WO2019021775A1

WO2019021775A1 - Gelled oil and method for producing same

Info

Publication number: WO2019021775A1
Application number: PCT/JP2018/025411
Authority: WO
Inventors: 坂西裕一; 島本周
Original assignee: 株式会社ダイセル
Priority date: 2017-07-24
Filing date: 2018-07-04
Publication date: 2019-01-31

Abstract

Provided is a method for producing a gelled oil wherein an oily substance has been homogeneously and stably gelled with a cellulose-based gelling agent. The method according to the present invention for producing a gelled oil comprises the following steps in the following order. Step I: Oxidizing cellulose in a state of being dispersed in water to give oxidized cellulose wherein at least one hydroxyl group at the C6-position of a glucose unit constituting the cellulose is converted into a carboxyl group. Step II: Defibrating the oxidized cellulose. Step III: Reacting the defibrated oxidized cellulose with a compound represented by formula (1) to give a salt of the oxidized cellulose. NH2-(AO)n-R1 (1) Step IV: Replacing the dispersion medium by one or more kinds of oily substances selected from among a hydrocarbon having 12 or more carbon atoms, a fatty acid having 12 or more carbon atoms, a fatty acid ester having 12 or more carbon atoms in total, an alcohol having 12 or more carbon atoms and a silicone oil.

Description

Gelled oil and method for producing the same

The present invention relates to a gelled oil in which an oil agent is gelled by cellulose, and a method for producing the same. The present application claims the priority of Japanese Patent Application No. 201-7142593 filed on July 24, 2017, the content of which is incorporated herein by reference.

Cellulose, which is a biological source, is used as a gelling agent for aqueous compositions because of its excellent safety. However, the gel obtained using cellulose had a problem that the viscosity change with temperature was large.

Patent Document 1 describes that viscosity change due to temperature can be suppressed by using, as a gelling agent, oxidized cellulose obtained by oxidizing the hydroxyl group at the C6 position of the glucose unit constituting cellulose and converting it to a carboxyl group. .

Further, in Patent Document 2, the hydroxyl group at the C6 position of the glucose unit constituting cellulose in water is oxidized to convert it into a carboxyl group, and then the dispersion medium is replaced from water with an organic solvent such as toluene, and then the above It is described that the cellulose can be hydrolysed by reacting polyetheramine with a carboxyl group and finally the organic solvent such as toluene can be gelled uniformly by disaggregating the hydrolyzed cellulose.

JP, 2011-57571, A JP, 2017-19896, A

However, since the oxidized cellulose described in Patent Document 1 coagulates in an oil, it has been difficult to use it as a gelling agent for cutting oil and oily cosmetic. Moreover, since the gel obtained by patent document 2 contains organic solvents, such as toluene, it was difficult to use as a thickener in cutting oil from a flammable viewpoint. Furthermore, it was also difficult to use in cosmetics from the viewpoint of irritation and the like.

Accordingly, an object of the present invention is to provide a method for producing a gelled oil in which an oil agent is gelled uniformly and stably by a cellulose gelator.
Another object of the present invention is to provide a gelled oil in which the oil agent is gelled uniformly and stably by a cellulose gelling agent.

As a result of intensive studies to solve the above problems, the inventors of the present invention oxidize cellulose dispersed in water to form a hydroxyl group at the C6 position of the glucose unit constituting the cellulose (specifically, the 6th position carbon having a hydroxyl group) The oxidized cellulose is obtained by converting the atom) into a carboxyl group, and the obtained oxidized cellulose is disintegrated, and then the carboxyl group contained in the oxidized cellulose is reacted with polyetheramine to hydrophobize the cellulose, and then the dispersion is carried out. By replacing the medium with the oil, the dispersion medium can be substituted with the oil while suppressing the strong aggregation due to hydrogen bonding between many hydroxyl groups present on the surface of the cellulose, and the oil as the dispersion medium is It has been found that a uniformly and stably gelled gelling oil is obtained. The present invention has been completed based on these findings.

That is, the present invention provides a method for producing a gelled oil comprising the following steps in the following order.
Step I: Oxidize cellulose in the state of being dispersed in water to obtain oxidized cellulose in which at least one of the hydroxyl groups at the C6 position of glucose unit constituting the cellulose is converted to carboxyl group Step II: Disaggregate oxidized cellulose Step III: The defibrated oxidized cellulose has the following formula (1)
NH _2- (AO) _n -R ¹ (1)
(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
Are reacted with each other to obtain a salt of oxidized cellulose. Step IV: The dispersion medium is a hydrocarbon having 12 or more carbon atoms, a fatty acid having 12 or more carbon atoms, a fatty acid ester having 12 or more carbon atoms in total, 12 carbon atoms. Replace with at least one oil selected from the above alcohols and silicone oils

The present invention also provides the method for producing a gelled oil as described above, wherein the reaction in step III is carried out after replacing the dispersion medium of the defibrated oxidized cellulose with water with an alcohol solvent having 1 to 5 carbon atoms. Do.

The present invention also provides the following formula (2)

(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
Salt of glucose-containing oxidized cellulose (A), hydrocarbon having 12 or more carbon atoms, fatty acid having 12 or more carbon atoms, fatty acid ester having 12 or more carbon atoms, alcohol having 12 or more carbon atoms, and silicone Provided is a gelled oil comprising at least one oil (B) selected from oils.

The present invention also provides the gelled oil as described above, wherein the content of the glucose unit represented by formula (2) in the oxidized cellulose salt (A) is 0.6 to 2.5 mmol / g.

The present invention also provides the gelled oil as described above, wherein the content of the salt (A) of oxidized cellulose is 0.01 to 20 parts by weight with respect to 100 parts by weight of the oil solution (B).

According to the production method of the present invention, a cellulose gelling agent provides a gelled oil in which a wide range of oils are gelled uniformly and stably. Therefore, the production method of the present invention is useful as a method for industrially producing a gelling oil.
In addition, the gelled oil obtained by the production method of the present invention can maintain its viscosity stably over time, and can suppress the viscosity change due to the temperature change extremely low. Therefore, the gelled oil of the present invention can be suitably used as a cutting oil or a cosmetic (in particular, an oily cosmetic). Moreover, it can be suitably used also as a thickener of cutting oil and cosmetics (especially oil based cosmetics).

[Method of producing gelled oil]
The method for producing a gelled oil of the present invention comprises the following steps in the following order.
Step I: Oxidize cellulose in the state of being dispersed in water to obtain oxidized cellulose in which at least one of the hydroxyl groups at the C6 position of glucose unit constituting the cellulose is converted to carboxyl group Step II: Disaggregate oxidized cellulose Step III: The defibrated oxidized cellulose has the following formula (1)
NH _2- (AO) _n -R ¹ (1)
(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
Are reacted with each other to obtain a salt of oxidized cellulose. Step IV: The dispersion medium is a hydrocarbon having 12 or more carbon atoms, a fatty acid having 12 or more carbon atoms, a fatty acid ester having 12 or more carbon atoms in total, 12 carbon atoms. Replace with at least one oil selected from the above alcohols and silicone oils

The production method of the present invention may have other steps (for example, purification step etc.) in addition to the above steps.

(Step I)
Step I is oxidation in which cellulose is oxidized in a state of being dispersed in water to convert at least one of the hydroxyl groups at the C6 position of the glucose unit constituting the cellulose (specifically, the —CH ₂ OH group) to carboxyl groups. This is a step of obtaining cellulose (in other words, obtaining oxidized cellulose in which a hydroxyl group at the C6 position (specifically, —CH ₂ OH group) is converted to a carboxyl group in at least one of glucose units constituting cellulose).

The cellulose includes cellulose types I and II having different crystal structures. Examples of cellulose type I include softwood pulp, hardwood pulp, cotton linters, straw pulp, bagasse pulp, bacterial cellulose, and natural cellulose such as cellulose isolated from seaweed. Examples of cellulose type II include regenerated cellulose. These can be used singly or in combination of two or more. In addition, when the above natural cellulose is stored without drying after isolation and purification, since the microfibrillar aggregate is easily swollen with water, the hydroxyl group at the C6 position of the glucose unit is The conversion efficiency to carboxyl group can be improved.

The crystal structure of cellulose can be identified by a diffraction profile obtained by wide-angle X-ray diffraction image measurement.

The concentration of cellulose dispersed in water is not particularly limited, and is, for example, about 0.5 to 10% by weight. For example, the cellulose concentration can be set higher by using an apparatus with high mechanical stirring power.

The oxidation of cellulose is preferably carried out by an oxidation catalyst. The amount of the oxidation catalyst used is, for example, in the range of 0.1 to 4 mmol / L (more preferably 0.2 to 2 mmol / L) in the reaction solution.

As the oxidation catalyst, an N-oxyl compound can be suitably used. Examples of the N-oxyl compounds include TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), TEMPO derivatives (eg, 4-acetamido TEMPO, 4-carboxy TEMPO, 4-phosphonooxy TEMPO 4-amino-TEMPO, 4- (2-bromoacetamido) -TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, etc.), 2-azaadamantane-N-oxyl and the like.

N-oxyl compounds may also be used in combination with co-catalysts. Examples of the cocatalyst include salts of halogen and an alkali metal or alkaline earth metal, ammonium salts, sulfates and the like. As a salt of halogen and an alkali metal or alkaline earth metal, for example, lithium bromide, potassium bromide, sodium bromide, lithium iodide, potassium iodide, sodium iodide, sodium iodide, lithium chloride, potassium chloride, sodium chloride, Calcium bromide, magnesium bromide, strontium bromide, calcium iodide, magnesium iodide, strontium iodide, calcium chloride, magnesium chloride, strontium chloride and the like can be mentioned. Examples of ammonium salts include ammonium bromide, ammonium iodide, ammonium chloride and the like. Moreover, as a sulfate, sodium sulfate, sodium hydrogensulfate, alum etc. are mentioned, for example. These can be used singly or in combination of two or more. The amount of the co-catalyst used is, for example, about 1 to 40 mol, preferably 10 to 20 mol, per 1 mol of the N-oxyl compound.

Furthermore, the oxidation catalyst is preferably used together with a co-oxidant. Examples of the co-oxidant include hypohalous acid, subhalic acid, perhalogen acid, hydrogen peroxide, perorganic acid, and salts thereof (eg, salts with alkali metals or alkaline earth metals), etc. can give. These can be used singly or in combination of two or more. In the present invention, in particular, an N-oxyl compound is used as an oxidation catalyst, together with an alkali metal salt of hypohalous acid (for example, sodium hypochlorite, sodium hypobromous acid, etc.) as a co-oxidant. It is preferred to use. The amount of co-oxidant used is, for example, in the range of 0.05 to 5 g / L in the reaction solution.

The pH of the reaction solution is preferably maintained in the range of about 8-11. The temperature of the reaction solution is, for example, in the range of 1 to 40.degree. The reaction time is, for example, about 0.5 to 10 hours.

In the above step I, the hydroxyl group at the C6 position in the glucose unit constituting the cellulose is oxidized to form an aldehyde group, which is further oxidized to form a carboxyl group. However, part of the aldehyde group may remain. In addition, a part of carbon atoms at 2- and 3-positions having a hydroxyl group may be oxidized to be a ketone group. However, when an aldehyde group or a ketone group is present in cellulose, the molecular chain of cellulose is broken to lower the degree of polymerization, which may lower the dispersion stability and gelling ability of cellulose. Therefore, after completion of the above step I, it is preferable to subject the cellulose to a reduction treatment to convert an aldehyde group or a ketone group to a hydroxyl group in terms of being able to suppress a decrease in dispersion stability and gelling ability.

As a reducing agent to be used for the reduction treatment, it is preferable to use one which reduces aldehyde groups and ketone groups to form hydroxyl groups, but does not reduce carboxyl groups generated in step I. Such reducing agents include, for _{_{example, LiBH 4, NaBH 3 CN,}} NaBH 4 , and the like.

The amount of reducing agent used is preferably, for example, 0.1 to 20% by weight of cellulose. The reaction of cellulose with the reducing agent after completion of step I is preferably carried out, for example, at a temperature of 1 to 40 ° C. for about 0.1 to 10 hours.

The total content of aldehyde group and ketone group in cellulose is, for example, preferably 0.3 mmol / g or less, more preferably 0.1 mmol / g or less, by the above reduction treatment, substantially not containing substantially It is particularly preferable to reduce the The content of aldehyde group and ketone group in cellulose can be measured by the semicarbazide method.

The content of the carboxyl group in the oxidized cellulose obtained through Step I is preferably, for example, in the range of 0.6 to 2.5 mmol / g.

Through the step I, a dispersion liquid in which oxidized cellulose is highly dispersed in water is obtained.

(Step II)
Process II is a process of disentanglement of the oxidized cellulose obtained through Process I. In the present invention, since the oxidized cellulose obtained in step I is disintegrated in step II and then subjected to step III, not only the cellulose exposed on the surface of the convergent body but also the inner side of the convergent body in step III The present cellulose can also be reacted with the compound represented by formula (1), and more hydrophobic groups can be provided.

Moreover, the oxidized cellulose obtained through the process I has a structure by which at least one of the hydroxyl groups at the C6 position of the glucose unit constituting the cellulose is converted to a carboxyl group. However, since a large number of hydroxyl groups still exist on the surface of oxidized cellulose, they are dispersed in water, but when the dispersion medium is replaced from an aqueous dispersion medium such as water with a non-aqueous dispersion medium such as oil, the hydroxyl groups are hydrogen bonded As a result, the oxidized cellulose is strongly coagulated. However, in the present invention, since the oxidized cellulose is subjected to the defibrillation treatment before replacing the dispersion medium with the non-aqueous dispersion medium, hydrogen bonding between hydroxyl groups can be suppressed, and the oxidized cellulose is strongly coagulated. It can be prevented.

For the disintegration of cellulose, for example, it is preferable to use a device having strong beating ability such as a mixer, a homomixer, a homogenizer, an ultrasonic dispersion treatment, a beater, a refiner, a grinder and the like.

The disintegration of cellulose is preferably performed until the maximum fiber diameter of cellulose is, for example, 1000 nm or less (preferably 500 nm or less, more preferably 100 nm or less, particularly preferably 30 nm or less, most preferably 10 nm or less). In addition, it is preferable to carry out until the number average fiber diameter of the cellulose fiber is, for example, 2 to 150 nm (preferably 2 to 100 nm, more preferably 5 to 100 nm, particularly preferably 5 to 30 nm).

Through the step II, a dispersion liquid in which the fibrillated oxidized cellulose is highly dispersed in water is obtained.

(Step III)
In step III, the defibrated oxidized cellulose obtained through step II has the following formula (1):
NH _2- (AO) _n -R ¹ (1)
(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
A step of obtaining a salt of oxidized cellulose by reacting (for example, neutralizing) the compound represented by

R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group to which these are bonded.

The aliphatic hydrocarbon group is preferably a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropyl group, a butyl group, an isobutyl group and an s-butyl group. A linear or branched alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3) such as a group, t-butyl group, pentyl group, hexyl group, decyl group and dodecyl group; Straight or branched alkenyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3) such as vinyl, allyl and 1-butenyl; carbons such as ethynyl and propynyl Examples include linear or branched alkynyl groups of the order of 2 to 20 (preferably 2 to 10, particularly preferably 2 to 3).

The alicyclic hydrocarbon group is preferably a saturated or unsaturated alicyclic hydrocarbon group having a carbon number of 3 to 20, and examples thereof include carbon such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cyclooctyl group. A cycloalkyl group having a number of about 3 to 20 (preferably 3 to 15, particularly preferably 5 to 8); a carbon number of 3 to 20 (preferably 3 to 15, particularly preferably 5), such as cyclopentenyl group or cyclohexenyl group -8) Cycloalkenyl group of about 8: perhydronaphthalen-1-yl group, norbornyl group, adamantyl group, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, tetracyclo [4.4. 0.1 ^2,5 . Examples thereof include bridged cyclic hydrocarbon groups such as a [1, ^{7 10} ] dodecane-3-yl group.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms (particularly, 6 to 10 carbon atoms), and examples thereof include a phenyl group and a naphthyl group.

Among them, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable as R ^{1 from the} viewpoint of excellent dispersion stability and gelling ability, and a linear or 1 to 20 carbon atoms is more preferable. It is preferably a branched alkyl group, particularly preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and most preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

A represents an alkylene group having a carbon number of 2 to 4, and examples thereof include a linear or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene and tetramethylene. It can be mentioned. n pieces of A may be the same or different. When n pieces of A are two or more different groups, the group represented by “— (AO) _n −” in the formula (1) is a graft copolymer of two or more AO It may be a block copolymer or a random copolymer.

N represents the number of repeating units of (AO), and when (AO) is two or more different groups, n represents the sum of the number of repeating units of two or more (AO). n is an integer of 15 to 200, preferably an integer of 20 to 150, more preferably an integer of 30 to 100, and particularly preferably an integer of 40 to 90, from the viewpoint of excellent dispersion stability and gelling ability. Most preferably, it is an integer of 50 to 90, particularly preferably an integer of 50 to 80.

The weight average molecular weight (Mw) of the compound represented by the formula (1) is, for example, 1000 to 10000, and preferably 1500 to 5000, and particularly preferably 2500 to 4500, in terms of excellent dispersion stability and gelling ability. Most preferably, it is 3000 to 4500.

As a compound represented by Formula (1), commercial items, such as JEFFAMINE M series and JEFFAMINE D series (above, the HUNTSMAN company make), can be used, for example.

In the above reaction, the amount of the compound represented by the formula (1) is preferably equimolar to the carboxyl group in the oxidized cellulose.

In addition, in the case of oxidizing cellulose in the presence of, for example, TEMPO and sodium hypochlorite in step I, the obtained oxidized cellulose has a hydroxyl group at the C6 position in the glucose unit constituting the cellulose is a carboxyl base (for example, -COONa group It may be converted to). In this case, it is preferable to convert the carboxyl base into a carboxyl group by reacting oxidized cellulose with hydrochloric acid or the like before reacting with the compound represented by the formula (1) in step III.

Furthermore, the reaction in step III is preferably carried out in the presence of a solvent. The solvent may be water, but an organic solvent showing solubility in both water and oil agent is preferable in that the dispersion medium can be more smoothly substituted to the oil agent in the subsequent step IV, for example, ethanol It is preferable to use one type alone or a combination of two or more types of alcohol solvents such as ethanol, propanol and isopropanol (particularly preferably an alcohol solvent having 1 to 5 carbon atoms).

Then, it is preferable to replace the dispersion medium of the dispersion liquid in which highly disintegrated oxidized cellulose obtained through the step II is highly dispersed in water, from water to the organic solvent. The substitution of the dispersion medium can be carried out, for example, by fractionating solid content (including oxidized cellulose) by centrifugal sedimentation, and dispersing the obtained solid content in the organic solvent.

Through step III, a gelled product in which the dispersion medium is gelled by the salt of oxidized cellulose is obtained.

(Step IV)
Step IV is a dispersion medium (for example, water or an organic solvent, preferably an organic solvent, particularly preferably an alcohol solvent) contained in the gelled product obtained through Step III, a hydrocarbon having 12 or more carbon atoms, and 12 carbon atoms. This is a step of substituting with the above-mentioned fatty acid, fatty acid ester having 12 or more carbon atoms in total, alcohol having 12 or more carbon atoms, and at least one oil agent selected from silicone oils. The replacement of the dispersion medium can be carried out, for example, by fractionating solid content (including oxidized cellulose) by centrifugal sedimentation, and dispersing the obtained solid content in the oil agent.

Examples of the hydrocarbon having 12 or more carbon atoms include isododecane, liquid paraffin and the like.

The fatty acid having 12 or more carbon atoms is preferably a saturated or unsaturated fatty acid having 12 to 25 carbon atoms. For example, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, etc. It can be mentioned.

Examples of the fatty acid ester having 12 or more carbon atoms in total include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, isostearyl isostearate, trimethylolpropane triisostearate, and 2-ethyl ester. Cetyl hexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, oleyl oleate, octyl lauryl oleate, olein Acid decyl, neopentyl glycol dicaprate, 2-ethylhexyl succinate, isocetyl stearate, butyl stearate, diisopropyl sebacate, cetyl lactate, myristyl lactate, octyl palmitate 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, phytosteryl oleate, diisostearyl malate, octyl paramethoxycinnamate, paramethoxycinnamic acid Isopropyl, rosin acid pentaerythritol, etc. may be mentioned.

The alcohol having 12 or more carbon atoms is preferably a saturated or unsaturated alcohol having 12 to 25 carbon atoms, and examples thereof include sethanol, stearyl alcohol, oleyl alcohol and the like.

The silicone oil includes linear or cyclic silicone oil. As silicone oil, for example, alkyl-modified silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclopentasiloxane, decamethylcyclohexasiloxane; higher fatty acid ester-modified silicones such as stearoxymethicone; The alkoxy modified silicone etc. are mentioned.

Among them, fatty acids having 12 or more carbon atoms and / or fatty acid esters having 12 or more carbon atoms in total are preferred as the oil agent in the present invention, since a gelled oil having higher viscosity is obtained, and particularly preferably 12 carbon atoms in total. The above fatty acid esters.

Through Step IV, the salt of oxidized cellulose is dissolved in the oil, and the oil is contained in the space of the three-dimensional cross-linked structure formed by the salt of oxidized cellulose, so that the oil loses fluidity. A gelled oil is obtained.

[Gelling oil]
The gelled oil of the present invention comprises a salt (A) of oxidized cellulose having a glucose unit represented by the following formula (2), a hydrocarbon having 12 or more carbon atoms, a fatty acid having 12 or more carbon atoms, a total of 12 or more carbon atoms And at least one oil agent (B) selected from an alcohol having 12 or more carbon atoms and a silicone oil. In the gelled oil of the present invention, when the salt (A) of oxidized cellulose dissolved in the oil agent (B) forms a three-dimensional crosslinked structure, the oil agent (B) loses fluidity and is gelled. It is a thing.

(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)

The content of the glucose unit represented by the above formula (2) in the oxidized cellulose salt (A) is preferably, for example, in the range of 0.6 to 2.5 mmol / g.

The gelled oil of the present invention can be produced, for example, by the method for producing the gelled oil described above.

The content of the salt (A) of oxidized cellulose in the gelled oil is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, particularly preferably 100 parts by weight of the oil agent (B). 0.1-5 parts by weight, most preferably 0.1-3 parts by weight.

The gelled oil of the present invention may contain components other than oxidized cellulose salt (A) and oil agent (B), but the content of components other than oxidized cellulose salt (A) and oil agent (B) Is, for example, at most 30 wt%, preferably at most 20 wt%, particularly preferably at most 10 wt%, most preferably at most 5 wt%, particularly preferably at most 1 wt% of the total amount of the gelling oil. The gelled oil of the present invention may be substantially free of other components, and may be composed of only the oxidized cellulose salt (A) and the oil agent (B).

The gelled oil of the present invention comprises an organic solvent [eg, a hydrocarbon having 1 to 11 carbon atoms (eg, an aromatic hydrocarbon such as benzene, toluene, xylene, etc.), a fatty acid having 1 to 11 carbon atoms, and 1 to 11 carbon atoms in total] 11 fatty acid esters and alcohols having 1 to 11 carbon atoms] may be contained alone or in combination of two or more. However, the content thereof in terms of safety when used for cosmetics and cutting oils, The total amount of the gelling oil is, for example, 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less, most preferably 1% by weight or less. It is particularly preferred not to contain.

The gelled oil of the present invention can stably maintain the gel state. In addition, since the oxidized cellulose salt (A) is excellent in dispersion stability in the oil agent (B), the viscosity of the gelled oil is uniform.

The gelled oil of the present invention can be suitably used as a cutting oil or a cosmetic (in particular, an oily cosmetic). In addition, it can be suitably used as a thickener for cutting oil and cosmetics (in particular, oil-based cosmetics such as foundation, concealer, eye shadow, lip gloss, mascara, hair gel, etc.).

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by these examples.

Example 1
In dry weight, 1 g equivalent of softwood bleached kraft pulp, 0.1 mmol TEMPO, 1 mmol sodium bromide, 3.8 mmol sodium hypochlorite are dispersed in 100 mL water and gently stirred at room temperature for 4 hours. By washing with distilled water and washing with water, oxidized cellulose (carboxyl group content: 1.69 mmol / g) was obtained.

Thereafter, distilled water was added to undried oxidized cellulose to prepare a suspension with a solid concentration of 0.1% by weight. Then, the suspension is subjected to a defibration treatment for 1 minute with a household mixer for 2 minutes by ultrasonic treatment, and thereafter subjected to a centrifugation treatment (12000 × g) to remove an unfibrillated portion, which is transparent. An aqueous dispersion of oxidized cellulose having a concentration of 0.1% by weight was obtained.

Next, 1 M hydrochloric acid was added to 100 mL of the oxidized cellulose aqueous dispersion to adjust the pH to 2, and stirring was continued for 60 minutes. Thereafter, centrifugation (12000 vg) was performed, the supernatant was discarded, distilled water was added, and the operation subjected to centrifugation again was repeated to wash the oxidized cellulose, thereby obtaining a hydrogel.

Next, ethanol is added to the obtained hydrogel so that the concentration of oxidized cellulose is about 0.1% (g / mL), and the process of centrifugation (12000 × g) is repeated to recover the lower layer five times. Thus, the water contained in the hydrogel was replaced with ethanol to obtain gelled ethanol.

Next, in gelled ethanol, the compound represented by the polyetheramine (1) (the following formula (1 ′), equimolar amount, n1 / n2 = 6/29) and the carboxyl group of oxidized cellulose contained in the gelled ethanol , Mw: 2000, trade name "JEFFAMINE M-2005", manufactured by HUNTSMAN). Thereafter, the oxidized cellulose was converted to a salt by ultrasonication for 3 minutes. The obtained salt of oxidized cellulose has a glucose unit represented by the following formula (2 ') (content of glucose unit: 1.69 mmol / g).

Next, olive oil (including oleic acid, palmitic acid, linoleic acid, stearic acid, and myristic acid) is added to the oxidized cellulose salt so that the concentration of oxidized cellulose salt becomes about 0.5% (g / mL). In addition, by repeating the process of applying centrifugation (12000 × g) and recovering the lower layer five times, ethanol contained in the gelled ethanol was replaced with olive oil to obtain a gelled oil.

Example 2
A gelled oil was obtained in the same manner as in Example 1 except that cetyl octanoate was used instead of olive oil.

Example 3
Instead of polyether amine (1), polyether amine (2) (a compound represented by the following formula (1 ′ ′), n 3 = 68, M w: 4000, trade name “JEFFAMINE D-4000, manufactured by HUNTSMAN”) A salt of oxidized cellulose having a glucose unit represented by the following formula (2 ′ ′) was obtained in the same manner as in Example 1 except that it was used, to obtain a gelled oil.

[Dispersibility]
The gelled oil obtained in the example was degassed and transferred to a glass bottle, and allowed to stand at 25 ° C. for 1 day to visually observe the state change of the gelled oil, and the dispersibility was evaluated based on the following criteria.
:: The cellulose fibers are uniformly dispersed without sedimentation, and the total light transmittance is 60% or more ○: The cellulose fibers are uniformly dispersed without settling, the total light transmittance is 40% or more and less than 60% Δ: Cellulose fiber dispersed uniformly without sedimentation, total light transmittance less than 40% ×: Cellulose fiber settled

[Thickening ability]
The gelled oil obtained in the example is deaerated, transferred to a glass bottle, and allowed to stand at 25 ° C. for a day, and then a tuning-fork vibration type viscometer (manufactured by A & D Corp., SV-10, The viscosity (mPa · s) was measured using 30 Hz: 3 minutes, 25 ° C.), and the viscosity was evaluated based on the following criteria.
◎: The viscosity of the gelled oil is 500 times or more compared to the viscosity of the oil agent used as the raw material ○: The viscosity of the gelled oil is 300 times or more and less than 500 times the viscosity of the oil agent used as the raw material Δ: The viscosity of the gelled oil is 100 times or more and less than 300 times the viscosity of the oil agent used as the raw material x: The viscosity of the gelled oil is less than 100 times the viscosity of the oil agent used as the raw material

〔safety〕
The gelled oil obtained in the example was applied to the skin after face washing to 30 healthy female panelists, and the safety was evaluated according to the following criteria from the number of panelists who complained of skin irritation.
○: Less than 5 panelists complaining of skin irritation (good safety)
X: 6 or more panelists complaining of skin irritation (poor safety)

The results are summarized in the following table.

As a summary of the above, the configuration of the present invention and the variations thereof will be additionally described below.
[1] A method for producing a gelled oil comprising the following steps in the following order.
Step I: Oxidize cellulose in the state of being dispersed in water to obtain oxidized cellulose in which at least one of the hydroxyl groups at the C6 position of glucose unit constituting the cellulose is converted to carboxyl group Step II: Disaggregate oxidized cellulose Step III: The defibrated oxidized cellulose has the following formula (1)
NH _2- (AO) _n -R ¹ (1)
(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
Are reacted with each other to obtain a salt of oxidized cellulose. Step IV: The dispersion medium is a hydrocarbon having 12 or more carbon atoms, a fatty acid having 12 or more carbon atoms, a fatty acid ester having 12 or more carbon atoms in total, 12 carbon atoms. [2] The carboxyl group content of the oxidized cellulose obtained through Step I is 0.6 to 2.5 mmol / g, replacing with the above-mentioned alcohol and at least one oil agent selected from silicone oils. The manufacturing method of the gelatinization oil as described in 1].
[3] The method for producing a gelling oil according to [1] or [2], wherein the weight average molecular weight (Mw) of the compound represented by the formula (1) is 1000 to 10000.
[4] Any one of [1] to [3], wherein the amount of the compound represented by the formula (1) is 0.5 to 2.0 mol per 1 mol of carboxyl group in oxidized cellulose The manufacturing method of the gelatinization oil as described in any one.
[5] The reaction in step III is carried out after replacing the dispersion medium of defibrated oxidized cellulose with water with an alcohol solvent having 1 to 5 carbon atoms, in any one of [1] to [4] The manufacturing method of the gelatinization oil of description.
[6] The method for producing a gelled oil according to any one of [1] to [5], wherein the oil agent in step IV is a fatty acid having 12 or more carbon atoms and / or a fatty acid ester having 12 or more carbon atoms in total. .
[7] The method for producing a gelled oil according to any one of [1] to [5], wherein the oil agent in step IV is a fatty acid ester having 12 or more carbon atoms in total.
[8] The gel according to any one of [1] to [7], wherein an N-oxyl compound is used as an oxidation catalyst and an alkali metal salt of hypohalous acid is used as a co-oxidant in step I. Oil production method.
[9] Salt (A) of oxidized cellulose having a glucose unit represented by the formula (2), hydrocarbon having 12 or more carbon atoms, fatty acid having 12 or more carbon atoms, fatty acid ester having 12 or more carbon atoms in total, carbon number 1. A gelled oil comprising 12 or more alcohols and at least one oil agent (B) selected from silicone oils.
[10] The gelled oil according to [9], wherein the content of the glucose unit represented by the formula (2) in the oxidized cellulose salt (A) is 0.6 to 2.5 mmol / g.
[11] The gelled oil according to [9] or [10], wherein the content of the oxidized cellulose salt (A) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the oil agent (B).
[12] The total content of the salt (A) of the oxidized cellulose and the oil agent (B) is 70% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the gelling oil The gelling oil according to any one of [9] to [11], which is at least wt%, particularly preferably at least 99 wt%).
[13] The total content of organic solvents (preferably, hydrocarbons having 1 to 11 carbon atoms, fatty acids having 1 to 11 carbon atoms, fatty acid esters having 1 to 11 total carbon atoms, and alcohols having 1 to 11 carbon atoms) 30% by weight or less (preferably 20% by weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less, most preferably 1% by weight or less) of the total amount of oil The gelling oil according to any one of the preceding claims.
[14] The gelling oil according to any one of [9] to [13], which is a cutting oil.
[15] The gelling oil according to any one of [9] to [13], which is an oily cosmetic.
[16] The gelled oil according to any one of [9] to [13], which is a thickener of cutting oil.
[17] The gelling oil according to any one of [9] to [13], which is a thickener for oily cosmetics.

According to the production method of the present invention, a cellulose gelling agent provides a gelled oil in which a wide range of oils are gelled uniformly and stably.
In addition, the gelled oil obtained by the production method of the present invention can maintain its viscosity stably with time, and the viscosity change due to the temperature change can be suppressed extremely low. Therefore, it can be suitably used for cutting oil and cosmetics.

Claims

The manufacturing method of the gelatinization oil which has the following process in order of the following.
Step I: Oxidize cellulose in the state of being dispersed in water to obtain oxidized cellulose in which at least one of the hydroxyl groups at the C6 position of glucose unit constituting the cellulose is converted to carboxyl group Step II: Disaggregate oxidized cellulose Step III: The defibrated oxidized cellulose has the following formula (1)
NH 2- (AO) n -R 1 (1)
(Wherein, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
Are reacted with each other to obtain a salt of oxidized cellulose. Step IV: The dispersion medium is a hydrocarbon having 12 or more carbon atoms, a fatty acid having 12 or more carbon atoms, a fatty acid ester having 12 or more carbon atoms in total, 12 carbon atoms. Replace with at least one oil selected from the above alcohols and silicone oils
The method for producing a gelled oil according to claim 1, wherein the reaction in step III is carried out after replacing the disaggregated dispersion medium of oxidized cellulose with water with an alcohol solvent having 1 to 5 carbon atoms.
Following formula (2)

(Wherein, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hydroxyl group or an amino group as a substituent, and n represents an integer of 15 to 200. n pieces) A is the same or different and represents an alkylene group having 2 to 4 carbon atoms)
Salt of glucose-containing oxidized cellulose (A), hydrocarbon having 12 or more carbon atoms, fatty acid having 12 or more carbon atoms, fatty acid ester having 12 or more carbon atoms, alcohol having 12 or more carbon atoms, and silicone A gelled oil comprising at least one oil (B) selected from oils.
The gelled oil according to claim 3, wherein the content of the glucose unit represented by the formula (2) in the oxidized cellulose salt (A) is 0.6 to 2.5 mmol / g.
The gelled oil according to claim 3 or 4, wherein the content of the salt (A) of oxidized cellulose is 0.01 to 20 parts by weight with respect to 100 parts by weight of the oil solution (B).