compared with normal shaving according to the following criteria, and the average value was shown.
Viscosity: Evaluated in comparison with the shavin gel etc. that are usually used.
Ease of application: Evaluates the spreadability when applying the shaving agent composition to the skin. The easier it is to spread, the higher the score.
Slipperiness: Evaluate the slipperiness when applying a razor. The more slippery it is, the higher the score.
Skin stress: Evaluate whether the blade feels like it is hitting when shaving. The score is so high that there is no stress.
Ease of rinsing: Evaluate the rinsability of the shaving composition after use. The higher the score, the easier it is to wash off.
Unshaving property: Check if there is any unshaving after use. The smaller the number, the higher the score.

(Phosphate-modified CNF)
A mixed solution of 13 g of sodium hydrogen phosphite pentahydrate, 10.8 g of urea, and 76.2 g of water was mixed, and 10 g (dry weight) of raw pulp (NBKP: 98.0% by mass of water) was mixed. , 105 ° C. was dried. The dried pulp was reacted at 130 ° C. for 2 hours. Next, washing with water and filtration were repeated twice to obtain a cellulose fiber (phosphorous acid-modified pulp) into which an ester of phosphorous acid containing a cation consisting of an inorganic substance was introduced. This phosphorous acid-modified pulp was micronized (defibrated) with a high-pressure homogenizer to obtain a phosphorous acid-modified CNF (average fiber diameter: 3 nm).

(Unmodified CNF)
The hardwood bleached pulp was roughly defibrated with a single disc refiner and then refined (defibrated) with a high-pressure homogenizer (average fiber diameter: 45 nm). Unmodified CNF was also blended with other components as a 2.0 mass% slurry.

(others)
CMC-Na: Made by Daicel FineChem Co., Ltd., Part No. 1330
C10-30) Copolymer: Acrylic acid / alkyl acrylate (C10-30) copolymer, manufactured by Sumitomo Seika Chemical Co., Ltd., AQPEC HV-803ERK (CT-1)
Polyethylene oxide: Product name Alcox, Meisei Chemical Works, Ltd. Glycerin: Product name "Purified glycerin", Sakamoto Yakuhin Kogyo Co., Ltd. Liquid paraffin: Fujifilm Wako Pure Chemical Industries, Ltd. Polysorbate 80: Polysorbate 80 Cafe de Savon
Menthol solution: Product name of Natural Science Research Institute: Ethanol: Ethanol (99.5) Made by Fujifilm Wako Pure Chemical Industries, Ltd. Adjusted to 10% concentration.
Phenoxyethanol: 2-phenoxyethanol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. TEA: 20W / V%, triethanolamine, manufactured by Hayashi Junyaku Kogyo Co., Ltd.

(water)
Purified water was used. In the table, water indicates the amount (g) of purified water.

(Discussion)
When CNF is included, the feeling of stress on the skin tends to be reduced. The viscosity of the composition tended to increase when CNF was contained, but the viscosity behavior of CNF did not appear in the viscosity of the composition itself, and in particular, the modified CNF did not affect the viscosity of the composition, and the feeling of use was improved. Suggests that it can be improved

The present invention can be used as a non-foaming shaving agent such as a shaving gel.

Claims (5)

Containing at least one of a phosphorous acid-modified fine fiber and an unmodified fine fiber,
The average fiber width of the fine fibers is 1 to 1000 nm, and the fine fibers can be discharged as a gel.
A shaving agent composition characterized by that. The ratio of the subphosphorus-modified fine fibers to the entire composition is 1 to 20% by mass.
The shaving agent composition according to claim 1. The amount of the phosphorous acid ester introduced exceeds 2.0 mmol / g.
The shaving agent composition according to claim 1 or 2. Contains oils and nonionic surfactants
The nonionic surfactant is HLB 10 or higher.
The shaving agent composition according to any one of claims 1 to 3. The gel has a viscosity of 1,000 to 30,000 cps.
The shaving agent composition according to any one of claims 1 to 4.