JP5550312B2 - Oil thickener and oil composition containing the same - Google Patents

Description

  The present invention relates to a thickener for oil that can thicken oil such as fats, oils, mineral oils, synthetic oils in a gel or elastic jelly form, and an oil composition containing the thickener. It relates to things (thickening oil).

Oil (oil) is often used in the fields of fuels, lubricants, cosmetics, foods and the like. There are various types of oils such as mineral oils, animal and vegetable oils, and synthetic oils. Depending on the application, it is desired to solidify these oils, and a wide variety of thickeners have been proposed (for example, , See Patent Documents 1 to 5). When these thickeners are added to the oil, a grease-like or wax-like oil can usually be obtained.
Here, for example, in the use of waste oil treatment using 12-hydroxystearic acid as described in Patent Document 1 and the use of solid fuel using fatty acid salt as described in Patent Document 2, the oil becomes a solid substance. If the fluidity is lost, the solid material can be used regardless of its properties. On the other hand, in applications such as cosmetics that are supposed to touch the body, not only does the oil solidify, but also the feel of the solid and the spread to the skin are important factors. Properties may be asked.

  As oil thickeners used in cosmetics and the like, for example, dextrin fatty acid ester, glycerin fatty acid ester, hydroxystearic acid, polyethylene and silica / alumina-coated titanium dioxide are known (for example, Patent Document 3). ~ 5). When these thickeners are used, solid or semi-solid oils can be obtained. These are all solid greases or waxy ones that do not recover solids that have changed when force is applied (plastic Solid). In addition, these thickeners do not gradually increase the viscosity of the oil even when the amount of oil added is adjusted, but it does not become grease or wax. Changes to a waxy or waxy shape. In addition, the viscosity index improver used in lubricating oil or the like can increase the viscosity of the oil but cannot be gelled. In other words, currently known oil thickeners are generally known only to give a grease-like or wax-like form, and give a gel-like or jelly-like oil (elastic solid) form. Oil thickeners have become unknown.

JP 55-106298 A JP-A-9-291295 JP 2004-099515 A JP 2006-160638 A JP 2008-115120 A

  Therefore, the problem to be solved by the present invention is to provide a thickener for oil that can give different forms to the thickener for oil, which has so far mainly been oily or waxy. More specifically, it is to provide a thickener for oil that can form gel oil, jelly oil or gummy oil.

  Thus, the present inventors have intensively studied and found a thickener for oil that can obtain gel-like oil, jelly-like or gummy-like oil, and led to the present invention. That is, the present invention is an oil thickener represented by the following general formula (1).

(In the formula, A ¹ and A ² each represent a group selected from an octyl group, a phenyl group, a naphthyl group, and a biphenyl group , R ¹ and R ⁴ each represent a C 4 alkylene group, and B ¹ and B ² is oxygen original frame other each represent a group represented by NH, ^{R 2} represents a hexylene group or a methyl phenylene group, ^{R 3} represents a hydrocarbon group having 4 carbon atoms, n represents 30 to 150 And m represents a number from 1 to 8 , x and y each represent a number from 0 to 10 , and p and q each represent a number of 1. )

  The effect of the present invention is to provide an oil thickener capable of forming a gel-like oil, jelly-like or gummy-like oil by adjusting the amount added to the oil.

1 is a GPC (gel permeation chromatography) chart showing the molecular weight distribution of the compound of Example 1. FIG. It is a figure showing the chart of GPC (gel permeation chromatography) about the molecular weight distribution of the compound of Example 12. It is a figure showing the chart of GPC (gel permeation chromatography) about the molecular weight distribution of the compound of Example 13.

  The oil thickener of the present invention is a compound represented by the following general formula (1).

(In the formula, each of A ¹ and A ² is a hydrocarbon having 1 to 30 carbon atoms which may have a substituent selected from a hydroxyl group, a nitro group, an ether group, a carbonyl group, an ester group, an amide group and an amino group. R ¹ and R ⁴ each represent an alkylene group having 2 to 4 carbon atoms, B ¹ and B ² each represent an oxygen atom, a nitrogen atom or a group represented by NH, and R ² represents An optionally substituted hydrocarbon group having 1 to 20 carbon atoms, R ³ represents a hydrocarbon group having 3 to 8 carbon atoms, n represents a number of 10 to 200, and m represents 0 to 10 And x and y each represent a number of 0 to 20, and p and q each represent a number of 1 or 2. However, when m is 0, R ¹ and R ⁴ each have 3 or 3 carbon atoms. 4 alkylene groups, and x and y are numbers from 1 to 20 .)

A ¹ and A ^{2 in} the general formula (1) each have 1 to 30 carbon atoms which may have a substituent selected from a hydroxyl group, a nitro group, an ether group, a carbonyl group, an ester group, an amide group and an amino group. Represents a hydrocarbon group, and examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, isopentyl group, 2 Primary pentyl, hexyl, isohexyl, secondary hexyl, heptyl, isoheptyl, secondary heptyl, octyl, isooctyl, secondary octyl, nonyl, isononyl, secondary nonyl, decyl Group, isodecyl group, secondary decyl group, undecyl group, isoundecyl group, secondary undecyl group, dodecyl group, isododecyl group, secondary dodecyl group Group, tridecyl group, isotridecyl group, secondary tridecyl group, tetradecyl group, isotetradecyl group, secondary tetradecyl group, hexadecyl group, isohexadecyl group, secondary hexadecyl group, stearyl group, eicosyl group, docosyl group, tetracosyl Group, triacontyl group, 2-butyloctyl group, 2-butyldecyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetra Alkyl groups such as decyl group, 2-dodecyl hexadecyl group, 2-hexadecyl octadecyl group, 2-tetradecyl octadecyl group, monomethyl branched-isostearyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl Group, isobutenyl group, pentenyl group, Alkenyl groups such as ntenyl, hexenyl, heptenyl, octenyl; phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethyl Phenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p -Aryl groups such as cumylphenyl group, phenylphenyl group, benzylphenyl group, α-naphthyl group, β-naphthyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, methylcyclohexyl group, methylcyclyl group Examples thereof include cycloalkyl groups such as a loheptyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, and a methylcycloheptenyl group. When there is a substituent, one or two or more hydrogen atoms of the above-described hydrocarbon group may be substituted, or substituted in a form introduced into one or more carbon-carbon bonds. Further, it may be hydroxypyridine, aminopyridine or the like in which a part of hydrocarbon of benzene ring such as phenol or aniline is substituted with nitrogen atom.

Among these groups, gelation and the like can be performed regardless of the type of oil. Therefore, an aryl group and a group obtained by substituting an aryl group with a substituent are preferable, and a group derived from phenols or anilines is more preferable. preferable. The group derived from phenol is a case where B ¹ or B ^{2 in} the general formula (1) is an oxygen atom derived from phenol or phenol, and the group derived from aniline is a group derived from B in the general formula (1). ^This is a case where ¹ or B ² is a nitrogen atom derived from aniline or anilines.

R ¹ and R ⁴ each represent an alkylene group having 2 to 4 carbon atoms. Examples of such an alkylene group include an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among these groups, an alkylene group having 3 or 4 carbon atoms is preferable because the effect of thickening and gelling oil is high, and an alkylene group having 4 carbon atoms can be used for gelation regardless of the type of oil. Is more preferable.

x and y represent a number of 0 to 20, but the number of 0 to 10 is preferable, the number of 0 to 5 is more preferable, and the number of 0 to 3 is more preferable because oil gelation can be easily performed. 0 is most preferred. The value of m is a number from 0 to 10, but the values of x and y when the value of m is 0 must be 1 to 20, preferably 3 to 20, and more preferably 8 to 20 . When x or y is a number of 2 or more, a plurality of oxyalkylene groups derived from R ¹ and R ⁴ are either a single polymer or a block copolymer consisting of a plurality of groups or a random polymer. There may be.

B ¹ and B ² each represent an oxygen atom, a nitrogen atom or a group represented by NH, and p and q each represent a number of 1 or 2. However, when p or q represents a number of 2, B ¹ and B ² corresponding to it represent a nitrogen atom.

R ³ represents a hydrocarbon group having 3 to 8 carbon atoms. Examples of such hydrocarbon groups include propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, isopentylene group, hexylene group, and isohexylene. Group, heptylene group, isoheptylene group, octylene group, isooctylene group, phenylethylene group and the like. Among these, an alkylene group having 3 or 4 carbon atoms is preferable, and an alkylene group having 4 carbon atoms is more preferable because gelation can be performed regardless of the type of oil and production is easy.

Although n represents the number of 10-200, the number of 10-150 is preferable, and the number of 20-100 is more preferable, since the effect of gelatinization of oil etc. is high and manufacture is easy, The number of 20-100 is more preferable. Numbers are more preferred. The plurality of oxyalkylene groups derived from R ³ may be either a single polymer or a block copolymer or a random polymer composed of a plurality of groups.

R ² represents a hydrocarbon group which may have a substituent having 1 to 20 carbon atoms. These hydrocarbon groups are in the range of 1 to 20 carbon atoms or 1 to 20 hydrocarbon groups substituted with substituents such as ether group, carbonyl group, ester group, amide group, urea group, etc. Any of them may be used, but a diisocyanate compound described later is preferably a group obtained by removing two isocyanate groups. A particularly preferred group is an alkylene group, which will be described in detail in the description of the diisocyanate compound described later.

  Although the value of m is a number of 0-10, the number of 1-8 is preferable and the number of 3-6 is more preferable. Since the value of m varies depending on the method for producing the compound represented by the general formula (1), it will be described in detail in the production method described later.

  The production method of the compound represented by the general formula (1) is not specified and may be produced by a known method. However, since the production is easy, the compounds of the following general formulas (2) to (5) Is preferably used as a raw material.

(In the formula, A ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent selected from a hydroxyl group, a nitro group, an ether group, a carbonyl group, an ester group, an amide group and an amino group; R ¹ represents an alkylene group having 2 to 4 carbon atoms, B ¹ represents any of an oxygen atom, a nitrogen atom or a group represented by NH, x represents a number of 0 to 20, and p represents 1 or 2 (However, when p is 2, B ¹ is a nitrogen atom.)

(In the formula, A ² represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent selected from a hydroxyl group, a nitro group, an ether group, a carbonyl group, an ester group, an amide group and an amino group; R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, B ² represents any of an oxygen atom, a nitrogen atom or a group represented by NH, y represents a number of 0 to 20 and q represents 1 or 2 (However, when q is 2, B ² is a nitrogen atom.)

(In the formula, R ³ represents a hydrocarbon group having 3 to 8 carbon atoms, and n represents a number of 10 to 200.)

（式中、Ｒ^２は置換基を有してもよい炭素数１〜２０の炭化水素基を表す。）

(Wherein, R ² represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)

The compounds represented by the general formulas (2) and (3) are compounds represented by (A ¹ ) _p -B ¹ -H and (A ² ) _q -B ² -H, respectively. It can be obtained by addition polymerization of an alkylene oxide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Among these, propylene oxide and butylene oxide are preferable, and butylene oxide is more preferable. These alkylene oxides may be subjected to addition polymerization of x mol and y mol, respectively. However, since the viscosity can be increased and gelled regardless of the type of oil, it is preferable that the number of addition is smaller and not added (x = 0, y = 0) is more preferable. However, when the compound of the general formula (4) is not used in the production of the compound of the general formula (1), the alkylene oxide that can be subjected to addition polymerization must be propylene oxide or butylene oxide. If an added ^one (R ¹ and R ⁴ are ethylene groups) is used, a thickener for oil having a thickening effect cannot be obtained. Furthermore, the value of x and y must be a number from 1 to 20, preferably a number from 3 to 20, and more preferably a number from 8 to 20.

As the compounds represented by (A ¹ ) _p -B ¹ -H and (A ² ) _q -B ² -H, when B ¹ and B ² are oxygen atoms, for example, methanol, ethanol, propanol, isopropanol , Butanol, isobutanol, tertiary butanol, pentanol, isopentanol, neopentanol, tertiary pentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, 2-ethylhexanol, isooctanol, nonanol, isononanol , Decanol, isodecanol, undecanol, isoundecanol, dodecanol, isododecanol, tridecanol, isotridecanol, tetradecanol, isotetradecanol, hexadecanol, isohexadecanol, o Tadecanol, isooctadecanol, oleyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, myricyl alcohol, lasserol, tetratriacontanol, 2-butyloctanol, 2-butyldecanol, 2-hexyl Octanol, 2-hexyldecanol, 2-octyldecanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, 2-hexadecyloctadecanol, 2-tetradecyl Octadecanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, benzyl alcohol, benzylide Alcohols such as sorbitol; phenol, cresol, dimethylphenol, ethylphenol, propylphenol, tertiary butylphenol, pentylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, dinonylphenol, decylphenol, undecylphenol, dodecylphenol, Examples include phenols such as phenylphenol, benzylphenol, styrenated phenol, p-cumylphenol, acetamidophenol, p-phenoxyphenol, p-hydroxybenzophenone, and hydroxypyridine. Among these, phenols are preferable because gelation can be performed without selecting the type of oil and a highly transparent gel can be obtained.

When B ¹ and B ² are a group represented by a nitrogen atom or NH, for example, methylamine, ethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, isohexylamine, Heptylamine, isoheptylamine, octylamine, isooctylamine, nonylamine, isononylamine, decylamine, isodecylamine, undecylamine, isoundecylamine, dodecylamine, isododecylamine, tridecylamine, isotridecylamine , Tetradecylamine, isotetradecylamine, hexadecylamine, isohexadecylamine, octadecylamine, isooctadecylamine, eicosylamine, isoeicosylamine, docosylamine, isodo Primary amines such as silamine (value of p or q is 1); dimethylamine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, dipentylamine, diisopentylamine, dihexylamine, diisohexylamine, diheptyl Amine, diisoheptylamine, dioctylamine, diisooctylamine, dinonylamine, diisononylamine, didecylamine, diisodecylamine, diundecylamine, diisoundecylamine, didodecylamine, diisododecylamine, ditridecylamine, diisotridecyl Amine, Ditetradecylamine, Diisotetradecylamine, Dihexadecylamine, Diisohexadecylamine, Dioctadecylamine, Diisooctadecylamine, Diaicosylamine, Diiso Secondary amines such as eicosylamine, didocosylamine, diisodocosylamine, diphenylamine (value of p or q is 2); aniline, methylaniline, dimethylaniline, methoxyaniline, ethoxyaniline, methoxymethylaniline, trimethylaniline, isopropyl And anilines (value of p or q is 1) such as aniline, tetramethylaniline, acetamidoaniline, aminopyridine and the like. Among these, anilines are preferable because gelation can be performed regardless of the type of oil and a highly transparent gel can be obtained.

When the compounds represented by (A ¹ ) _p -B ¹ -H and (A ² ) _q -B ² -H are not phenols or anilines (such as alcohols or amines), or phenols or anilines However, when alkylene oxide is added (when the value of x or y is 1 or more), the oil that can be gelled may be limited. More specifically, low polarity oils such as hydrocarbons typified by paraffin and mineral oil are oils that are difficult to thicken or gel, and even the thickener for oils of the present invention (A ¹ ) When the compounds represented by _p- B ¹ -H and (A ² ) _q -B ² -H are not phenols or anilines, or even if they are phenols or anilines, alkylene oxide is added. In some cases, the thickening effect may be low or the thickening effect may not be obtained. In addition, even if it is these thickeners, if it is oil with high polarity, such as ester oil, gelatinization of oil etc. is realizable.

The polyalkylene glycol represented by the general formula (4) is an oxyalkylene group polymer having 3 to 8 carbon atoms, and even a polymer composed of one kind of oxyalkylene group is a block composed of two or more kinds of oxyalkylene groups. It may be a polymer or a random polymer. Among these, block or random polymer of R ³ is a 3 to 4 carbon atoms are preferred, R ³ is the number 3 and and a rate of 4 carbon atoms at least 50 mol% of the total oxyalkylene groups in the fourth block or random polymers of carbon It is more preferable that R ³ has 4 carbon atoms (general formula (4) is polybutylene glycol). Moreover, although the value of n which is a polymerization degree is a number of 10-200, the number of 10-150 is preferable from the point that the effect of gelatinization of oil etc. is high and manufacture is easy, and the number of 20-100 Is more preferable, and a number of 30 to 70 is still more preferable. The weight average molecular weight of the polyalkylene glycol represented by the general formula (4) is determined by the value of the type of ^{R 3} and n, preferably 2,000 to 10,000, 3,000 to 7,000 are more preferable.

The polyalkylene glycol represented by the general formula (4) is generally produced by polymerizing an alkylene oxide, but an alkylene oxide having 5 or more carbon atoms has a slow polymerization reaction and produces a polymer having the above preferred molecular weight. This takes a lot of time and is not realistic. Further, in terms of performance, when polyethylene glycol having R ³ of 2 carbon atoms is used, it is insoluble in oil and cannot be thickened or gelled. When polyalkylene glycol having 5 or more carbon atoms is used, it dissolves in oil. The effect of the conversion becomes lower than that of polypropylene glycol or polybutylene glycol. In addition, when comparing polypropylene glycol and polybutylene glycol, polypropylene glycol has a thickening effect or gelling effect in a highly polar oil (for example, ester oil). The effect of gelation is low. On the other hand, polybutylene glycol has effects such as gelation on all kinds of oils.

  Examples of the diisocyanate compound represented by the general formula (5) include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, and 2,2-dimethylpentane. Diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate , Metaxylylene diisocyanate, para Aliphatic diisocyanates such as silylene diisocyanate and tetramethylxylylene diisocyanate; metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine Diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate , Diphenylmethane-4,4′-diisocyanate, 2 2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′, 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4- Isocyanatophenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane-3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′- Diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane 4,4′-diisocyanate, 3,3′-dichlorodiphenyldimethylmethane-4,4′-diisocyanate, benzophenone-3,3′-diisocyanate, etc. Aromatic diisocyanates; hydrogenated xylylene diiso Examples thereof include alicyclic isocyanates such as cyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. Among these diisocyanate compounds, aliphatic diisocyanates are preferable because of high effects such as oil gelation, methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate are more preferable, More preferred is hexamethylene diisocyanate.

  Examples of the method for producing the compound represented by the general formula (1) using the compounds represented by the general formulas (2) to (5) as raw materials include 1 mol of the compound represented by the general formula (2). And the compound represented by General formula (4) is 0.3-1.7 mol with respect to 2 mol in total of 1 mol of compounds represented by General formula (3), Preferably 0.5-1.5 Mol, more preferably 0.8 to 1.2 mol, and 1.5 to 3.0 mol, preferably 1.8 to 2.7 mol, more preferably 2 to 0.5 mol of the compound represented by the general formula (5). What is necessary is just to make it react for 0.0-2.5 mol. When the compound represented by the general formula (4) is less than 0.3 mol or the compound represented by the general formula (5) is more than 3.0 mol, the compound represented by the general formula (1) to be obtained In this case, a large amount of a compound having a small molecular weight (small value of m) is generated, which is not preferable. On the other hand, when the compound represented by the general formula (4) is more than 1.7 mol, or when the compound represented by the general formula (5) is less than 1.5 mol, the obtained general formula (1) Of the compounds represented, a large number of compounds having a large molecular weight (m has a large value) are not preferable. The value of m will be described in detail in a specific reaction method.

  When the compound represented by the general formula (4) is not used, a compound having a value of m of 0 in the general formula (1) is obtained. In this case, the compound 1 represented by the general formula (2) is obtained. 1.5 to 3.0 mol, preferably 1.8 to 2. mol of the compound represented by the general formula (5) with respect to 2 mol in total of 1 mol of the compound represented by mol and the general formula (3). The reaction may be 7 mol, more preferably 2.0 to 2.5 mol. In any reaction, the compound represented by the general formula (2) and the general formula (3) is preferably the same because the thickener for oil of the present invention is easy to produce.

  As a specific reaction method, for example, all necessary compounds may be mixed and reacted together at 60 to 100 ° C. for 1 to 10 hours, but preferably represented by the general formula (4) After adding a compound represented by the general formula (5) to a system containing a compound and a catalyst, preferably further containing a solvent, and reacting at 60 to 100 ° C. for 1 to 5 hours, the general formula (2) What is necessary is just to add the compound represented by the compound represented by General formula (3), and to react at 60-100 degreeC for 1 to 5 hours. When the compound represented by the general formula (2) and the compound represented by the general formula (3) are phenol or aniline, the reacting group is a phenolic hydroxyl group or an amino group, and is represented by the general formula (4). The group with which the compound reacts is an alcoholic hydroxyl group. Each of these reacts with the isocyanate group of the compound represented by the general formula (5), but since the reaction rates are different from each other, when all the compounds are mixed and reacted together, the reaction may not proceed uniformly. In some cases, unreacted raw materials remain, or in the general formula (1), many compounds having a m value of 0 may be formed.

  Use of a solvent facilitates handling because the viscosity of the final product is reduced. In addition, if the solvent is not used, the entire system becomes highly viscous, and the reaction may proceed locally in the system, resulting in a heterogeneous reaction. Therefore, the use of a solvent is preferable to promote the reaction uniformly. . When a solvent is used, the oil thickener of the present invention is obtained in a state dissolved in the solvent. Even in this state, it is a product, but the solvent may be removed to obtain a product having a purity of 100%. Any method may be used for removing the solvent as long as it is a known method, and examples thereof include distillation under reduced pressure, drying by heating, spray drying, or a combination of these methods.

  Examples of the solvent that can be used in the above reaction include oils that can be used in the oil thickener of the present invention described later, toluene, xylene, cyclohexane, methyl isobutyl ketone, ethyl lactate, butyl lactate, ethyl acetate, butyl acetate, and the like. A low molecular weight solvent may be mentioned. What is necessary is just to mix | blend the usage-amount of a solvent so that it may become 95-30 mass% with respect to the whole system, Preferably it is 90-50 mass%. However, when the oil that can be used for the oil thickener of the present invention is used as a solvent, the system may gel after the completion of the reaction. Therefore, it is preferable to use a low molecular weight solvent that is difficult to gel. Low molecular weight solvents also have the advantage of being easy to remove when purifying the oil thickener of the present invention as a 100% pure product.

  Examples of catalysts that can be used in the above reaction include strong acids such as sulfuric acid and toluenesulfonic acid; titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride. Metal halides such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium carbonate and other alkali metal and alkaline earth metal hydroxides, alcoholates, carbonates; aluminum oxide, calcium oxide, barium oxide Metal oxides such as sodium oxide; organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis (2-ethylhexylthioglycolate); sodium octylate, potassium octylate, sodium laurate, Lau Soap potassium phosphate, etc., may be reacted by adding 0.01 to 1 weight% for the entire system. Although the reaction proceeds without using a catalyst, the use of a catalyst increases the reaction rate, so that the effect of shortening the reaction time can be obtained.

  In the compound represented by the general formula (1) obtained by the above reaction, when the amount of the compound represented by the general formula (4) is 0, the value of m in the general formula (1) becomes 0. When the usage-amount of the compound represented by General formula (4) is more than 0, the mixture whose m value in General formula (1) is about 0-10 produces | generates. A compound having a m value of 1 or more is preferred to a compound having a m value of 0 because of the effect of gelation and the like. Usually, the oil thickener of the present invention obtained by the above reaction is a mixture of compounds represented by the general formula (1), and the mixing ratio is represented by the general formulas (2) to (5). Although it varies depending on the compounding ratio and reaction conditions of each compound, since the effect of gelation of oil and the like is good, the ratio of compounds having m values of 3 and 4 is 20% by mass or more of the whole. It is preferable that it reacts with 30% by mass or more. If the ratio of compounds with m values of 3 and 4 is less than 20% by mass and the ratio of compounds with m value of 7 or more increases, the product viscosity becomes high and handling becomes difficult, or oil gelation occurs. In some cases, when the ratio of the compound having a value of m of 2 or less is increased, it is difficult to dissolve in the oil, or the effect of gelation of the oil may be decreased. In particular, when the ratio of compounds having a value of m of 2 or less increases, the gelation effect may be remarkably inferior.

  The oil that can be used for the oil thickener of the present invention may be natural oil or synthetic oil, and any oil that does not dissolve in water or hardly soluble in water can be used. Specifically, the oil has a solubility in water of less than 5 g / 100 ml, preferably less than 1 g / 100 ml, more preferably less than 0.5 g / 100 ml. Examples of such oils include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol; poly-α-olefin, ethylene-α-olefin copolymer, polybutene, alkylbenzene, alkylnaphthalene. , Polyphenyl ether, alkyl-substituted diphenyl ether, polyol ester, dibasic acid ester, carbonate ester, GTL (Gas to Liquids), polybutene, hexyl acetate, decyl acetate, butyl propionate, hydrogenated polybutene myristyl myristate, hexyl laurate , Decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate Synthetic oils such as octyl oxystearate; hydrocarbons such as paraffinic mineral oil, naphthenic mineral oil, liquid paraffin, petrolatum, squalane, petroleum, gasoline, light oil, heavy oil; lanolin, mink oil, cocoa butter, coconut oil, palm kernel oil And oils such as camellia oil, sesame oil, castor oil, olive oil and the like. Although most of the silicone oils and derivatives thereof, and halogenated oils and derivatives thereof such as fluorine oil are not soluble or hardly soluble in water, thickening is possible even when the oil thickener of the present invention is used. Things and gels cannot be obtained.

  The thickening oil of the present invention contains 0.1 to 30% by mass of the thickener for oil of the present invention based on the total amount of the composition in the composition containing the oil thickener and oil of the present invention. It has a form of gel-like oil, jelly-like or gummy-like oil.

  Gel-like oil is an oil having a thixotropic property that has a high viscosity at rest and hardly exhibits fluidity, but flows when force is applied. For example, the oil in such a form has properties such that the oil exhibits periodic vibration when it is shaken lightly in a container.

  The jelly-like or gummy-like oil is, for example, a solid having no fluidity and elastic properties, and has a property of returning to its original shape even when deformed by applying force. As in the case of gel-like oil, when the oil is put in a container and shaken lightly, the oil exhibits periodic vibrations. However, when a force of a certain level or more is applied, the oil remains in a solid state and does not show fluidity.

  The thickener for oils of the present invention can be obtained in one or two forms of thickened oil as described above by changing the amount added to the oil. Among the oil thickeners of the present invention, those having good performance can be obtained, for example, a fluid thickened oil can be obtained with a small addition amount, and a gel oil can be obtained by further increasing the addition amount. When the amount added is increased, a jelly-like or gummy-like oil can be obtained. As described above, the oil thickener of the present invention has a characteristic that various forms of oil that have not been obtained so far can be easily obtained simply by changing the amount of the oil. In addition, these forms change continuously with the addition amount of the thickener for oils of this invention, and the point that these forms change is not necessarily clear. In addition, the thickener for oil of the present invention does not necessarily obtain the above two types, and depending on the type of oil, etc., there may be obtained only one type of the two types. is there. Further, there is a case where a part of the oil becomes a gel and floats in the liquid oil and then changes into one of the above two forms. In any case, the oil can be obtained in a form that has not been obtained so far, so that the utility value in various applications is great.

  Further, the grease-like or wax-like oil obtained by using a known oil thickener only gives a colored appearance such as white or milky white, but the thickening oil of the present invention is completely transparent. Or it has a slightly turbid appearance. The appearance of products in cosmetics and the like is important in selling products, and in particular, having a transparent appearance is preferable because a product with high added value can be obtained and variations in products can be increased.

  When producing the thickened oil of the present invention, the oil thickener of the present invention may be added to the oil and mixed until uniform. The temperature at the time of mixing is not specifically limited, For example, what is necessary is just to mix until it heats to room temperature-about 200 degreeC, and becomes uniform. The thickening oil of the present invention is obtained by adding 1 to 30% by mass, preferably 5 to 30% by mass of the oil thickener of the present invention to the oil. Viscosity or gelation effect may not appear, and if it exceeds 30% by mass, the thickened oil becomes too hard, the thickener for oil does not completely dissolve in the oil, or the effect commensurate with the amount added May not be obtained. In addition, what is necessary is just to adjust the addition amount with the form of the thickening oil requested.

  The use of the thickened oil of the present invention is not limited and can be applied to any use as long as the oil is used. Examples of such applications include the fields of fuels, lubricants, cosmetics, pharmaceuticals, fragrances, various battery electrolytes, paints, fibers, inks, etc. It is preferable to use it for cosmetics in which the touch is an important factor as a product.

  The cosmetic of the present invention is a cosmetic containing the thickening oil of the present invention. Specific products as cosmetics include, for example, sunscreens, foundations, W / O emulsions, creams, cleansing oils, hair waxes and the like containing various ultraviolet light inhibitors. In order to produce these cosmetics, water, surfactants, powders (pigments, dyes, resins), antibacterial agents, fragrances, moisturizers, physiologically active ingredients, salts, as long as the effects of the present invention are not impaired. Components such as a solvent, an antioxidant, a chelating agent, a pearling agent, a neutralizing agent, a pH adjusting agent, and an enzyme can be appropriately blended.

  Hereinafter, the present invention will be specifically described by way of examples. In the following examples and the like,% is based on mass unless otherwise specified. The specific manufacturing method or structure name of the compound (Examples 1-11 and Comparative Examples 1-4) used for experiment below is described.

<Production of Compound of Example 1>
300 g (0.1 mol) of polyoxybutylene glycol (compound represented by the general formula (4)) having a weight average molecular weight of 3000 in a 3000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, a solvent As a catalyst, 1200 g of butyl acetate and 0.5 g of dibutyltin bis (2-ethylhexylthioglycolate) as a catalyst were charged. After the system was purged with nitrogen, the temperature was raised to 75 ° C., and then hexamethylene diisocyanate (general formula (5) 33.6 g (0.2 mol) was added and reacted at 70-80 ° C. for 2 hours. After completion of the reaction, 18.6 g (0.2 mol) of aniline (compounds represented by the general formulas (2) and (3)) was added and reacted at 70 to 80 ° C. for 3 hours. ) To confirm that there was no isocyanate absorption (all the isocyanate had reacted), and the reaction was completed. The solvent of butyl acetate was removed from the obtained reaction product with an evaporator to obtain the compound of Example 1.

<Production of compounds of Examples 2 to 11 and Comparative Example 1>
Using the same reaction apparatus as in Example 1, the compounds of general formulas (2) to (5) were reacted in the same amount (the same number of moles) as in Example 1 and in the same manner according to the formulation table in Table 2. Thus, the compounds of Examples 2 to 11 and Comparative Example 1 were obtained. In each reaction, 1200 g of butyl acetate was used as a solvent, and 0.5 g of dibutyltin bis (2-ethylhexylthioglycolate) was used as a catalyst.

<Production of Compound of Example 12>
Except having changed the hexamethylene diisocyanate (compound represented by General formula (5)) to 50.4 g (0.3 mol) according to the compounding table | surface of Table 2 using the reaction apparatus similar to Example 1. FIG. The compound of Example 12 was obtained by reacting in the same manner as in Example 1.

<Production of Compound of Example 13>
Except having changed the hexamethylene diisocyanate (compound represented by General formula (5)) to 25.2g (0.15mol) according to the compounding table | surface of Table 2 using the reactor similar to Example 1, it is. By reacting in the same manner as in Example 1, the compound of Example 13 was obtained.

As Comparative Example 2-4, the following compounds were used as oil thickeners.
Comparative Example 2: 12-hydroxystearic acid Comparative Example 3: Sodium stearate Comparative Example 4: Dextrin palmitate

A predetermined amount of the above sample was added to the following three types of oils according to the blending amounts shown in Table 3, heated to 100 ° C., and stirred for 1 hour to make uniform. 50 ml of the obtained solution was placed in a 100 ml glass bottle, left in a thermostatic bath at 25 ° C. for 24 hours, and the state and appearance of the oil after standing were observed and evaluated according to the following criteria.
Oil 1: Liquid paraffin (viscosity 22 mm ² / S (20 ° C.), density 0.83 g / ml (20 ° C.))
Oil 2: Isopropyl myristate Oil 3: Triglyceride decanoate

PBG: Polybutylene glycol PPG: Polypropylene glycol HDI: Hexamethylene diisocyanate TDI: Tolylene diisocyanate PEG: Polyethylene glycol BO: Butylene oxide
Examples 5 and 9 are reference examples.

<GPC analysis>
The molecular weight distribution of the compounds of Example 1, Example 12 and Example 13 was measured using GPC (gel permeation chromatography). The equipment and conditions used for the measurement are as follows. The results of Example 1 are shown in FIG. 1, the results of Example 12 are shown in FIG. 2, and the results of Example 13 are shown in FIG.
Column used: TSKgel G4000Hxl, G3000Hxl, G2000Hxl (all manufactured by Tosoh Corporation) connected in series.
Eluent: THF (tetrahydrofuran)
Flow rate: 1 ml / min Detector: HLC-8120GPC (RI)
Sample concentration: 0.1% by mass (THF solution)
Sample volume: 200 μl
Column temperature: 40 ° C

  In the GPC chart, a compound having a large molecular weight appears as a peak at an early time. In FIG. 1, the peak numbered 5 is a compound having a value of m of 1 in the general formula (1), the peak of 4 is a compound of m value of 2, and the peak of 3 is a value of m of 3. The 2 peak has a m value of 4, and the 1 peak has a m value of 5 or more. Similarly, in FIG. 2, the peak 4 has a m value of 1, the peak 3 has a m value of 2, the peak 2 has a m value of 3, and the peak 1 has a m value of 4 or more. The same applies to FIG. The peak appearing around 27 minutes is an impurity peak.

The area ratio of each peak correlates with the compounding ratio (mass basis) of each substance. The area ratio of each peak is summarized in Table 5 below. As is apparent from a comparison of this result and the thickening result of oil, it can be seen that the result of thickening the oil greatly changes depending on the molecular weight distribution even when the same raw material is used. Specifically, the higher the total amount of m = 3 and m = 4, the better the result. In addition, although the exact value of m = 4 of Example 12 has not come out, it can estimate with about 3-5 in general.
Further, when manufactured by the manufacturing method of Example 1, the amount of impurities is clearly reduced as compared with Examples 12 and 13, and this manufacturing method also has an advantage as a manufacturing method with a small amount of generation of impurities.

Claims (4)

An oil thickener represented by the following general formula (1).

(In the formula, A ¹ and A ² each represent a group selected from an octyl group, a phenyl group, a naphthyl group, and a biphenyl group , R ¹ and R ⁴ each represent an alkylene group having 4 carbon atoms, and B ¹ and B ² is oxygen original frame other each represent a group represented by NH, ^{R 2} represents a hexylene group or a methyl phenylene group, ^{R 3} represents a hydrocarbon group having 4 carbon atoms, n represents 30 to 150 And m represents a number from 1 to 8 , x and y each represent a number from 0 to 10 , and p and q each represent a number of 1. ) Oil thickener of claim 1 where R ² is equal to or hexylene group. An oil composition comprising 1 to 30% by mass of the oil thickener according to claim 1 or 2 based on the total amount of the composition. A cosmetic using the oil composition according to claim 3 .

Images