WO2020158543A1 - Agent émulsifiant huile-dans-eau et préparation cosmétique - Google Patents

Agent émulsifiant huile-dans-eau et préparation cosmétique Download PDF

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WO2020158543A1
WO2020158543A1 PCT/JP2020/002146 JP2020002146W WO2020158543A1 WO 2020158543 A1 WO2020158543 A1 WO 2020158543A1 JP 2020002146 W JP2020002146 W JP 2020002146W WO 2020158543 A1 WO2020158543 A1 WO 2020158543A1
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fibrous cellulose
mass
group
oil
fine fibrous
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PCT/JP2020/002146
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English (en)
Japanese (ja)
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敬子 村社
美里 和田
利奈 田中
郁絵 杉山
Original Assignee
日光ケミカルズ株式会社
株式会社コスモステクニカルセンター
王子ホールディングス株式会社
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Publication of WO2020158543A1 publication Critical patent/WO2020158543A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/69—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/14—Preparations for removing make-up
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the present invention relates to an oil-in-water emulsifier and a cosmetic used to form a cosmetic.
  • an external preparation for skin containing water and oil in a stable manner has been used in order to provide appropriate moisturization to the skin.
  • an emulsification technique such as oil-in-water emulsification or water-in-oil emulsification in which emulsion particles are finely stabilized by using a surfactant is used.
  • a surfactant is blended in an amount of about 10% of the oil amount, and the stickiness caused by the surfactant lowers the feeling of use, or the surfactant used. Depending on the situation, there was a problem that it had a slight stimulative property.
  • Patent Document 1 a technique of combining a water-swelling clay mineral and a polyether-modified silicone oil in order to reduce the amount of a surfactant used (Patent Document 1), and an alkyl-modified water-soluble alkyl-modified carboxyvinyl polymer, etc.
  • Patent Document 2 A technique (Patent Document 2) in which a polymer is used to emulsify without adding a surfactant is known.
  • the alkyl-modified water-soluble polymer include acrylates/alkyl acrylate crosspolymer, stearoxyhydroxypropyl methylcellulose, and the like, and these alkyl-modified water-soluble polymers also have unique stickiness due to the water-soluble polymer. ..
  • Patent Document 3 a water-in-oil type emulsion composition is characterized by containing at least one kind of fine particles selected from the group of cellulose fine particles and cellulose composite fine particles having an average particle diameter of 10 to 500 nm. Is disclosed.
  • the water-in-oil emulsion composition of Patent Document 3 contains a hydrophilic surfactant in addition to the lipophilic surfactant.
  • Patent Document 4 discloses an emulsifier containing fine cellulose fibers in which a hydrophobic group and a cationic group or an anionic group are introduced into cellulose.
  • the stability thereof may not be sufficiently obtained in some cases.
  • JP, 2007-39612 A Japanese Patent Laid-Open No. 08-217624 JP, 2006-342140, A [Patent Document 1] JP-A-2005-044168
  • the present invention has an object to provide a cosmetic having excellent emulsion stability and a feeling of use even without using a surfactant.
  • the present inventors have found that fine fibrous cellulose having a fiber width of 1000 nm or less has a function as an emulsifier for cosmetics which is an oil-in-water emulsion composition, and such fine fibers are used. It was found that a cosmetic having excellent emulsion stability and a feeling of use can be obtained by using the cellulose-like cellulose.
  • the present invention has the following configurations.
  • An oil-in-water emulsifier used for forming a cosmetic An oil-in-water emulsifier containing fibrous cellulose having a fiber width of 1000 nm or less.
  • the fibrous cellulose has an anionic group, and is the oil-in-water emulsifier according to [1] or [2].
  • a cosmetic comprising the oil-in-water emulsifier according to any one of [1] to [3] and an oily component, Cosmetics in which the mass ratio of oily component/fibrous cellulose is 0.1 or more and 350 or less.
  • the content of the fibrous cellulose is 0.01% by mass or more and 5% by mass or less and the content of the oily component is 0.1% by mass or more and 50% by mass or less based on the total mass of the cosmetic. 4] The cosmetic according to [4].
  • the present invention it is possible to provide a cosmetic composition which is excellent in emulsion stability and excellent in feeling of use, even without using a surfactant.
  • the present invention also provides a novel oil-in-water emulsifier using fine fibrous cellulose having a fiber width of 1000 nm or less.
  • FIG. 1 is a graph showing the relationship between the amount of dropped NaOH and electrical conductivity with respect to fine fibrous cellulose having a phosphate group.
  • FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and the electrical conductivity with respect to the fine fibrous cellulose having a carboxyl group.
  • FIG. 3 is a graph showing the relationship between the amount of dropped NaOH and pH for fibrous cellulose having a phosphate group.
  • the oil-in-water emulsifier of the present invention contains fibrous cellulose having a fiber width of 1000 nm or less.
  • the present invention relates to an oil-in-water emulsifier used for forming a cosmetic, and such an oil-in-water emulsifier is also referred to as an oil-in-water emulsifier for cosmetics.
  • the oil-in-water emulsifier of the present invention may contain other components such as water in addition to the fibrous cellulose having a fiber width of 1000 nm or less, but is made of fibrous cellulose having a fiber width of 1000 nm or less. May be In the present specification, fibrous cellulose having a fiber width of 1000 nm or less may be referred to as fine fibrous cellulose.
  • the oil-in-water emulsifier of the present invention has the above constitution, it is possible to obtain a cosmetic having excellent emulsion stability without using a surfactant. Furthermore, when the oil-in-water type emulsifier of the present invention is used, the obtained cosmetic has an excellent feeling in use. Since the oil-in-water emulsifier of the present invention contains a natural material as a main component, it is highly safe and has low irritation.
  • the content of the fine fibrous cellulose contained in the oil-in-water emulsifier is, for example, 5% by mass or more based on the total mass of the oil-in-water emulsifier. Is preferable, 10% by mass or more is more preferable, 15% by mass or more is further preferable, and 20% by mass or more is particularly preferable.
  • the upper limit of the content of the fine fibrous cellulose contained in the oil-in-water emulsifier is not particularly limited, but is, for example, 99.5% by mass. be able to. By setting the content of the fine fibrous cellulose within the above range, an oil-in-water emulsifier having excellent handling properties can be obtained.
  • the content of the solvent contained in the oil-in-water emulsifier is preferably 90% by mass or less based on the total mass of the oil-in-water emulsifier, It is more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 70% by mass or less.
  • the upper limit of the content of the solvent is within the above range, a fine fibrous cellulose-containing material excellent in handleability can be obtained.
  • the lower limit of the content of the solvent contained in the oil-in-water emulsifier is not particularly limited, and may be 0% by mass, for example.
  • the content of the solvent contained in the oil-in-water emulsifier can be, for example, 0.5% by mass or more based on the total mass of the fine fibrous cellulose-containing material.
  • the content of fine fibrous cellulose contained in the oil-in-water emulsifier is 0.1% by mass or more and 5.0% by mass or less based on the total mass of the oil-in-water emulsifier. It is preferably 0.3 mass% or more and 3.0 mass% or less, more preferably 0.5 mass% or more and 3.0 mass% or less.
  • the content of the solvent contained in the oil-in-water emulsifier is preferably 60% by mass or more and 99.9% by mass or less based on the total mass of the oil-in-water emulsifier, 90
  • the content is more preferably not less than 9% by mass and not more than 99.7% by mass, further preferably not less than 97% by mass and not more than 99.5% by mass.
  • the hydrophobic group is a functional group exhibiting hydrophobicity, specifically, a hydrophobic bulky group.
  • the hydrophobic group is not particularly limited, but is a saturated or unsaturated, straight-chain or branched chain, aromatic ring-containing hydrocarbon group, or saturated or unsaturated ring-containing hydrocarbon group or acyl having 2 to 50 carbon atoms. A group etc. can be mentioned.
  • hydrophobic group examples include acetyl group, acryloyl group, methacryloyl group, propionyl group, propioroyl group, butyryl group, 2-butyryl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group.
  • dodecanoyl group myristoyl group, palmitoyl group, stearoyl group, pivaloyl group and other acyl groups, methyl group, ethyl group, propyl group, 2-propyl group, butyl group, 2-butyl group, tert-butyl group, pentyl group , Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, palmityl group, alkyl group such as stearyl group, and aromatic ring such as benzyl group, benzoyl group, naphthoyl group A functional group etc. are mentioned.
  • the content of the hydrophobic group in the fibrous cellulose is preferably less than 0.1 mmol/g, and particularly preferably 0 mmol/g.
  • the fine fibrous cellulose does not substantially have a hydrophobic group if the content of the hydrophobic group is less than 0.1 mmol/g.
  • the content of the hydrophobic group contained in the fine fibrous cellulose can be measured by extracting the hydrophobic group contained in the fine fibrous cellulose by an appropriate pretreatment and subjecting the extract to a quantitative analysis.
  • a quantitative analysis for example, gas chromatography-mass spectrometry (GC/MS) can be used.
  • the hydrophobic group when the hydrophobic group is bound to the hydroxyl group on the surface of the fibrous cellulose by an ester bond, the hydrophobic group can be extracted by a pretreatment such as acid hydrolysis.
  • the hydrophobic group when the hydrophobic group is bound to the anionic functional group existing on the surface of the fibrous cellulose by ionic bond, the hydrophobic group can be extracted by pretreatment such as acid treatment.
  • the oil-in-water emulsifier of the present invention contains fibrous cellulose (fine fibrous cellulose) having a fiber width of 1000 nm or less.
  • Fine fibrous cellulose is manufactured from a fiber raw material containing cellulose.
  • fiber raw materials containing cellulose include papermaking pulp, cotton-based pulp such as cotton linter and cotton lint, hemp, straw, non-wood-based pulp such as bagasse, cellulose isolated from squirts and seaweed, and the like. It is not particularly limited. Among these, paper-making pulp is preferable in terms of easy availability, but is not particularly limited. Examples of the pulp for papermaking include 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 the softwood kraft pulp include bleached kraft pulp (NBKP), unbleached kraft pulp (NUKP), and oxygen bleached kraft pulp (NOKP).
  • chemical pulp, semi-chemical pulp, mechanical pulp, non-wood pulp, and deinked pulp made from waste paper are mentioned, but not particularly limited.
  • Examples of the chemical pulp include sulfite pulp (SP) and soda pulp (AP).
  • Examples of the semi-chemical pulp include semi-chemical pulp (SCP) and chemiground wood pulp (CGP).
  • Mechanical pulp includes groundwood pulp (GP), thermomechanical pulp (TMP, BCTMP), and the like.
  • non-wood pulp there are those made from raw materials such as Japanese pomegranate, Japanese pepper, hemp, and kenaf. Of these, kraft pulp, deinked pulp, and sulfite pulp are preferable because they are more easily available, but are not particularly limited.
  • the cellulose raw materials may be used alone or in combination of two or more.
  • the average fiber width of the fine fibrous cellulose is, for example, 1000 nm or less.
  • the average fiber width of the fine fibrous cellulose is, for example, preferably 2 nm or more and 1000 nm or less, more preferably 2 nm or more and 100 nm or less, further preferably 2 nm or more and 50 nm or less, and 2 nm or more and 10 nm or less. Is particularly preferable.
  • the fine fibrous cellulose is, for example, monofilament cellulose.
  • the average fiber width of the fine fibrous cellulose is measured, for example, using an electron microscope as follows. First, an aqueous suspension of fine fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and this suspension is cast on a hydrophilized carbon film-coated grid for TEM observation. Use as a sample. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. Then, observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times or 50000 times according to the width of the fiber to be observed. However, the sample, observation conditions and magnification are adjusted so as to satisfy the following conditions.
  • One straight line X is drawn at an arbitrary position in the observed image, and 20 or more fibers intersect the straight line X.
  • 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 fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 ⁇ m or more and 1000 ⁇ m or less, more preferably 0.1 ⁇ m or more and 800 ⁇ m or less, and 0.1 ⁇ m or more and 600 ⁇ m or less. More preferable.
  • the fiber length of the fine fibrous cellulose can be determined by image analysis using TEM, SEM, or AFM, for example.
  • the fine fibrous cellulose preferably has a type I crystal structure.
  • the ratio of the crystal part contained in the fine fibrous cellulose is not particularly limited, but it is preferable to use cellulose having a crystallinity of 60% or more determined by an X-ray diffraction method.
  • the crystallinity is preferably 65% or more, more preferably 70% or more, and in this case, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion coefficient expression.
  • the crystallinity can be determined by measuring the X-ray diffraction profile and using the pattern in a conventional manner (Seagal et al., Textile Research Journal, 29, 786, page 1959).
  • the fine fibrous cellulose preferably has an anionic group.
  • the anionic group for example, a phosphoric acid group or a substituent derived from a phosphoric acid group (sometimes simply referred to as a phosphoric acid group), a carboxyl group or a substituent derived from a carboxyl group (sometimes simply referred to as a carboxyl group), And at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes referred to simply as a sulfone group), and at least one selected from a phosphoric acid group and a carboxyl group
  • a phosphoric acid group is more preferable, and a phosphoric acid group is particularly preferable.
  • the phosphoric acid group or the substituent derived from the phosphoric acid group is, for example, a substituent represented by the following formula (1), and is generalized as a phosphorous acid group or a substituent derived from a phosphorous acid.
  • the phosphoric acid group is a divalent functional group which corresponds to, for example, phosphoric acid from which a hydroxyl group has been removed. Specifically, it is a group represented by —PO 3 H 2 .
  • Substituents derived from a phosphoric acid group include substituents such as salts of phosphoric acid groups and phosphoric acid ester groups.
  • the substituent derived from the phosphate group may be contained in the fine fibrous cellulose as a group in which the phosphate group is condensed (for example, a pyrophosphate group).
  • the phosphoric acid group may be, for example, a phosphorous acid group (phosphonic acid group), and the substituent derived from the phosphoric acid group may be a salt of a phosphorous acid group, a phosphorous acid ester group, or the like. Good.
  • Each R is a hydrogen atom.
  • ⁇ b+ is a monovalent or higher cation composed of an organic substance or an inorganic substance.
  • monovalent or more cations composed of organic substances include aliphatic ammonium and aromatic ammonium
  • examples of monovalent or more cations composed of inorganic substances include alkali metal ions such as sodium, potassium, or lithium
  • examples thereof include cations of divalent metals such as calcium and magnesium, and hydrogen ions, but are not particularly limited. These may be applied alone or in combination of two or more.
  • the cation having a valence of 1 or more consisting of an organic substance or an inorganic substance is preferably sodium or potassium ion, which is less likely to yellow when the fiber raw material containing ⁇ is heated and is industrially usable, but is not particularly limited.
  • the amount of anionic groups introduced into the fine fibrous cellulose is, for example, preferably 0.10 mmol/g or more, and 0.20 mmol/g or more per 1 g (mass) of the fine fibrous cellulose. Is more preferable, 0.50 mmol/g or more is more preferable, and 1.00 mmol/g or more is particularly preferable.
  • the amount of the anionic group introduced into the fine fibrous cellulose is, for example, preferably 5.20 mmol/g or less, more preferably 3.65 mmol/g or less, per 1 g (mass) of the fine fibrous cellulose. It is more preferably 3.50 mmol/g or less, and particularly preferably 3.00 mmol/g or less.
  • the unit mmol/g indicates the amount of the substituent per 1 g of the mass of the fine fibrous cellulose when the counter ion of the anionic group is a hydrogen ion (H + ).
  • the amount of anionic groups introduced into the fine fibrous cellulose can be measured, for example, by a conductivity titration method.
  • the introduced amount is measured by determining the change in conductivity while adding an alkali such as an aqueous sodium hydroxide solution to the obtained slurry containing fine fibrous cellulose.
  • FIG. 1 is a graph showing the relationship between the amount of dropped NaOH and the electrical conductivity with respect to the fine fibrous cellulose having a phosphate group.
  • the amount of phosphate groups introduced into the fine fibrous cellulose is measured, for example, as follows. First, a slurry containing fine fibrous cellulose is treated with a strongly acidic ion exchange resin. If necessary, a defibration process similar to the defibration process step described below may be performed on the measurement target before the treatment with the strongly acidic ion exchange resin. Next, a change in electric conductivity is observed while adding an aqueous sodium hydroxide solution, and a titration curve as shown in FIG. 1 is obtained. As shown in FIG.
  • first region the electrical conductivity sharply decreases at first
  • second region the conductivity starts to slightly increase
  • third region the increment of conductivity increases
  • the boundary point between the second region and the third region is defined as the point where the second derivative of the conductivity, that is, the amount of change in the increment (slope) of the conductivity is maximum.
  • the amount of alkali required in the first region is equal to the amount of strong acidic groups in the slurry used for titration
  • the amount of alkali required in the second region is the amount of weak acidic groups in the slurry used for titration. Will be equal.
  • the amount of strongly acidic groups is the same as the amount of phosphorus atoms regardless of the presence or absence of condensation.
  • the term "phosphoric acid group introduced amount (or phosphoric acid group amount)" or “substituent group introduced amount (or substituent amount)” simply means the strongly acidic group amount. Therefore, the value obtained by dividing the alkali amount (mmol) required in the first region of the titration curve obtained above by the solid content (g) in the slurry to be titrated is the phosphate group introduction amount (mmol/ g).
  • FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and the electric conductivity for the fine fibrous cellulose having a carboxyl group.
  • the amount of the carboxyl group introduced into the fine fibrous cellulose is measured, for example, as follows. First, a slurry containing fine fibrous cellulose is treated with a strongly acidic ion exchange resin. If necessary, a defibration process similar to the defibration process step described below may be performed on the measurement target before the treatment with the strongly acidic ion exchange resin. Then, a change in electric conductivity is observed while adding an aqueous sodium hydroxide solution, and a titration curve as shown in FIG. 2 is obtained. In the titration curve, as shown in FIG.
  • the boundary point between the first region and the second region is defined as the point at which the change amount of the differential value of the conductivity, that is, the increment (slope) of the conductivity becomes maximum.
  • the value obtained by dividing the amount of alkali (mmol) required in the first region of the titration curve by the solid content (g) in the fine fibrous cellulose-containing slurry to be titrated is the amount of introduced carboxyl group ( mmol/g).
  • the method of chemically treating the cellulose raw material is not particularly limited as long as it is a method capable of obtaining fine fibers. Examples thereof include, but are not limited to, acid treatment, ozone treatment, TEMPO oxidation treatment, enzyme treatment, and treatment with a compound capable of forming a covalent bond with a functional group in cellulose or fiber raw material. Further, when the fine fibrous cellulose has a substituent derived from phosphoric acid, for example, as a chemical treatment method, it is preferable to perform treatment with a compound having a phosphoric acid group and/or a salt thereof.
  • the production process of the fine fibrous cellulose includes a phosphate group introduction step.
  • the phosphoric acid group introducing step at least one compound selected from compounds capable of introducing a phosphoric acid group by reacting with a hydroxyl group of a fiber raw material containing cellulose (hereinafter, also referred to as “compound A”) Is a step of acting on a fiber raw material containing. By this step, a phosphoric acid group-introduced fiber is obtained.
  • the reaction of the fiber raw material containing cellulose and the compound A is performed in the presence of at least one kind selected from urea and its derivatives (hereinafter, also referred to as “compound B”). May be.
  • the reaction of the fiber raw material containing cellulose with the compound A may be carried out in the state where the compound B does not exist.
  • the method of allowing the compound A to act on the fiber raw material in the coexistence with the compound B there is a method of mixing the compound A and the compound B with the fiber raw material in a dry state, a wet state or a slurry state.
  • a fiber raw material in a dry state or a wet state it is preferable to use a fiber raw material in a dry state, and particularly preferable to use a fiber raw material in a dry state, since the reaction is highly uniform.
  • the form of the fiber raw material is not particularly limited, but is preferably cotton-like or thin sheet-like, for example.
  • Compound A and compound B may be added to the fiber raw material in the form of powder or solution dissolved in a solvent, or heated to a melting point or higher and melted.
  • the reaction since the reaction is highly uniform, it is preferable to add them in the form of a solution dissolved in a solvent, particularly in the state of an aqueous solution.
  • the compound A and the compound B may be added to the fiber raw material at the same time, may be added separately, or may be added as a mixture.
  • the method of adding the compound A and the compound B is not particularly limited, but when the compound A and the compound B are in the form of a solution, the fiber raw material may be immersed in the solution to absorb the liquid, and then taken out. The solution may be added dropwise. Further, the required amounts of compound A and compound B may be added to the fiber raw material, or excess amounts of compound A and compound B may be respectively added to the fiber raw material, and then excess compound A and compound B may be squeezed or filtered. May be removed.
  • the compound A used in this embodiment may be a compound having a phosphorus atom and capable of forming an ester bond with cellulose, such as phosphoric acid or a salt thereof, phosphorous acid or a salt thereof, dehydrated condensed phosphoric acid or a salt thereof.
  • phosphoric acid examples thereof include salts and phosphoric anhydride (diphosphorus pentoxide), but are not particularly limited.
  • phosphoric acid those having various purities can be used, and for example, 100% phosphoric acid (orthophosphoric acid) or 85% phosphoric acid can be used.
  • the dehydrated condensed phosphoric acid is one in which two or more molecules of phosphoric acid are condensed by a dehydration reaction, and examples thereof include pyrophosphoric acid and polyphosphoric acid.
  • examples of the phosphates and dehydrated condensed phosphates include lithium salts, sodium salts, potassium salts, ammonium salts of phosphoric acid or dehydrated condensed phosphoric acids, and these may have various degrees of neutralization.
  • phosphoric acid and phosphoric acid A sodium salt, a potassium salt of phosphoric acid, or an ammonium salt of phosphoric acid is preferable, and phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, or ammonium dihydrogen phosphate is more preferable.
  • the addition amount of the compound A to the fiber raw material is not particularly limited, but when the addition amount of the compound A is converted into the phosphorus atomic weight, the addition amount of the phosphorus atom to the fiber raw material (absolute dry mass) is 0.5% by mass or more. It is preferably 100% by mass or less, more preferably 1% by mass or more and 50% by mass or less, still more preferably 2% by mass or more and 30% by mass or less.
  • the amount of phosphorus atoms added to the fiber raw material within the above range, the yield of fine fibrous cellulose can be further improved.
  • the amount of phosphorus atoms added to the fiber raw material to be not more than the above upper limit, the effect of improving the yield and the cost can be balanced.
  • the compound B used in this embodiment is at least one selected from urea and its derivatives as described above.
  • Examples of the compound B include urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like.
  • the compound B is preferably used as an aqueous solution. From the viewpoint of further improving the homogeneity of the reaction, it is preferable to use an aqueous solution in which both compound A and compound B are dissolved.
  • the amount of the compound B added to the fiber raw material is not particularly limited, but is preferably 1% by mass or more and 500% by mass or less, more preferably 10% by mass or more and 400% by mass or less, More preferably, it is 100% by mass or more and 350% by mass or less.
  • the heat treatment temperature it is preferable to select a temperature at which phosphoric acid groups can be efficiently introduced while suppressing thermal decomposition or hydrolysis reaction of the fiber.
  • the heat treatment temperature is, for example, preferably 50° C. or higher and 300° C. or lower, more preferably 100° C. or higher and 250° C. or lower, and further preferably 130° C. or higher and 200° C. or lower.
  • equipment having various heat mediums can be used, and for example, a stirring dryer, a rotary dryer, a disk dryer, a roll type heater, a plate type heater, a fluidized bed dryer, an air stream.
  • a drying device, a reduced pressure drying device, an infrared heating device, a far infrared heating device, or a microwave heating device can be used.
  • the compound A is added to a thin sheet-shaped fiber raw material by a method such as impregnation and then heated, or the fiber raw material and the compound A are heated while kneading or stirring with a kneader or the like. Can be adopted. This makes it possible to suppress unevenness in the concentration of the compound A in the fiber raw material and more uniformly introduce the phosphate group into the surface of the cellulose fiber contained in the fiber raw material.
  • the heating device used for the heat treatment always keeps, for example, the water held by the slurry and the water generated by the dehydration condensation (phosphoric acid esterification) reaction between the compound A and the hydroxyl group contained in the cellulose or the like in the fiber raw material. It is preferable that the device can be discharged to the outside of the device system.
  • An example of such a heating device is a blower type oven.
  • the heat treatment time is, for example, preferably 1 second or more and 300 minutes or less, more preferably 1 second or more and 1000 seconds or less, and more preferably 10 seconds or more and 800 seconds or less after water is substantially removed from the fiber raw material. Is more preferable.
  • the introduction amount of the phosphate group can be set within a preferable range by setting the heating temperature and the heating time within appropriate ranges.
  • the phosphate group introduction step may be performed at least once, but may be repeated twice or more. By carrying out the phosphate group introduction step twice or more, many phosphate groups can be introduced into the fiber raw material.
  • an example of a preferable mode is a case where the phosphate group introducing step is performed twice.
  • the amount of the phosphate group introduced into the fiber raw material is, for example, preferably 0.10 mmol/g or more, more preferably 0.20 mmol/g or more, and 0.50 mmol/g per 1 g (mass) of the fine fibrous cellulose. It is more preferably at least g, and particularly preferably at least 1.00 mmol/g.
  • the amount of phosphate groups introduced into the fiber raw material is, for example, preferably 5.20 mmol/g or less per 1 g (mass) of fine fibrous cellulose, more preferably 3.65 mmol/g or less. More preferably, it is not more than 00 mmol/g. When the amount of the phosphate group introduced is within the above range, the fiber raw material can be easily made finer and the stability of the fine fibrous cellulose can be increased.
  • the fine fibrous cellulose production step includes a carboxyl group introduction step.
  • a fiber raw material containing cellulose is subjected to oxidation treatment such as ozone oxidation, Fenton's method, TEMPO oxidation treatment or the like, a compound having a group derived from a carboxylic acid or a derivative thereof, or a group derived from a carboxylic acid. It is carried out by treating the compound with an acid anhydride or a derivative thereof.
  • the compound having a group derived from a carboxylic acid is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and citric acid and aconitic acid. Examples include tricarboxylic acid compounds.
  • the derivative of the compound having a group derived from a carboxylic acid is not particularly limited, and examples thereof include an imidized product of an acid anhydride of a compound having a carboxyl group and a derivative of an acid anhydride of a compound having a carboxyl group.
  • the imidization product of an acid anhydride of a compound having a carboxyl group is not particularly limited, and examples thereof include imidization products of dicarboxylic acid compounds such as maleimide, succinimide, and phthalic acid imide.
  • the acid anhydride of the compound having a group derived from a carboxylic acid is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride.
  • An acid anhydride is mentioned.
  • the derivative of the acid anhydride of the compound having a carboxylic acid-derived group is not particularly limited, and examples thereof include compounds having a carboxyl group such as dimethyl maleic anhydride, diethyl maleic anhydride, and diphenyl maleic anhydride.
  • An acid anhydride in which at least a part of hydrogen atoms is substituted with a substituent such as an alkyl group or a phenyl group can be used.
  • the TEMPO oxidation treatment may be performed under the condition that the pH is 10 or more and 11 or less. Such treatment is also referred to as alkaline TEMPO oxidation treatment.
  • the alkaline TEMPO oxidation treatment can be performed, for example, by adding nitroxy radicals such as TEMPO as a catalyst, sodium bromide as a cocatalyst, and sodium hypochlorite as an oxidant to pulp as a fiber raw material. ..
  • the amount of the carboxyl group introduced into the fiber raw material varies depending on the kind of the substituent, but when the carboxyl group is introduced by TEMPO oxidation, for example, it is preferably 0.10 mmol/g or more per 1 g (mass) of the fine fibrous cellulose. , 0.20 mmol/g or more is more preferable, 0.50 mmol/g or more is further preferable, and 0.90 mmol/g or more is particularly preferable. Further, it is preferably 2.5 mmol/g or less, more preferably 2.20 mmol/g or less, and further preferably 2.00 mmol/g or less. In addition, when the substituent is a carboxymethyl group, it may be 5.8 mmol/g or less per 1 g (mass) of fine fibrous cellulose.
  • a washing step can be performed on the anionic group-introduced fiber, if necessary.
  • the washing step is performed, for example, by washing the anionic group-introduced fiber with water or an organic solvent.
  • the cleaning step may be performed after each step described below, and the number of times of cleaning performed in each cleaning step is not particularly limited.
  • the fiber raw material may be subjected to an alkali treatment between the anionic group introduction step and the defibration treatment step described later.
  • the method of alkali treatment is not particularly limited, and examples thereof include a method of immersing the anionic group-introduced fiber in an alkaline solution.
  • the alkaline compound contained in the alkaline solution is not particularly limited, and may be an inorganic alkaline compound or an organic alkaline compound.
  • sodium hydroxide or potassium hydroxide is preferably used as the alkali compound because of its high versatility.
  • the solvent contained in the alkaline solution may be either water or an organic solvent.
  • the solvent contained in the alkaline solution is preferably a polar solvent containing water or a polar organic solvent exemplified by alcohol, and more preferably an aqueous solvent containing at least water.
  • an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable because of its high versatility.
  • the temperature of the alkaline solution in the alkaline treatment step is not particularly limited, but is preferably 5° C. or higher and 80° C. or lower, and more preferably 10° C. or higher and 60° C. or lower.
  • the time for immersing the anionic group-introduced fiber in the alkali solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or more and 30 minutes or less, and more preferably 10 minutes or more and 20 minutes or less.
  • the amount of the alkaline solution used in the alkaline treatment is not particularly limited, but is preferably 100% by mass or more and 100000% by mass or less and 1000% by mass or more and 10000% by mass or less based on the absolute dry mass of the anionic group-introduced fiber. Is more preferable.
  • the anionic group-introduced fiber may be washed with water or an organic solvent after the anionic group introduction step and before the alkaline treatment step. After the alkali treatment step and before the defibration treatment step, it is preferable to wash the alkali-treated anionic group-introduced fiber with water or an organic solvent from the viewpoint of improving handleability.
  • Fine fiber cellulose is obtained by defibrating the anionic group-introduced fiber in the defibrating process.
  • a defibration processing device can be used.
  • the defibration processing device is not particularly limited, but includes, for example, a high-speed defibration machine, a grinder (stone crusher), a high-pressure homogenizer or an ultra-high pressure homogenizer, a high-pressure collision crusher, a ball mill, a bead mill, a disc refiner, a conical refiner, a twin screw refiner.
  • a kneader, a vibration mill, a homomixer under high speed rotation, an ultrasonic disperser, a beater, or the like can be used.
  • the anionic group-introduced fiber is preferably diluted with a dispersion medium to form a slurry.
  • a dispersion medium water and one or more selected from organic solvents such as polar organic solvents can be used.
  • the polar organic solvent is not particularly limited, but for example, alcohols, polyhydric alcohols, ketones, ethers, esters, aprotic polar solvents and the like are preferable.
  • alcohols include methanol, ethanol, isopropanol, n-butanol, isobutyl alcohol and the like.
  • polyhydric alcohols include ethylene glycol, propylene glycol, glycerin and the like.
  • ketones examples include acetone and methyl ethyl ketone (MEK).
  • ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, and the like.
  • esters include ethyl acetate, butyl acetate and the like.
  • the aprotic polar solvent examples include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP) and the like.
  • the present invention also relates to a cosmetic having the above-mentioned oil-in-water emulsifier for cosmetics and an oily component.
  • the cosmetic of the present invention is an oil-in-water emulsion composition.
  • the cosmetic also contains an aqueous component.
  • oily ingredients contained in cosmetics include liquid paraffin, squalane, isododecane, hemisqualane, hydrogenated polyisobutene, cetyl octanoate, isopropyl palmitate, myristyl myristate, cetyl palmitate, macadamia nut oil, jojoba oil, and meadow homeo.
  • the oily component may be used alone
  • the oily component contained in the cosmetic is preferably at least one selected from hydrocarbon oils, ester oils, vegetable oils, silicone oils, fluorine oils, ultraviolet absorbers and fragrances.
  • the oil component may contain an oil-soluble component.
  • oil-soluble components include surfactants and emulsification aids. Above all, it is preferable to further add an emulsification aid to the cosmetic, and it is more preferable to further add at least one selected from higher fatty acids and higher alcohols as the emulsification aid.
  • the aqueous component contained in the cosmetic examples include water or various aqueous solutions. Further, the aqueous component also includes a water-soluble component, and for example, glycerin, saccharides, alcohols, salts such as sodium chloride or potassium carbonate, and acids such as citric acid and phosphoric acid can be added.
  • a water-soluble component for example, glycerin, saccharides, alcohols, salts such as sodium chloride or potassium carbonate, and acids such as citric acid and phosphoric acid can be added.
  • the oil-in-water emulsifier contains the above-mentioned fine fibrous cellulose as a main component.
  • the content of the surfactant is preferably 0.1% by mass or less based on the total mass of the cosmetic. In the present specification, it can be said that the cosmetic material does not substantially contain the surfactant if the content of the surfactant is 0.1% by mass or less.
  • the content of the oil-in-water emulsifier in the cosmetic is not particularly limited, but in order to exhibit sufficient emulsification performance and emulsion stability, the oil component/emulsifier mass ratio is 0.1 or more and 350 or more. It is preferably the following or less, more preferably 0.1 or more and 300 or less, still more preferably 5 or more and 200 or less.
  • the mass ratio of oily component/fine fibrous cellulose is preferably 0.1 or more and 350 or less, more preferably 0.1 or more and 300 or less, and further preferably 5 or more and 200 or less.
  • the content of the oil-in-water emulsifier with respect to the total mass of the cosmetic is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and More preferably, it is 1% by mass or more and 1% by mass or less.
  • the content of the fine fibrous cellulose is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, based on the total mass of the cosmetic. It is more preferable that the content is 0.1% by mass or more and 1% by mass or less.
  • the content of the oily component relative to the total mass of the cosmetic is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.5% by mass or more and 30% by mass or less.
  • the content of the oil-in-water emulsifier, the fine fibrous cellulose and the oil component in the cosmetic is within the above range, a cosmetic having better emulsion stability can be obtained.
  • the cosmetics of the present invention may contain additives depending on the intended use of the cosmetics within a range that does not impair the effects of the present invention.
  • the additive include an ultraviolet absorber, an inorganic/organic pigment, a coloring material, a polyhydric alcohol, a saccharide, a polymer compound, a physiologically active ingredient, a percutaneous absorption promoter, a solvent, an antioxidant, a pH adjusting agent, and a chelate.
  • examples include, but are not limited to, agents, fragrances, antiseptics, and the like.
  • the method for producing the cosmetic of the present invention can be appropriately selected according to the type of components used and the like, and is not particularly limited.
  • the method for producing a cosmetic preferably includes a step of mixing an oil component with an aqueous component containing fine fibrous cellulose. Since the cosmetic of the present invention contains an aqueous component and an oily component, the cosmetic which is the oil-in-water emulsion composition of the present invention can be produced by mixing the aqueous phase and the oil phase.
  • an aqueous phase containing fine fibrous cellulose and an aqueous component is prepared, each component in the aqueous phase is dissolved, then uniformly dispersed in advance, and mixed with an oil phase (including an oily component) adjusted at an appropriate temperature. To do.
  • a cosmetic which is an oil-in-water emulsion composition, can be produced by emulsifying with a homomixer or the like.
  • the cosmetics of the present invention are preferably used as, for example, skin cosmetics, makeup cosmetics, hair cosmetics, UV protective cosmetics, and further preshave lotions, aftershave lotions, perfumes, ointments and the like.
  • skin cosmetics include lotions, emulsions, creams, beauty essences, packs, foundations, sunscreens, suntan cosmetics, and various lotions.
  • the cream include cold cream, vanishing cream, massage cream, emollient cream, cleansing cream, moisture cream, hand cream, body cream and the like.
  • makeup cosmetics include makeup bases, foundations, eye shadows, and cheeks.
  • hair cosmetics include hair styling agents (hair foams, gel-like hair styling agents, etc.), hair waxes, hair treatment agents, hair dyes and the like.
  • hair treatment agent examples include hair cream, treatment lotion, hair milk and the like.
  • 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.
  • the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by the examples.
  • the blending amount in the table represents% by mass.
  • a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass of the raw material pulp (absolute dry mass) to give 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, and 150 parts by mass of water.
  • the obtained chemical liquid-impregnated pulp was heated for 200 seconds with a hot air dryer at 165° C. to introduce a phosphoric acid group into the cellulose in the pulp to obtain phosphorylated pulp. Then, the phosphorylated pulp obtained was subjected to a washing treatment.
  • the washing treatment was carried out by repeating the operation of filtering and dehydrating the pulp dispersion obtained by pouring 10 L of ion-exchanged water per 100 g of phosphorylated pulp (absolute dry mass), stirring the pulp to uniformly disperse the pulp. went. When the electric conductivity of the filtrate became 100 ⁇ S/cm or less, the washing end point was set. Next, the phosphorylated pulp after washing was subjected to neutralization treatment as follows. First, the washed phosphorylated pulp was diluted with 10 L of ion-exchanged water, and 1N aqueous sodium hydroxide solution was added little by little while stirring to obtain a phosphorylated pulp slurry having a pH of 12 or more and 13 or less. ..
  • the phosphorylated pulp slurry was dehydrated to obtain a neutralized phosphorylated pulp.
  • the above washing treatment was performed on the phosphorylated pulp after the neutralization treatment.
  • the infrared absorption spectrum of the phosphorylated pulp thus obtained was measured using FT-IR. As a result, absorption based on the phosphate group was observed around 1230 cm ⁇ 1 , and it was confirmed that the phosphate group was added to the pulp.
  • ION-exchanged water was added to the obtained phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass.
  • This slurry was treated once with a wet atomizer (Starburst manufactured by Sugino Machine Ltd.) at a pressure of 200 MPa to obtain a fine fibrous cellulose dispersion liquid containing fine fibrous cellulose 1. It was confirmed by X-ray diffraction that the fine fibrous cellulose 1 maintained the cellulose type I crystal.
  • ⁇ Production Example 2 Production of fine fibrous cellulose 2> Fine fibrous cellulose dispersion liquid containing fine fibrous cellulose 2 in the same manner as in Production Example 1 except that the cellulose suspension was treated 10 times at a pressure of 200 MPa with a wet atomization device (Starburst manufactured by Sugino Machine Ltd.). Got It was confirmed by X-ray diffraction that the fine fibrous cellulose 2 maintained the cellulose type I crystal.
  • Fine fibrous cellulose 3 was produced in the same manner as in Production Example 1 except that the phosphorylated pulp before the neutralization treatment was further subjected to the phosphorylation treatment for 200 seconds, the washing treatment, and the neutralization treatment. A fine fibrous cellulose dispersion liquid containing was obtained. It was confirmed by X-ray diffraction that the fine fibrous cellulose 3 maintained the cellulose type I crystal.
  • Fine fibrous cellulose 4 was prepared in the same manner as in Production Example 1 except that the phosphorylated pulp before the neutralization treatment was further subjected to the phosphorylation treatment for 150 seconds, the washing treatment, and the neutralization treatment. A fine fibrous cellulose dispersion liquid containing was obtained. It was confirmed by X-ray diffraction that the fine fibrous cellulose 4 maintained the cellulose type I crystal.
  • ⁇ Production Example 5 Production of fibrous cellulose 5> The same procedure as in Production Example 1 was carried out except that the content of ammonium dihydrogen phosphate in the chemical liquid-impregnated pulp was adjusted to 4.5 parts by mass, but clogging occurred in the wet atomizer and the slurry was allowed to pass through. I could't. That is, a fibrous cellulose dispersion liquid containing fibrous cellulose 5 which was not subjected to the wet atomization treatment was obtained. It was confirmed by X-ray diffraction that the fibrous cellulose 5 maintained the cellulose type I crystal.
  • the washing treatment is performed by dewatering the pulp slurry after TEMPO oxidation to obtain a dewatering sheet, pouring 5000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. It was When the electric conductivity of the filtrate became 100 ⁇ S/cm or less, the washing end point was set.
  • Ion-exchanged water was added to the obtained TEMPO oxidized pulp to prepare a slurry having a solid content concentration of 2% by mass.
  • This slurry was treated once with a wet atomizer (Starburst manufactured by Sugino Machine Ltd.) at a pressure of 200 MPa to obtain a fine fibrous cellulose dispersion liquid containing fine fibrous cellulose 6. It was confirmed by X-ray diffraction that the fine fibrous cellulose 6 maintained the cellulose type I crystal.
  • Viscosity measurement Water was added to the fine fibrous cellulose-containing dispersions obtained in Production Examples 1 to 4 and 6 and the fibrous cellulose-containing dispersion obtained in Production Example 5 to adjust the concentration of each fibrous cellulose to 0. It was adjusted to 0.4% by mass. Each suspension thus obtained was allowed to stand at 25° C. for 24 hours, and then using a B-type viscometer (Analog viscometer T-LVT manufactured by BLOOKFIELD) at 25° C., a rotation speed of 3 rpm ⁇ 3 minutes. The viscosity was measured with.
  • B-type viscometer Analog viscometer T-LVT manufactured by BLOOKFIELD
  • the supernatant of the fine fibrous cellulose dispersion was diluted with water to a concentration of 0.01 to 0.1% by mass and added dropwise to the hydrophilized carbon grid film. After drying, it was stained with uranyl acetate and observed with a transmission electron microscope (JEOL-2000EX manufactured by JEOL Ltd.).
  • the fibrous cellulose dispersion was diluted with water to a concentration of 0.01 to 0.1% by mass and the supernatant was observed in the same manner, but no fibers were present. Therefore, the fiber width of the fibers present in the precipitate was used as the fiber width of Production Example 5.
  • the diluted solution of Production Example 5 was stirred and added dropwise to a slide glass. It was covered with a cover glass and observed with a digital microscope (KH-7700, manufactured by Hirox).
  • Crystallinity Index (Crystallinity) The crystallinity of the fine fibrous celluloses 1 to 4 and 6 and the fibrous cellulose 5 was measured using an X-ray diffractometer and calculated from the following formula. The “crystallization index” in the following calculation formula is also referred to as “crystallinity”.
  • Cellulose type I crystallization index (%) [(I22.6-I18.5)/I22.6] ⁇ 100 (1)
  • Indicates strength 0.45 ⁇ (m ⁇ rad/sec) (2) [ ⁇ represents one-sided amplitude (m), and ⁇ represents angular velocity (rad/sec). ].
  • the phosphoric acid group amount of the fine fibrous cellulose obtained in Production Examples 1 to 4 and 6 is the fine fibrous cellulose containing the target fine fibrous cellulose.
  • a fibrous cellulose-containing slurry prepared by diluting a cellulose dispersion with ion-exchanged water to a content of 0.2% by mass is treated with an ion-exchange resin, and then titrated with an alkali.
  • the treatment with the ion-exchange resin was carried out by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amber Jet 1024; Organo Co., Ltd., already conditioned) to the above-mentioned fibrous cellulose-containing slurry and performing a shaking treatment for 1 hour. , And the resin and the slurry were separated by pouring onto a mesh having an opening of 90 ⁇ m. Further, titration with an alkali is performed by adding 50 ⁇ L of a 0.1 N sodium hydroxide aqueous solution to the fibrous cellulose-containing slurry after the treatment with the ion exchange resin once every 30 seconds, and showing the electric conductivity of the slurry.
  • a strongly acidic ion-exchange resin Amber Jet 1024; Organo Co., Ltd., already conditioned
  • the phosphate group amount (mmol/g) was obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 1 in the measurement result by the solid content (g) in the titration target slurry. Calculated by The amount of carboxy groups in the fine fibrous cellulose is produced by diluting the fine fibrous cellulose dispersion liquid containing the target fine fibrous cellulose with ion-exchanged water to a content of 0.2% by mass. The contained slurry was treated with an ion exchange resin and then titrated with an alkali to measure.
  • the treatment with the ion-exchange resin was carried out by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amber Jet 1024; Organo Co., Ltd., already conditioned) to the above-mentioned fibrous cellulose-containing slurry and performing a shaking treatment for 1 hour. , And the resin and the slurry were separated by pouring onto a mesh having an opening of 90 ⁇ m.
  • titration with an alkali was carried out by adding 50 ⁇ L of a 0.1 N sodium hydroxide aqueous solution to the slurry containing fibrous cellulose after treatment with an ion exchange resin once every 30 seconds, and measuring the electric conductivity of the slurry. This was done by measuring the change in value.
  • the amount of carboxy groups was obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 2 of the measurement result by the solid content (g) in the titration target slurry. It was calculated.
  • the amount of phosphate groups introduced into the fibrous cellulose 5 obtained in Production Example 5 was measured by the neutralization titration method. First, the fibrous cellulose was diluted with ion-exchanged water, 1N hydrochloric acid was added with stirring, and then the fibrous cellulose was recovered by filtration and dehydration. This operation was repeated to completely convert the phosphate group of the fibrous cellulose into the acid form. Then, the obtained fibrous cellulose was diluted with ion-exchanged water and then filtered and dehydrated to obtain a dehydrated sheet. By repeating the operation, excess hydrochloric acid was sufficiently washed out.
  • the fine fibrous celluloses obtained in Production Examples 1 to 4 and 6 exhibited sufficient viscosity.
  • the fibrous cellulose 5 obtained in Production Example 5 the phosphorylation reaction was not sufficient, and only coarse fibers having a fiber width of 10 ⁇ m or more were observed even after defibration, and fine single fibers having a fiber width of 1000 nm or less were observed.
  • the phosphorylation reaction was not sufficient, and only coarse fibers having a fiber width of 10 ⁇ m or more were observed even after defibration, and fine single fibers having a fiber width of 1000 nm or less were observed.
  • Examples 1 to 5 and Comparative Examples 1 to 8 The ingredients were mixed so that the compositions shown in Tables 2 and 3 were mixed to prepare a cosmetic.
  • the aqueous phase was uniformly mixed. Separately, the oil phase was heated if necessary and uniformly mixed. While the aqueous phase was being stirred, the oil phase was added and emulsified using a homomixer or the like. The blending amount of each component in the table is% by mass.
  • Comparative Example 1 the oil could not be emulsified because the fibrous cellulose was coarse.
  • Comparative Examples 2 and 3 since the water-soluble polymer which was not alkyl-modified was used, it did not exhibit an emulsifying action and could not be emulsified.
  • Comparative Example 4 since the alkyl-modified water-soluble polymer was used, it showed an emulsifying action, but the stickiness derived from the water-soluble polymer was strong and the usability was poor.
  • Comparative Examples 5 to 6 the surfactant was blended, so that the emulsion stability of the cosmetic was good, but the stickiness derived from the surfactant was strong and the usability was poor.
  • Example 6 to 12 Each component was mixed so that the composition shown in Table 4 might be obtained, and the cosmetics were prepared. The respective components were mixed in the same manner as in Examples 1 to 5 described above.
  • An application example of the cosmetic of the present invention was prepared as follows.
  • Examples 13 to 21 were evaluated in the same manner as described above for the stability of emulsifier and the feeling of use (presence or absence of stickiness), and good evaluations were obtained in all of the application examples.
  • Example 13 lotion
  • Fine fibrous cellulose 1 0.15 (mass%) 2.
  • Butylene glycol 5.00 3.
  • Glycerin 5.00 4.
  • Preservative suitable amount 5.
  • Citric acid 0.03
  • Purified water balance 7.
  • Ethyl linoleate 1.00 8.
  • Hydrogenated retinol 1.00 9.
  • Ascorbyl tetrahexyl decanoate 1.00 Total 100.00
  • the above components 1 to 5 were uniformly mixed.
  • Ingredients 6-8 were mixed uniformly. While stirring 1-5, 6-8 were added and mixed until uniform.
  • Example 14 Watery fragrance
  • Fine fibrous cellulose 2 0.15 (mass%) 2. Propanediol 3.00 3. Preservative suitable amount 4. pH adjusting agent 5. Purified water balance 6. Fragrance 5.00 Total 100.00
  • the above components 1 to 5 were uniformly mixed. Ingredients 1 to 5 were added to Component 6 with stirring and mixed until uniform.
  • Example 15 Cleansing gel
  • Fine fibrous cellulose 3 0.7 (mass%) 2.
  • Dipropylene glycol 10.0 3.
  • Preservative suitable amount 4.
  • pH adjusting agent 5.
  • Purified water balance 6.
  • Cetyl isooctanoate 10.0 7.
  • Triethylhexanoin 10.0 8.
  • Dimethicone 5.0 9.
  • the above components 1 to 5 were uniformly mixed.
  • Ingredients 6-9 were mixed uniformly.
  • Ingredients 1-5 were added with stirring and ingredients 6-9 were mixed with a homomixer until uniform.
  • Example 16 Hair milk
  • Fine fibrous cellulose 4 0.2 (mass%) 2.
  • Preservative suitable amount 5.
  • pH adjusting agent 6.
  • Purified water balance 7.
  • Cyclomethicone 15.0 9.
  • the above components 1 to 6 were uniformly mixed. Ingredients 7-9 were mixed uniformly. Ingredients 1 to 6 were added with stirring and ingredients 7 to 9 were mixed with a homomixer until uniform.
  • Example 17 hair treatment
  • Fine fibrous cellulose 6 1.0 (mass%) 2. Polyvinylpyrrolidone 0.2 3. Ethanol 6.0 4. Preservative suitable amount 5. pH adjusting agent 6. Purified water balance 7. High Polymerization Dimethicone 8.0 8. Cyclomethicone 15.0 9. Isostearyl alcohol 1.0 Total 100.0
  • the above components 1 to 6 were uniformly mixed. Ingredients 7-9 were mixed uniformly. Ingredients 1 to 6 were added with stirring and ingredients 7 to 9 were mixed with a homomixer until uniform.
  • Example 18 Sunscreen milk
  • Butylene glycol 5.0 3.
  • Preservative suitable amount 4.
  • pH adjusting agent 5.
  • Purified water balance 7.
  • SSQP50ZJEJ 20.0 9.
  • Polysilicone-15 1.0 Total 100.0 *SSQP50ZJEJ: squalane, zinc oxide, polyhydroxystearic acid, jojoba ester (Nikko Chemicals)
  • the above components 1 to 6 were uniformly mixed.
  • Ingredients 7 to 10 were mixed uniformly.
  • Ingredients 1-6 were added with stirring and ingredients 7-10 were mixed with a homomixer until uniform.
  • Example 19 Sunscreen gel
  • Fine fibrous cellulose 3 0.6 (mass%) 2. Preservative suitable amount 3. pH adjusting agent 4. Butylene glycol 5.0 5. Purified water balance 6. Ethylhexyl methoxycinnamate 7.5 7. t-Butyl methoxydibenzoylmethane 6.0 8. Bisethylhexyloxyphenol methoxyphenyl triazine 3.0 9. Homosalate 3.0 10. Isopropyl adipate 3.0 11. Isostearic acid 1.0 Total 100.0 The above components 1 to 5 were uniformly mixed. Ingredients 6 to 11 were heated and uniformly mixed, and cooled to room temperature. Ingredients 1 to 5 were added with stirring, and ingredients 6 to 11 were added and mixed by a homomixer until uniform.
  • Oxidative hair dye Oxidative hair dye 1 agent A) Oleic acid 1.0 (mass%) Cetanol 8.0 Mineral oil 2.0 B) Propylene glycol 5.0 Sodium erythorbate 0.4 Sodium sulfite 0.5 Paraphenylenediamine 0.2 Resorcin 1.0 Para-aminophenol 0.5 2,5-diaminopyridine 0.2 Fine fibrous cellulose 1 10.0 Chelating agent Suitable amount C) Ammonia water 8.0 Water balance Total 100.0 After heating and dissolving A and B at 80° C., emulsifying with a homomixer while adding B to A. After stirring and cooling, C is added at 40°C. Oxidizing hair dye 2 agents A) Hydrogen peroxide (30% aqueous solution) 20.0 (mass %) Water balance Total 100.0 Mix A homogeneously.
  • Example 21 Liquid foundation
  • A) Isostearic acid 0.8 (mass%) Methylheptyl laurate 10.0 Pigment grade titanium oxide 9.0 Yellow iron oxide 3.0 Red iron oxide 1.5 Black iron oxide 1.5
  • a and B are homogenized at room temperature and emulsified with a homomixer while adding A to B.
  • the oil-in-water emulsifier of the present invention can provide a highly stable cosmetic product without using a surfactant.
  • the oil-in-water emulsifier of the present invention makes it possible to provide a cosmetic material having high safety and excellent feeling in use.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
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  • Biotechnology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Cosmetics (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une préparation cosmétique qui présente une excellente stabilité sans utiliser de tensioactif, et qui a une excellente sensation d'utilisation. La présente invention concerne : un agent émulsifiant huile-dans-eau qui est utilisé pour la formation d'une préparation cosmétique, et qui contient de la cellulose fibreuse présentant une largeur de fibre inférieure ou égale à 1000 nm ; et une préparation cosmétique qui contient cet agent émulsifiant huile-dans-eau.
PCT/JP2020/002146 2019-01-30 2020-01-22 Agent émulsifiant huile-dans-eau et préparation cosmétique WO2020158543A1 (fr)

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JP2019014490A JP7220088B2 (ja) 2019-01-30 2019-01-30 水中油型乳化剤および化粧料
JP2019-014490 2019-01-30

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WO2022097544A1 (fr) * 2020-11-05 2022-05-12 日本製紙株式会社 Préparation nettoyante
JP7412472B2 (ja) * 2022-03-31 2024-01-12 大王製紙株式会社 皮膚外用剤

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017014115A (ja) * 2015-06-26 2017-01-19 花王株式会社 皮膚化粧料
JP2017109986A (ja) * 2016-08-08 2017-06-22 第一工業製薬株式会社 日焼け止め化粧料
WO2018230228A1 (fr) * 2017-06-16 2018-12-20 株式会社マツモト交商 Produit cosmétique anti-solaire de type huile-dans-eau

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017014115A (ja) * 2015-06-26 2017-01-19 花王株式会社 皮膚化粧料
JP2017109986A (ja) * 2016-08-08 2017-06-22 第一工業製薬株式会社 日焼け止め化粧料
WO2018230228A1 (fr) * 2017-06-16 2018-12-20 株式会社マツモト交商 Produit cosmétique anti-solaire de type huile-dans-eau

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