Composition and cellulose derivative

Abstract

Provided are: a cellulose derivative having excellent compatibility with respect to various oil agents; and a composition containing the cellulose derivative.　The present invention provides a composition that contains: a cellulose derivative containing monovalent organic groups (La) that are substituted at at least some of hydrogen atoms constituting hydroxy groups in a cellulose, that have a hydrocarbon group having six or more carbon atoms at ends thereof, and that do not have an ether bond, wherein the average substitution degree of the monovalent organic groups (La) is equal to or greater than 1.1; and an oil agent. It is preferable that the oil agent be at least one type of oil selected from the group consisting of hydrocarbon oils, ester oils, and silicone oils.

Description

Composition and cellulose derivatives

[0001] The present disclosure relates to a composition and a cellulose derivative. More specifically, the present disclosure relates to a composition containing a cellulose derivative and an oil, and a cellulose derivative. This application claims priority to Japanese Patent Application No. 2021-193177 filed in Japan on November 29, 2021, and Japanese Patent Application No. 2021-196936 filed in Japan on December 3, 2021, the contents of which are incorporated herein by reference.

[0002] Cellulose is a polymeric compound formed by the polymerization of numerous glucose units (glucopyranose units) via β-1,4-glucosidic bonds. Currently, cellulose and its derivatives are used in a wide range of applications, including paper, cosmetics applied to the skin, coatings, paints, and film-forming agents.

[0003] For example, Patent Documents 1 and 2 disclose cosmetics containing specific cellulose derivatives, Patent Document 3 discloses an external skin preparation containing a specific cellulose derivative, and Patent Document 4 discloses a film-forming agent containing a specific cellulose derivative.

[0004] Japanese Patent Application Laid-Open No. 2017-105757 Japanese Patent Application Laid-Open No. 2007-527861 Japanese Patent Application Laid-Open No. 8-175929 Japanese Patent Application Laid-Open No. 2014-12852

[0005] When cellulose and its derivatives are used as product components or materials, it is important that they have excellent compatibility with solvents, such as solubility, swelling, and dispersibility in the solvent. However, the cosmetic preparation of Patent Document 1 requires the use of a solvent containing a hydrocarbon oil and an ester oil mixed in a specific ratio as the oil agent in order to achieve excellent film-forming properties, and does not disclose or suggest the use of hydrocarbon oil alone or ester oil alone as the oil agent. The cosmetic composition disclosed in Patent Document 2 contains a non-volatile oil agent such as wax, and the solubility and swelling of the cellulose derivative in volatile oil alone is not examined. Since non-volatile oil agents remain as a film together with the cellulose derivative after application, high compatibility is not necessarily required. Patent Document 3 only discloses an emulsified topical skin preparation. Patent Document 4 only examines the solubility of cellulose esters in acetone as an organic solvent, but does not examine their solubility in oil agents.

[0006] As described above, Patent Documents 1 to 4 disclose only methods using emulsification or acetone without using an oil agent, or methods using a non-volatile oil agent or a specific mixed solvent as an oil agent, for compositions containing a cellulose derivative, and the range of oil agents that can be used is limited. Therefore, there is a demand for a composition that contains a cellulose derivative and that can use a variety of oil agents.

[0007] Therefore, an object of the present disclosure is to provide a cellulose derivative that has excellent affinity for various oily agents, and a composition containing the cellulose derivative.

[0008] As a result of intensive research to solve the above problems, the inventors of the present disclosure have found that a specific cellulose derivative has excellent affinity for various oils. The present disclosure relates to a product completed based on these findings.

[0009] That is, the present disclosure provides a monovalent organic group (L) having a hydrocarbon group having 6 or more carbon atoms at its terminal and no ether bond, which is substituted for at least a portion of the hydrogen atoms constituting the hydroxyl groups in cellulose. a ), and the monovalent organic group (L aThe present invention provides a composition comprising a cellulose derivative having an average degree of substitution of 1.1 or more and an oil agent.

[0010] The oil is preferably one or more selected from the group consisting of hydrocarbon oils, ester oils, and silicone oils.

[0011] The content of the hydrocarbon oil is preferably more than 80% by mass.

[0012] The content of the ester oil is preferably more than 50% by mass.

[0013] The cellulose derivative has a monovalent organic group (L c ) is preferably provided.

[0014] In the cellulose derivative, the monovalent organic group (L a The average degree of substitution of the monovalent organic group (L c ) or more.

[0015] In the cellulose derivative, the monovalent organic group (L c ) preferably has an average degree of substitution of 1.0 or less.

[0016] The monovalent organic group (L a ) is represented by the following formula (1) -X 1 -R 1 (1) [wherein, R 1 represents the hydrocarbon group having 6 or more carbon atoms, and X 1 represents a direct bond or a group that can bond to an oxygen atom constituting a hydroxy group in the cellulose to form a linking group. The bond extending to the left bonds to an oxygen atom in the cellulose skeleton.

[0017] The composition is preferably for use as an oil-based cosmetic.

[0018] The present disclosure also provides a cellulose derivative represented by the following formula (2): -O-R 2(2) [wherein, R 2 represents a hydrocarbon group having 6 or less carbon atoms] at the terminal thereof. b The present invention provides a cellulose derivative comprising:

[0019] The monovalent organic group (L b ) preferably contains two or more ether bonds.

[0020] The monovalent organic group (L b ) is preferably bonded to the cellulose skeleton via an ester bond with the oxygen atom constituting the hydroxy group as a constituent atom.

[0021] The monovalent organic group (L b ) preferably contains a (poly)oxyalkylene chain.

[0022] a monovalent organic group (L) having a hydrocarbon group having 6 or more carbon atoms at its terminal and no ether bond, which is substituted for at least a portion of the hydrogen atoms constituting the hydroxyl groups in the cellulose; a ) is preferably provided.

[0023] The monovalent organic group (L a The average degree of substitution of the monovalent organic group (L b ) is preferably greater than the average degree of substitution.

[0024] The present disclosure also provides a composition comprising the cellulose derivative and an oil agent.

[0025] The present disclosure also provides an oil-based cosmetic comprising the above composition.

[0026] The composition of the present disclosure exhibits excellent affinity of the cellulose derivative to the oil even when various oils are used, and therefore tends to exhibit excellent solubility and swelling of the cellulose derivative and excellent film-forming properties, even when the content of, for example, hydrocarbon oil or ester oil is high.

[0027] The cellulose derivative prepared in Example 9 1 The H-NMR spectrum is shown.

[0028] The composition of the present disclosure includes at least a cellulose derivative and an oil. The cellulose derivative has at least a monovalent organic group having a terminal hydrocarbon group having 6 or more carbon atoms and no ether bond, the monovalent organic group substituting at least a portion of the hydrogen atoms constituting the hydroxyl groups in the cellulose, and the average substitution degree of the monovalent organic group is 1.1 or more.

[0029] In this specification, "cellulose" refers to a substance with the molecular formula (C6H 10 O5)n. For example, the cellulose does not include substituents substituted on cellulose, such as the hydroxypropyl group in hydroxypropyl cellulose (CAP), the hydroxyethyl group in hydroxyethyl cellulose (HEC), or the acyl group in cellulose acetate butyrate (CAB). The cellulose derivative is specifically a bonded body of repeating units represented by the following formula (A). The cellulose derivative of the present disclosure is a cellulose derivative represented by the formula (A) in which one or more of the three groups bonded to the oxygen atom (i.e., the group to which the bonds extending from the three oxygen atoms are bonded) is a monovalent organic group (L a ) or a monovalent organic group (L b In this specification, the term "cellulose skeleton" refers to groups excluding groups bonded to oxygen atoms derived from hydroxy groups in cellulose.

[0030] In this specification, the monovalent organic group having the above-mentioned hydrocarbon group having 6 or more carbon atoms at its terminal and having no ether bond is referred to as a “monovalent organic group (L a ) is sometimes referred to as such.

[0031] Monovalent organic group (L a ) may substitute a hydrogen atom of any of the three hydroxy groups in the glucose unit of cellulose. a ) may be bonded to the oxygen atom of any of the three hydroxy groups in the glucose unit of the cellulose. a) may be present in only one kind or in two or more kinds.

[0032] Monovalent organic group (L a ) has a hydrocarbon group having 6 or more carbon atoms at its terminal. a ), the cellulose derivative (A) has excellent affinity for various oils. The number of carbon atoms in the hydrocarbon group is preferably 7 or more, more preferably 10 or more, and even more preferably 12 or more. The number of carbon atoms in the hydrocarbon group is preferably 24 or less, more preferably 18 or less. When the number of carbon atoms is 24 or less, the monovalent organic group (L a ) and has excellent affinity for oils.

[0033] Monovalent organic group (L a The hydrocarbon group at the end of the alkyl group (B) may be linear or branched, but is preferably a linear group having 6 or more carbon atoms. The hydrocarbon group may be saturated or unsaturated.

[0034] Examples of the hydrocarbon group include a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an undecyl group, a dodecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a myristyl group, a pentadecyl group, a myristyl group, a heptadecyl group, a stearyl group, and an oleyl group.

[0035] Monovalent organic group (L a ) does not have an ether bond (—O—). Note that the oxygen atom in the hydroxy group in cellulose, i.e., the monovalent organic group (L a The oxygen atom that connects the cellulose skeleton to the monovalent organic group (L a Therefore, the monovalent organic group (L a) may be bonded to the cellulose skeleton via an ether bond with the oxygen atom constituting the hydroxy group in cellulose as a constituent atom. In addition, for example, a group in which an organic group is substituted with an ether bond to the hydroxy group in a hydroxypropyl group in CAP has an ether bond derived from the hydroxypropyl group in a portion not contained in the cellulose skeleton, and therefore, a monovalent organic group (L a ) does not apply.

[0036] Monovalent organic group (L a ) is directly bonded to an oxygen atom constituting a hydroxy group in cellulose, or is bonded via a linking group having the oxygen atom (oxygen atom in the cellulose skeleton) as a constituent atom. The linking group is a group formed by bonding the oxygen atom to a monovalent organic group (L a ) The linking group may be an ether bond, an ester bond, a urethane bond, a phosphinic acid group, a thionoester bond, or the like. Among these, an ester bond is preferred from the viewpoint of ease of introduction.

[0037] Monovalent organic group (L a ) is preferably a group represented by the following formula (1): 1 -R 1 (1) [wherein, R 1 represents the hydrocarbon group having 6 or more carbon atoms, and X 1 indicates a direct bond or a group that can bond with an oxygen atom constituting a hydroxy group in cellulose to form a linking group. The bond extending to the left bonds to an oxygen atom in the cellulose skeleton.

[0038] X 1 Examples of the linking group that can be formed by X include those mentioned above. 1 Examples of X include a direct bond, a carbonyl group (-C(=O)-), an amide group (-C(=O)-N(-R)-), (-P(=O)(-R)-), and a thiocarbonyl group (-C(=S)-). R is a hydrogen atom or a monovalent organic group. 1 Among them, a carbonyl group is preferable. a ) is preferably an acyl group.

[0039] In the cellulose derivative (A), the monovalent organic group (L a ) average degree of substitution (DS a ) is 1.1 or more, preferably 1.4 or more, more preferably 1.7 or more, even more preferably 2.0 or more, and particularly preferably 2.2 or more. a When the DS is 1.1 or more, the cellulose derivative (A) has excellent affinity for various oils. a is 3.0 or less, preferably 2.9 or less, and may be 2.8 or less, or 2.7 or less. a When the value of the monovalent organic group (L b ) can be introduced, and the cellulose derivative has better affinity for oily agents.

[0040] The average degree of substitution in this specification refers to the number (average value) of groups per repeating unit represented by the above formula (A) in the cellulose derivative. The average degree of substitution in this specification can be measured by a known or conventional method, for example, 1 H-NMR and 13 Specifically, for example, the protons in the cellulose skeleton and the monovalent organic group (L a In addition, when the peak of the monovalent organic group in the cellulose derivative overlaps with the peak derived from the cellulose skeleton in the NMR spectrum, the cellulose derivative obtained by benzoylating all the remaining hydroxy groups in the cellulose skeleton in the cellulose derivative can be calculated from the integral ratio of the proton of the terminal methyl group of the hydrocarbon group having 6 or more carbon atoms in the cellulose skeleton. 1 It may be calculated from the integral ratio of characteristic peaks by H-NMR analysis, assuming that the average number of substituents including the benzoyl group is 3.0.

[0041] Monovalent organic group (L a The total number of carbon atoms in the cellulose derivative is preferably 6 to 30, more preferably 7 to 20. When the total number of carbon atoms is within the above range, the affinity of the cellulose derivative for oil agents is superior.

[0042] The cellulose derivative (A) is a monovalent organic group (L) having a group represented by the following formula (2) at its terminal, which is substituted for at least a part of the hydrogen atoms constituting the hydroxyl groups in the cellulose: b ) may be provided. b ) is provided, the packing of the cellulose derivative in the oil agent is suppressed due to its flexibility, and the affinity for the oil agent is further improved. 2 (2) [wherein, R 2 represents a hydrocarbon group having 6 or less carbon atoms.

[0043] R 2 is a hydrocarbon group having 6 or less carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 4 or less, and more preferably 2 or less. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group.

[0044] Monovalent organic group (L b The hydrocarbon group at the end of the alkyl group (B) may be linear or branched. The hydrocarbon group may be saturated or unsaturated.

[0045] Monovalent organic group (L b The total number of carbon atoms in the cellulose derivative is preferably 1 to 20, more preferably 2 to 15. When the total number of carbon atoms is within the above range, packing of the cellulose derivative is further suppressed.

[0046] Monovalent organic group (L b ) preferably contains a (poly)oxyalkylene chain. In this case, packing of the cellulose derivative is further suppressed. The alkylene group in the (poly)oxyalkylene chain is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 2 to 4 carbon atoms). Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

[0047] The average degree of polymerization of the oxyalkylene groups in the (poly)oxyalkylene chain is preferably from 1 to 5, more preferably from 2 to 3. When the average degree of polymerization is within the above range, packing of the cellulose derivative is further suppressed.

[0048] Monovalent organic group (L b ) has at least one ether bond, and preferably has two or more. The number of ether bonds is preferably 6 or less, and more preferably 4 or less. When the average degree of polymerization is within the above range, packing of the cellulose derivative is further suppressed.

[0049] Monovalent organic group (L b ) is bonded to an oxygen atom in the cellulose skeleton directly or via a linking group having the oxygen atom as a constituent atom. The linking group is a group formed by bonding the oxygen atom to a monovalent organic group (L b ) The linking group may be an ether bond, an ester bond, a urethane bond, a phosphinic acid group, a thionoester bond, or the like. Among these, an ester bond is preferred from the viewpoint of ease of introduction.

[0050] Monovalent organic group (L b ) is particularly preferably a group represented by the following formula (3): 2 -R 4 (-O-R 3 ) n-O-R 2 (3) [wherein, R 2 is the same as above. 3 represents an alkylene group, and n represents (—O—R 3 ) indicates the degree of polymerization, and R 4 represents a direct bond or a divalent organic group, and X 2 indicates a group that can bond with an oxygen atom constituting a hydroxy group in cellulose to form a linking group. The bond extending to the left bonds to an oxygen atom in the cellulose skeleton.

[0051] (-O-R 3 ) n represents the (poly)oxyalkylene chain. 3represents an alkylene group, and examples thereof include those exemplified and explained above as the alkylene group. n represents a natural number, preferably 1 to 5, and more preferably 2 or 3.

[0052] R 4 is a direct bond or a divalent organic group. The divalent organic group is preferably a divalent hydrocarbon group. The divalent hydrocarbon group may be saturated or unsaturated, and may be linear or branched. The divalent hydrocarbon group preferably has 1 to 8 carbon atoms. The divalent hydrocarbon group is preferably an alkylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group.

[0053] X 2 The linking group that can be formed by the above-mentioned X 1 Examples of the linking group that can be formed by X include those exemplified and explained above. 2 Examples of R include a carbonyl group (-C(=O)-), an amide group (-C(=O)-N(-R)-), (-P(=O)(-R)-), and a thiocarbonyl group (-C(=S)-). R is a hydrogen atom or a monovalent organic group. Of these, a carbonyl group is preferred.

[0054] In the cellulose derivative (A), the monovalent organic group (L b ) average degree of substitution (DS b ) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. b When DS is 0.1 or more, packing of the cellulose derivative is further suppressed. b is preferably 1.9 or less, more preferably 1.5 or less, and even more preferably 1.3 or less.

[0055] In the cellulose derivative (A), the monovalent organic group (L a The average degree of substitution of the monovalent organic group (L b ) or more, and the monovalent organic group (L b It is more preferable that the average degree of substitution of the monovalent organic group (L a ) average degree of substitution (DS a ) and a monovalent organic group (Lb ) average degree of substitution (DS c ) difference [DS a -DS b ] is preferably 0.1 to 2.5, more preferably 0.4 to 2.0, and even more preferably 0.4 to 1.0. When the difference is within the above range, the affinity for oil agents is superior.

[0056] Monovalent organic group (L a ) average degree of substitution (DS a ) monovalent organic group (L b ) average degree of substitution (DS b ) to [DS a / DS b ] is preferably 1 to 2.5, more preferably 1.3 to 2.2. When the ratio is within the above range, the affinity for oil agents is superior.

[0057] Monovalent organic group (L b ) may be substituted for the hydrogen atom of any of the three hydroxy groups in the glucose unit of the cellulose. b ) may be present in only one kind or in two or more kinds.

[0058] The cellulose derivative (A) is a monovalent organic group (L) having 5 or less carbon atoms and no ether bond, which has a hydrocarbon group at its terminal and which substitutes for at least a part of the hydrogen atoms constituting the hydroxyl groups in the cellulose. c ) may be provided. c When the monovalent organic group (L c The hydrocarbon group at the end of the alkyl group (B) may be saturated or unsaturated, and may be linear or branched. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group.

[0059] Monovalent organic group (L c ) is bonded to an oxygen atom in the cellulose skeleton directly or via a linking group having the oxygen atom as a constituent atom. The linking group is a group formed by bonding the oxygen atom to a monovalent organic group (Lc ) The linking group may be an ether bond, an ester bond, a urethane bond, a phosphinic acid group, a thionoester bond, or the like. Among these, an ester bond is preferred from the viewpoint of ease of introduction.

[0060] Monovalent organic group (L c The total number of carbon atoms in the alkyl group is preferably 1 to 5, and more preferably 2 to 4.

[0061] Monovalent organic group (L c ) is particularly preferably a group represented by the following formula (4): 3 -R 4 (4) [wherein, R 4 represents the hydrocarbon group, and X 3 indicates a direct bond or a group that can bond with an oxygen atom in cellulose to form a linking group. The bond extending to the left bonds to an oxygen atom in the cellulose backbone.

[0062] X 3 The linking group that can be formed by the above-mentioned X 1 Examples of the linking group that can be formed by X include those exemplified and explained above. 3 Examples of X include a direct bond, a carbonyl group (-C(=O)-), an amide group (-C(=O)-N(-R)-), (-P(=O)(-R)-), and a thiocarbonyl group (-C(=S)-). R is a hydrogen atom or a monovalent organic group. 3 Among them, a carbonyl group is preferable. c ) is preferably an acyl group.

[0063] In the cellulose derivative (A), the monovalent organic group (L a The average degree of substitution of the monovalent organic group (L c ) or more, and the monovalent organic group (L c It is more preferable that the average degree of substitution of the monovalent organic group (L a ) average degree of substitution (DS a ) and a monovalent organic group (L c ) average degree of substitution (DS c ) difference [DS a -DSc ] is preferably 1.1 to 2.9, more preferably 1.4 to 2.7. When the difference is within the above range, the affinity for oil agents is superior.

[0064] In the cellulose derivative (A), the monovalent organic group (L c ) average degree of substitution (DS c ) may be 0.05 or more, or may be 0.1 or more. c is preferably 1.0 or less, more preferably 0.5 or less, and even more preferably 0.25 or less.

[0065] Monovalent organic group (L a ) average degree of substitution (DS a ) monovalent organic group (L c ) average degree of substitution (DS c ) to [DS a / DS c ] is preferably 5 to 20, more preferably 7 to 16. When the ratio is within the above range, the affinity to the oil agent is superior.

[0066] Monovalent organic group (L c ) may be substituted for the hydrogen atom of any of the three hydroxy groups in the glucose unit of the cellulose. c ) may be present in only one kind or in two or more kinds.

[0067] Monovalent organic group (L a ) average degree of substitution (DS a ), a monovalent organic group (L b ) average degree of substitution (DS b ), and a monovalent organic group (L c ) average degree of substitution (DS c ) is 1.1 or more, preferably 1.5 or more, more preferably 2.0 or more, even more preferably 2.5 or more, and particularly preferably 2.7 or more. The higher the total, the better the affinity for the oil agent.

[0068] In the cellulose derivative (A), at least a part of the hydrogen atoms constituting the hydroxyl groups in the cellulose may be unsubstituted. That is, the cellulose derivative (A) may have hydroxyl groups derived from cellulose. In addition, the cellulose derivative (A) may have a monovalent organic group (L a ), a monovalent organic group (L b ), and a monovalent organic group (L c In addition to the above, the cellulose derivative (A) may have other substituents that substitute for at least a portion of the hydrogen atoms constituting the hydroxy groups in the cellulose. The cellulose derivative (A) may have only one or two or more of the above other substituents.

[0069] The monovalent organic group (L) in all the substituents (100 mol%) substituted for the hydrogen atoms constituting the hydroxyl groups in the cellulose in the cellulose derivative (A) a ), a monovalent organic group (L b ), and a monovalent organic group (L c The total proportion of one or more substituents selected from the group consisting of (a) and (b) is preferably 50 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more. In the cellulose derivative (A), the proportion of the other substituents (particularly, monovalent substituents having a hydroxy group at the terminal) in the total substituents (100 mol %) substituted for hydrogen atoms constituting hydroxy groups in cellulose is preferably 50 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less.

[0070] As the oil, for example, known or conventional oils used in cosmetic compositions and the like can be used, such as hydrocarbon oils, ester oils, and silicone oils. The oil is preferably a liquid having fluidity at 25°C. The oil may be volatile. Only one type of the oil may be used, or two or more types may be used.

[0071] The hydrocarbon oil has a flash point of, for example, 35 to 87° C. Examples of the hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene; and cyclic paraffinic hydrocarbon oils such as cyclodecane and cyclododecane.

[0072] Examples of the ester oil include isotridecyl isononanoate, diisostearyl malate, isostearyl myristate, octyldodecyl ricinoleate, neopentyl glycol dicaprate, diglyceryl diisostearate, glyceryl monomyristate monoisostearate, 2-ethylhexyl paramethoxycinnamate, tocopherol acetate, diglyceryl monoisostearate, etc. Vegetable oils also fall under the category of the ester oil.

[0073] Examples of the silicone oil include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0074] Of the above oils, hydrocarbon oils and ester oils are preferred.

[0075] The content of the cellulose derivative (A) in the composition is preferably 0.06 to 30% by mass, more preferably 0.1 to 20% by mass, based on 100% by mass of the total amount of the composition. When the content is 0.06% by mass or more, the film-forming ability is superior. When the content is 30% by mass or less, the affinity of the cellulose derivative for the oil agent is superior.

[0076] The content of the oil in the composition is preferably 50 to 99.99% by mass, more preferably 60 to 99.9% by mass, based on 100% by mass of the total amount of the composition. When the content is 50% by mass or more, the affinity of the cellulose derivative for the oil is superior. When the content is 99.99% by mass or less, the film-forming ability is superior.

[0077] When the oil agent is mainly composed of a hydrocarbon oil, the content of the hydrocarbon oil in the composition is preferably more than 50% by mass, more preferably 70% by mass or more, even more preferably more than 80% by mass, and particularly preferably 90% by mass or more, relative to 100% by mass of the total amount of the composition. Because cellulose derivatives have excellent affinity for various oil agents, even if the content of the hydrocarbon oil is more than 50% by mass (particularly more than 80% by mass), the cellulose derivative has excellent affinity for the oil agent.

[0078] When the oil agent contains ester oil as a main component, the content of the ester oil in the composition is preferably more than 50% by mass, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to 100% by mass of the total amount of the composition. Because cellulose derivatives have excellent affinity for various oil agents, even if the content of ester oil exceeds 50% by mass, the cellulose derivative has excellent affinity for the oil agent.

[0079] The concentrations of the various components in the composition may be adjusted appropriately by dilution or concentration depending on the conditions at the time of production or use.

[0080] The composition may contain other components in addition to the cellulose derivative (A) and the oil. Examples of the other components include powders, surfactants, lower alcohols, polyhydric alcohols, polymeric compounds other than the cellulose derivative (A), UV absorbers, antioxidants, dyes, fragrances, colorants, antifouling agents, moisturizers, and water. Only one of the other components may be used, or two or more may be used. The content of the oil in the organic solvent contained in the composition is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more, relative to 100% by mass of the total amount of the organic solvent.

[0081] The dosage form of the composition may be any of solid, semi-solid, gel, liquid, etc.

[0082] The composition containing the cellulose derivative (A) can be obtained by dispersing or dissolving the cellulose derivative (A) in a solvent, or by swelling the cellulose derivative (A) in a solvent and gelling it.

[0083] [Cellulose Derivative] The present disclosure also provides a cellulose derivative having a monovalent organic group (L) at its terminal, which is substituted for at least a portion of the hydrogen atoms constituting the hydroxyl groups in cellulose and has a group represented by the following formula (2): b -OR) 2 (2) [wherein, R 2 represents a hydrocarbon group having 6 or less carbon atoms.

[0084] In this specification, the monovalent organic group (L b A cellulose derivative having at least the above-mentioned cellulose derivative (B) may be referred to as a “cellulose derivative (B).” The cellulose derivative (B) is a novel compound and tends to be excellent in suppressing packing.

[0085] The monovalent organic group (L) in the cellulose derivative (B) b ) is a monovalent organic group (L) that may be contained in the cellulose derivative (A). b The monovalent organic group (L) in the cellulose derivative (B) may be any of those exemplified and explained above. b A preferred embodiment of the monovalent organic group (L) which the cellulose derivative (A) may have is b ) is the same as

[0086] In the cellulose derivative (B), the monovalent organic group (L b ) average degree of substitution (DS b ) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. b When DS is 0.1 or more, packing of the cellulose derivative is further suppressed. bmay be 2.9 or less, 2.5 or less, 1.9 or less, 1.5 or less, or 1.3 or less.

[0087] The cellulose derivative (B) contains a monovalent organic group (L a The cellulose derivative (B) may or may not have a monovalent organic group (L c In the cellulose derivative (B), at least a portion of the hydrogen atoms constituting the hydroxy groups in the cellulose may be unsubstituted. That is, the cellulose derivative (B) may have hydroxy groups derived from cellulose.

[0088] The cellulose derivative (B) also contains a monovalent organic group (L a ), a monovalent organic group (L b ), and a monovalent organic group (L c In addition to the above, the cellulose derivative (B) may have other substituents that substitute for at least a portion of the hydrogen atoms constituting the hydroxy groups in the cellulose. The cellulose derivative (B) may have only one or two or more of the above other substituents.

[0089] The preferred embodiments of the cellulose derivative (B) are the same as the preferred embodiments of the cellulose (A).

[0090] A composition containing the cellulose derivative (B) can be obtained by dispersing or dissolving the cellulose derivative (B) in a solvent, or by swelling and gelling the cellulose derivative (B) with a solvent. An oil is preferably used as the solvent.

[0091] As the oil agent, known or conventional oil agents can be used, for example, hydrocarbon oil, ester oil, and silicone oil. The oil agent is preferably a liquid having fluidity at 25°C. Among these, hydrocarbon oil and ester oil are preferred. Examples of the silicone oil, ester oil, and hydrocarbon oil include those exemplified and explained as oil agents in the composition containing the cellulose derivative (A) described above. Only one type of oil agent can be used, or two or more types can be used.

[0092] The content of the cellulose derivative (B) in the composition is preferably 0.06 to 30% by mass, more preferably 0.1 to 20% by mass, based on 100% by mass of the total amount of the composition. When the content is 0.06% by mass or more, the film-forming ability is superior. When the content is 30% by mass or less, the affinity of the cellulose derivative for the oil agent is superior.

[0093] The content of the oil in the composition is preferably 50 to 99.99% by mass, more preferably 60 to 99.9% by mass, based on 100% by mass of the total amount of the composition. When the content is 50% by mass or more, the affinity of the cellulose derivative for the oil is superior. When the content is 99.99% by mass or less, the film-forming ability is superior.

[0094] When the oil agent is mainly composed of a hydrocarbon oil, the content of the hydrocarbon oil in the composition is preferably more than 50% by mass, more preferably 70% by mass or more, even more preferably more than 80% by mass, and particularly preferably 90% by mass or more, relative to 100% by mass of the total amount of the composition. Because cellulose derivatives have excellent affinity for various oil agents, even if the content of the hydrocarbon oil is more than 50% by mass (particularly more than 80% by mass), the cellulose derivative has excellent affinity for the oil agent.

[0095] When the oil agent contains ester oil as a main component, the content of the ester oil in the composition is preferably more than 50% by mass, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to 100% by mass of the total amount of the composition. Because cellulose derivatives have excellent affinity for various oil agents, even if the content of ester oil exceeds 50% by mass, the cellulose derivative has excellent affinity for the oil agent.

[0096] The concentrations of the various components in the composition may be adjusted appropriately by dilution or concentration depending on the conditions at the time of production or use.

[0097] The composition may contain other components in addition to the cellulose derivative (B) and the oil agent. Examples of the other components include those exemplified and explained as other components in the composition containing the cellulose derivative (A). Only one type of other component may be used, or two or more types may be used.

[0098] The dosage form of the composition may be any of solid, semi-solid, gel, liquid, etc.

[0099] [Method for Producing Cellulose Derivatives] The cellulose derivatives (A) and (B) can be produced by, for example, (i) reacting cellulose with an acyl group donor in an ionic liquid, or (ii) reacting cellulose with an acyl group donor in a highly polar solvent (dimethylacetamide) in the presence of lithium chloride. Each of the various components, such as the ionic liquid, the acyl group donor, and the highly polar solvent, may be used singly or in combination of two or more.

[0100] The ionic liquid used in (i) serves as a solvent for dissolving cellulose and also functions as a powerful organic molecular catalyst. Only one type of ionic liquid may be used, or two or more types may be used.

[0101] The constituent anions of the ionic liquid are not particularly limited, but examples thereof include carboxylate anions such as formate anion, acetate anion, and propionate anion, PF6 - ion, CF3SO3 - ion, (CF3SO2)2N - ions, Cl - Ion, BF4 - When a carboxylate anion is used as the anion, a substituent derived from the carboxylate anion can be introduced into the cellulose skeleton by the method (i). For example, when an acetate anion is used as the anion, a monovalent organic group (L c ) can be introduced as an acetyl group.

[0102] The constituent cations of the ionic liquid are preferably organic cations, such as ammonium cations, heterocyclic onium cations, etc. Examples of the ammonium cations include aliphatic quaternary ammonium ions such as trimethylpropylammonium ion, trimethylhexylammonium ion, tetrapentylammonium ion, and diethyltrimethyl(2-methoxyethyl)ammonium ion, and alicyclic quaternary ammonium ions such as N-butyl-N-methylpyrrolidinium ion.

[0103] Examples of heterocyclic onium cations include imidazolium cations, pyridinium cations, piperidinium cations, pyrrolidinium cations, etc. Examples of imidazolium cations include dialkylimidazolium cations such as 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, and 1-propyl-3-methylimidazolium ion, trialkylimidazolium cations such as 1-(1,2 or 3-hydroxypropyl)-3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, and 1-butyl-2,3-dimethylimidazolium ion, 1-allyl-3-alkylimidazolium cations such as 1-allyl-3-ethylimidazolium ion and 1-allyl-3-butylimidazolium ion, and 1,3-diallylimidazolium cations. Examples of pyridinium cations include N-propylpyridinium ion, N-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-butyl-2,4-dimethylpyridinium ion, etc. Examples of piperidinium cations include N-methyl-N-ethylpiperidinium ion, N-methyl-N-propylpiperidinium ion, N-methyl-N-butylpiperidinium ion, etc. Examples of pyrrolidinium cations include N-methyl-N-ethylpyrrolidinium ion, N-methyl-N-propylpyrrolidinium ion, N-methyl-N-butylpyrrolidinium ion, etc.

[0104] The acyl group donor is, for example, a compound that can react with a hydroxy group in cellulose to replace a hydrogen atom with an acyl group, and has a monovalent organic group (L a ) and a monovalent organic group (L b ) can be appropriately selected depending on the type of compound. Examples of such compounds include linear or cyclic esters (e.g., vinyl carboxylic acid esters), aldehydes, carboxylic acid halides, and carboxylic acid anhydrides. Examples of carboxylic acid halides include fluorides, chlorides, bromides, and iodides.

[0105] The amount of the acyl group donor used is not particularly limited and can be adjusted appropriately depending on the degree of substitution of the substituent to be introduced. The amount of the acyl group donor used is, for example, 100 to 6,000 parts by mass, and preferably 100 to 3,000 parts by mass, relative to 100 parts by mass of the total amount of cellulose. The amount of the acyl group donor used is, for example, 1 to 20 equivalents, and preferably 3 to 9 equivalents, relative to 1 glucose equivalent (i.e., 3 equivalents of hydroxy groups) in cellulose.

[0106] In the reaction of (i), a solvent other than the ionic liquid may be added. As the solvent, known or commonly used organic solvents or water can be used. This allows for a reduction in production costs while maintaining the affinity of cellulose for the oil agent. Specifically, the highly polar solvents mentioned above are preferred as the solvent.

[0107] The reaction temperature is, for example, 40 to 120°C, and the reaction time is, for example, 1 minute to 48 hours. After the reaction, the solution is reprecipitated using a solvent such as methanol, filtered, etc., so that the acyl group donor is introduced onto the oxygen atom of the hydroxy group in the cellulose, forming a monovalent organic group (L a ), a monovalent organic group (L b ), or a monovalent organic group (L c In addition, the ionic liquid used in the reaction can be recovered and reused.

[0108] The highly polar solvent used in (ii) is used as a solvent for dissolving cellulose. Examples of the highly polar solvent include amide solvents such as dimethylformamide, N,N-dimethylacetamide, N-methylpiperidone, and 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; sulfolane; γ-butyrolactone; and hexamethylphosphoric triamide. Among these, amide solvents are preferred, and N,N-dimethylacetamide is more preferred, from the viewpoint of excellent cellulose solubility.

[0109] Examples of the acyl group donor include those exemplified and explained as the acyl group donor used in (i) above. The amount of the acyl group donor used is not particularly limited and can be adjusted appropriately depending on the degree of substitution of the substituent to be introduced. The amount of the acyl group donor used is, for example, 100 to 6,000 parts by mass, preferably 100 to 3,000 parts by mass, per 100 parts by mass of the total amount of cellulose. The amount of the acyl group donor used is, for example, 1 to 20 equivalents, preferably 3 to 15 equivalents, per 1 equivalent of glucose in cellulose (i.e., 3 equivalents of hydroxy groups).

[0110] The amount of lithium chloride used is not particularly limited, but is, for example, 1 to 12 parts by mass, and preferably 3 to 9 parts by mass, per 100 parts by mass of the total amount of the highly polar solvent.

[0111] In (ii), it is preferable to use a basic catalyst, such as a tertiary amine, for example, triethylamine, pyridine, dimethylaminopyridine, or triphenylphosphine.

[0112] The reaction temperature is, for example, 40 to 120°C, and the reaction time is, for example, 1 minute to 48 hours. After the reaction, the solution is reprecipitated using a solvent such as methanol, filtered, etc., so that the acyl group donor is introduced onto the oxygen atom of the hydroxy group in the cellulose, forming a monovalent organic group (L a ), a monovalent organic group (L b ), or a monovalent organic group (L c ) can be obtained.

[0113] [Uses of the composition] The composition (a composition containing the cellulose derivative (A) and / or the cellulose derivative (B)) exhibits excellent affinity for the cellulose derivative with various oils, even when various oils are used. Therefore, for example, even when the content of hydrocarbon oil or ester oil is high, the cellulose derivative exhibits excellent affinity for the oil, and tends to exhibit excellent film-forming properties (film-forming properties). Furthermore, because the cellulose derivative exhibits excellent affinity for the oil even when the content of hydrocarbon oil is high, the content of ester oil can be kept low, and the stickiness of the film formed from the composition is also suppressed. Furthermore, the cellulose derivative can be produced using cellulose as a raw material, and does not require CAP or CAB, which shortens the synthesis process of the cellulose derivative, leading to reduced environmental impact and production costs.

[0114] The composition can be used in various fields, such as packaging paper, printing, textiles, medicine, and cosmetics. For example, it can be used in cosmetics, topical skin preparations, coating agents, paints, etc. In the above applications, it can also be used as a film-forming agent.

[0115] The above-mentioned cosmetics (cosmetic compositions) are applied to the skin, lips, nails, and other skin areas, as well as to eyelashes and hair. Specific examples of the above-mentioned cosmetics include lip cosmetics such as lipstick, lip gloss, and lip liner; makeup cosmetics such as mascara, eyeliner, eye shadow, blush, foundation (cream foundation, pressed foundation, liquid foundation, etc.), and concealer; creams, emulsions, lotions, all-in-one gels, serums, facial cleansers, solid soaps, massage aids, deodorants, sunscreens, hair growth agents, shampoos, conditioners, hair colors, hair oils, hair waxes, hair styling sprays, hair foams, and waterproof cosmetics. The above-mentioned cosmetics may be in a liquid, semi-solid, or solid form at room temperature. The above-mentioned cosmetics are preferably oil-based cosmetics.

[0116] The cosmetic may be filled in a container, such as a bottle, a jar, or a tube.

[0117] The coatings can be used on automobiles, wood, plastics, metals, etc. They can also be used in the printing industry, for example, for solvent casting of films, etc. Examples of such applications include photographic films and protective films for liquid crystal displays.

[0118] The medical field includes drug delivery applications. In drug delivery applications, the cellulose derivatives can act as film-forming agents, for example, as coating agents for tablets or particles. The cellulose derivatives can also be used to form amorphous mixtures of poorly soluble drugs, thereby improving the solubility and bioavailability of the drug. The cellulose derivatives can also be used in controlled drug delivery, where the drug can be released from the cellulose derivative in response to an external stimulus, such as a change in pH.

[0119] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration and combination thereof in each embodiment is an example, and addition, omission, substitution, and other modifications of configurations are possible as appropriate within the scope of the present disclosure. Furthermore, each invention according to this disclosure is not limited by the embodiments or the following examples, but is limited only by the scope of the claims.

[0120] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples.

[0121] Example 1: Under a nitrogen atmosphere, 1.5 g (9.4 mmol) of microcrystalline cellulose (Avicel, manufactured by Asahi Kasei Corporation) was added to a mixed solvent of 29 g of ethyl methylimidazolium acetate and 38 g of dimethyl sulfoxide and dissolved at 80°C. 8.1 g (36 mmol) of vinyl laurate was added thereto, and the mixture was allowed to react at 80°C for 30 minutes. The mixture was then precipitated in methanol, purified, and dried to produce a cellulose derivative (cellulose acetate laurate) in which acetyl and lauroyl groups were substituted on the oxygen atoms of the cellulose skeleton. The resulting cellulose derivative was then heated to 70°C in isododecane to produce a swollen gel of the cellulose derivative (concentration 10% by mass).

[0122] Example 2: Under a nitrogen atmosphere, 1.0 g (6.2 mmol) of microcrystalline cellulose (Avicel, manufactured by Asahi Kasei Corporation) was added to a mixed solvent of 19 g of ethyl methylimidazolium acetate and 24 g of dimethyl sulfoxide and dissolved at 80°C. 4.8 g (18 mmol) of vinyl myristate was added, and the mixture was allowed to react at 80°C for 40 minutes. The mixture was then precipitated in methanol, purified, and dried to produce a cellulose derivative (cellulose acetate myristate) in which acetyl and myristoyl groups were substituted on the oxygen atoms of the cellulose skeleton. The resulting cellulose derivative was then heated to 70°C in isododecane to produce a swollen gel of the cellulose derivative (concentration 10% by mass).

[0123] Example 3 3.9 g of a cellulose derivative (cellulose acetate palmitate) in which acetyl groups and palmitoyl groups were substituted on oxygen atoms of the cellulose skeleton was prepared in the same manner as in Example 2, except that 5.8 g (20 mmol) of vinyl palmitate was added instead of vinyl myristate and the reaction was carried out for 30 minutes at 80° C. The obtained cellulose derivative was then heated to 70° C. in isododecane to prepare a swollen gel of the cellulose derivative (concentration: 10% by mass).

[0124] Example 4 A cellulose derivative (cellulose acetate stearate) in which acetyl and stearoyl groups were substituted on oxygen atoms of the cellulose skeleton was prepared in the same manner as in Example 2, except that 4.2 g (13 mmol) of vinyl stearate was added instead of vinyl myristate. The obtained cellulose derivative was then heated to 70°C in isododecane to prepare a swollen gel of the cellulose derivative (concentration: 10% by mass).

[0125] Example 5 A cellulose derivative (cellulose acetate stearate) was prepared in the same manner as in Example 4, except that the amount of vinyl stearate added was 5.4 g (17 mmol) and the reaction was carried out for 30 minutes at 80° C. The obtained cellulose derivative was then heated to 70° C. in isododecane to prepare a swollen gel of the cellulose derivative (concentration: 10% by mass).

[0126] Example 6 A cellulose derivative (cellulose acetate stearate) was prepared in the same manner as in Example 5, except that the amount of vinyl stearate added was 7.3 g (23 mmol). The obtained cellulose derivative was then added to isododecane and dissolved at 70°C to prepare a cellulose derivative solution (concentration: 10% by mass).

[0127] Example 7: Under a nitrogen atmosphere, 0.50 g (3.1 mmol) of microcrystalline cellulose (Sigma-Aldrich) was added to 21.43 g (6.7% by mass) of dimethylacetamide solution containing lithium chloride and dissolved therein. 1.13 g (9.3 mmol) of dimethylaminopyridine and 4.51 g (27.8 mmol) of octanoic acid chloride were added thereto, and the mixture was stirred at 80°C for 3 hours to carry out the reaction. A large amount of methanol was then added to precipitate the product, which was then recovered by filtration. The resulting product was dissolved in 20 g of tetrahydrofuran (THF) and purified by adding dropwise to a large amount of methanol. The precipitate was recovered by filtration and dried to obtain 1.01 g of a cellulose derivative (cellulose octanoate) in which octanoyl groups were substituted on the oxygen atoms of the cellulose skeleton. The resulting cellulose derivative was then added to isododecane and dissolved at 70°C to prepare a cellulose derivative solution (10% by mass).

[0128] Example 8: In the same manner as in Example 7, except for adding 6.07 g (27.8 mmol) of lauric acid chloride instead of octanoic acid chloride, 1.64 g of a cellulose derivative (cellulose laurate) in which lauroyl groups were substituted on oxygen atoms of the cellulose skeleton was prepared. The obtained cellulose derivative was then added to isododecane and dissolved at 70°C to prepare a cellulose derivative solution (concentration: 10% by mass).

[0129] Preparation Example 1: Under a nitrogen atmosphere, thionyl chloride (14.69 g, 0.12 mol) was slowly added dropwise to [2-(2-methoxyethoxy)ethoxy]acetic acid (20.00 g, 0.11 mol) at room temperature. After the addition was completed, the mixture was stirred at about 40°C for about 3 hours to carry out the reaction, and then the temperature was raised to 60°C to complete the reaction. After GC analysis confirmed the disappearance of the raw materials, the mixture was cooled to room temperature, and excess thionyl chloride was distilled off to obtain an acid chloride having a hydrophilic group (21.43 g, 0.11 mol, concentration 97.1% by mass).

[0130] Example 9 Under a nitrogen atmosphere, 0.80 g (4.9 mmol) of Tencel (registered trademark) (manufactured by Fujibo Holdings Co., Ltd.) was added to 32.22 g (concentration 6.7% by mass) of dimethylacetamide solution containing dissolved lithium chloride and dissolved. A mixture of 1.81 g (14.8 mmol) of dimethylaminopyridine, 14.37 g (22.2 mmol) of the acid chloride prepared in Preparation Example 1, and 4.86 g (22.2 mmol) of lauric acid chloride was added thereto, and the mixture was stirred at 80 ° C. for 3 hours to carry out the reaction. A large amount of methanol was then added to precipitate the product, which was then collected by filtration. The resulting product was dissolved in 32 g of THF and purified by adding dropwise to a large amount of methanol. The precipitate was collected by filtration and dried to obtain 3.370 g of a cellulose derivative in which lauroyl groups and groups derived from the acid chloride (sometimes referred to as "ether bond-containing groups") were substituted on the oxygen atoms of the cellulose skeleton. The obtained cellulose derivative was added to isododecane and dissolved at 70°C to prepare a cellulose derivative solution (concentration: 10% by mass). 1 The H-NMR spectrum is shown in FIG.

[0131] Example 10: Under a nitrogen atmosphere, 0.40 g (2.5 mmol) of microcrystalline cellulose (Sigma-Aldrich) was added to 16.11 g (concentration 6.7% by mass) of dimethylacetamide solution containing lithium chloride and dissolved therein. A mixture of 0.90 g (7.4 mmol) of dimethylaminopyridine, 2.18 g (11.1 mmol) of the acid chloride prepared in Preparation Example 1, and 2.43 g (11.1 mmol) of lauric acid chloride was added thereto, and the mixture was stirred at 80 ° C. for 3 hours to carry out the reaction. A large amount of methanol was then added to precipitate the product, which was then collected by filtration. The resulting product was dissolved in 32 g of THF and purified by adding dropwise to a large amount of methanol. The precipitate was collected by filtration and dried to obtain 0.997 g of a cellulose derivative in which lauroyl groups and groups derived from the acid chloride (ether bond-containing groups) were substituted on the oxygen atoms of the cellulose skeleton. The obtained cellulose derivative was added to isododecane and dissolved at 100° C. to prepare a cellulose derivative solution (concentration: 10% by mass).

[0132] Example 11 The cellulose derivative prepared in Example 1 was added to isotridecyl isononanoate and dissolved at 70°C to prepare a cellulose derivative solution (concentration: 10% by mass).

[0133] Comparative Example 1 Cellulose acetate (manufactured by Daicel Corporation) was added to isododecane to prepare a cellulose derivative mixed solution (mixing ratio: 10% by mass).

[0134] Comparative Example 2 A cellulose derivative (cellulose acetate laurate) in which acetyl groups and lauroyl groups were substituted on oxygen atoms of the cellulose skeleton was prepared in the same manner as in Example 2, except that 1.3 g (5.7 mmol) of vinyl laurate was added instead of vinyl myristate and the reaction was carried out for 30 minutes at 80° C. The obtained cellulose derivative was then added to isododecane to prepare a cellulose derivative mixed solution (mixing ratio 10% by mass).

[0135] Comparative Example 3: Under a nitrogen atmosphere, 10 g of hydroxyethyl cellulose (average substitution degree of hydroxyethyl groups: 1.8 to 2.3) was added to 100 g of dimethyl sulfoxide and dissolved by stirring at 80°C for 4 hours. After dissolution, 30 g of pyridine was added. 40 g of stearic acid chloride was added to the mixture, and the mixture was reacted at 80°C for 8 hours. The mixture was then precipitated in methanol, purified, and dried to prepare a cellulose derivative in which stearoyl groups were substituted on the oxygen atoms of hydroxyethyl cellulose. The obtained cellulose derivative was then added to isododecane to prepare a cellulose derivative mixture (mixing ratio: 10% by mass).

[0136] <Evaluation> The cellulose derivatives, cellulose derivative solutions, cellulose derivative swollen gels, and mixed solutions prepared or used in the Examples and Comparative Examples were evaluated as follows, and the results are shown in the Table.

[0137] (1) Average Degree of Substitution The cellulose derivatives obtained in the Examples and Comparative Examples were 1 H-NMR analysis was performed. In the esterified cellulose derivative, the proton of the terminal methyl group of the acyl group derived from a fatty acid ester having 6 or more carbon atoms appears near 0.9 ppm, and the seven protons of the cellulose skeleton appear near 3.2-5.2 ppm. Based on this, the average degree of substitution of the acyl group derived from the above fatty acid ester introduced was calculated from the calculated integral value. The average degree of substitution of the acetyl group was also calculated from the methyl proton derived from the acetyl group that appears near 2 ppm. Note that for Examples 9 and 10, since it was difficult to clearly determine the integral value of the protons of the cellulose skeleton, the following benzoylation reaction was further carried out to replace the remaining hydroxy groups, and the total average degree of substitution of all substituents including benzoyl groups for the obtained cellulose derivative was set to 3.0, which was calculated from the ratio of the integral values ​​of the protons derived from the benzoyl group, the protons derived from the ether bond-containing group, and the protons derived from the lauroyl group.

[0138] (Benzoylation reaction) 100 mg of the cellulose derivative obtained in Example 9 or 10 and 4 g of pyridine were added to a test tube and heated to 115°C under nitrogen to dissolve. 100 mg of an excess of benzoyl chloride was added dropwise to the mixture, and the mixture was reacted at 115°C for 5 hours. The reaction solution was then added dropwise to 15 g of methanol, a poor solvent, to perform reprecipitation purification, and the precipitate was dried to obtain a cellulose derivative in which unreacted hydroxy groups had been benzoylated.

[0139] (2) Affinity The cellulose derivative solutions, swollen gels, and mixed solutions obtained in the Examples and Comparative Examples were evaluated for affinity of the cellulose derivatives for oils according to the following criteria: A: Dissolves when heated at 70°C. B: Forms a swollen gel when heated at 70°C. C: Dissolves when heated at 100°C. D: Does not dissolve or disperse even when heated at 100°C, and does not form a swollen gel.

[0140] (3) Film Formability The cellulose derivative solutions, swollen gels, and mixed solutions obtained in the Examples and Comparative Examples were each spread with a spatula onto an aluminum cup to a thickness of approximately 3 mm and heated at 70°C for 1 hour. Also, a thin layer was spread onto a glass plate with a spatula and heated at 70°C for 5 minutes to volatilize the solvent. After cooling to room temperature, the state of the films formed on the aluminum cup and the glass plate was visually observed and evaluated according to the following criteria: A: A transparent film was formed on both the aluminum cup and the glass plate. B: A film was formed on both the aluminum cup and the glass plate, but the film was translucent or white in color. C: A film was formed on both the aluminum cup and the glass plate, but the film cracked. D: A transparent film was formed on both the aluminum cup and the glass plate, but it was thicker than A to C (it could not be spread thinly). E: A film was not formed on either the aluminum cup or the glass plate.

[0141]

[0142]

[0143] As shown in Tables 1 and 2, the cellulose derivative solutions or swollen gels of the Examples had excellent affinity between the cellulose derivative and oils, and the cellulose derivative dissolved in isododecane or isotridecyl isononanoate or formed a swollen gel at 70 to 100°C, and had excellent affinity for both oils consisting of hydrocarbon oils only and ester oils only. The cellulose derivative solutions of the Examples also had excellent film-forming properties. In particular, the better the affinity, the better the film-forming properties. Furthermore, if a thin film can be easily formed, the spreadability during application will be good and the feel after application will be good. On the other hand, the monovalent organic group (L a When the cellulose derivatives did not have the above-mentioned substituents or had an average degree of substitution of less than 1.1 (Comparative Examples 1 and 2), or when an organic group was introduced into a hydroxyalkyl cellulose (Comparative Example 3), they were not soluble or dispersible in isododecane, did not form a swollen gel, and had poor film-forming properties.

[0144] Example 12 (Preparation of Liquid Foundation) A liquid foundation was prepared by mixing the components shown in Table 3, stirring thoroughly, and filling a container. A small amount of the obtained liquid foundation was applied to the skin, and it was found to have water resistance and sebum resistance, as well as a soft texture that did not leave a filmy feeling.

[0145] Example 13 (Preparation of Sunscreen) A sunscreen was prepared by mixing the components shown in Table 4, stirring thoroughly, and filling a container. When the obtained sunscreen was applied to the skin, it felt good to the touch and had waterproof properties.

Claims

1. A monovalent organic group (L) having a hydrocarbon group having 6 or more carbon atoms at its terminal and no ether bond, which is substituted for at least a portion of the hydrogen atoms constituting the hydroxyl groups in the cellulose. ａ ), and the monovalent organic group (L ａ a cellulose derivative having an average degree of substitution of 1.1 or more; and an oil agent.

2. The composition according to claim 1 , wherein the oil is at least one selected from the group consisting of hydrocarbon oils, ester oils, and silicone oils.

3. The composition according to claim 2, wherein the content of the hydrocarbon oil is more than 80% by mass.

4. The composition according to claim 2, wherein the content of the ester oil is greater than 50% by mass.

5. The cellulose derivative has a monovalent organic group (L ｃ The composition of any one of claims 1 to 4, comprising:

6. In the cellulose derivative, the monovalent organic group (L ａ The average degree of substitution of the monovalent organic group (L ｃ 6. The composition of claim 5, wherein the average degree of substitution is equal to or greater than 1.

7. In the cellulose derivative, the monovalent organic group (L ｃ 6. The composition of claim 5, wherein the average degree of substitution of 2.0 is 1.0 or less.

8. The monovalent organic group (L ａ ) is expressed by the following formula (1): -X １ -R １ (1) [In the formula, R １ represents the hydrocarbon group having 6 or more carbon atoms, and X １ represents a direct bond or a group that can bond with an oxygen atom constituting a hydroxy group in the cellulose to form a linking group. The bond extending to the left bonds to an oxygen atom in the cellulose skeleton. The composition according to any one of claims 1 to 4, wherein the group is represented by:

9. An oily cosmetic comprising the composition according to any one of claims 1 to 4.

10. At least a part of the hydrogen atoms constituting the hydroxyl groups in cellulose is substituted, and the hydroxyl group is represented by the following formula (2): -O-R ２ (2) [In the formula, R ２ represents a hydrocarbon group having 6 or less carbon atoms. A monovalent organic group (L ｂ ) A cellulose derivative comprising:

11. The monovalent organic group (L ｂ 11. The cellulose derivative according to claim 10, wherein the cellulose derivative comprises two or more ether bonds.

12. The monovalent organic group (L ｂ 12. The cellulose derivative according to claim 10, wherein the hydroxyl group is an oxygen atom constituting the hydroxyl group and the hydroxyl group is an oxygen atom constituting the cellulose skeleton via an ester bond.

13. The monovalent organic group (L ｂ 12. The cellulose derivative according to claim 10 or 11, wherein the (poly)oxyalkylene chain comprises a (poly)oxyalkylene chain.

14. a monovalent organic group (L) having a hydrocarbon group having 6 or more carbon atoms at its terminal and having no ether bond, which is substituted for at least a portion of the hydrogen atoms constituting the hydroxyl groups in the cellulose; ａ 12. The cellulose derivative according to claim 10 or 11, comprising:

15. The monovalent organic group (L ａ The average degree of substitution of the monovalent organic group (L ｂ 15. The cellulose derivative according to claim 14, wherein the average degree of substitution is greater than 1.

16. A composition comprising the cellulose derivative according to claim 10 or 11 and an oil agent.

17. An oil-based cosmetic comprising the composition according to claim 16.