JP2015110523A - Pasty composition and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrocarbon composition which has a reduced amount of impurities content other than a target component as compared with the existing hydrocarbon composition, is excellent in storage stability, slippage at the time of application (smoothness), gloss after application, stability under light irradiation, lubricity, and mold releasability, and has a reduced environmental load, and to provide a production method thereof.SOLUTION: The invention provides a method for producing a pasty composition which comprises performing decarboxylation dimerization reaction against fatty acid composition in which (1) the content of a branched chain fatty acid is 70 mass% or more, (2) the content of a branched chain fatty acid which is liquid at 25°C and has one carboxylic acid is 65 mass% or less, and (3) the content ratio of a branched chain fatty acid which is liquid at 25°C and has two or three carboxylic acids to the branched chain fatty acid is 10 mass% or more, and subsequently performing hydrodeoxygenation reaction against the obtained aliphatic ketone.

Description

  The present invention relates to a paste-like composition suitable as a substitute for petrolatum and a method for producing the same.

  In the recent rapid development of industry, industrial products having various chemical structures are used around us. Among these, hydrocarbon compounds using crude oil as raw materials have been distributed in various processing methods, forms, and compositions along with the development of the petroleum industry, and are widely used for extremely familiar industrial materials. Among them, compounds called paraffinic hydrocarbons are mainly crude oil separated and refined and fractionated by differences in boiling point, melting point, etc., and are liquid liquid paraffin, solid paraffin wax, mainly distillation residues thereof. It is classified as a certain petrolatum. These materials called paraffinic hydrocarbons are used in the food, chemical industry, pharmaceuticals, and cosmetics industries because they are manufactured at a very low price because of their huge production scale. One of the materials. In various industries, for example, liquid liquid paraffin is used as a base oil for lubricants and cosmetics, and solid paraffin wax is a mold release agent, moldability improver, polish, waterproof / water repellent and products. It is used as a base material for imparting a form. Furthermore, petrolatum, which is a pasty hydrocarbon known in Japan as petrolatum, shows a shape intermediate between liquid and solid, and is used as a release agent / lubricant for ointment bases in pharmaceuticals and industrial products.

  Paraffinic hydrocarbons generally contain contaminants other than the intended physical properties (eg, boiling point / melting point) because the desired fraction is extracted from crude oil containing a large number of compound groups by an operation such as distillation. It is known. For this reason, when using the paraffinic hydrocarbon refined from crude oil for various purposes, some problems occur due to the presence of impurities and contaminants resulting from the origin of the crude oil.

  In particular, petrolatum, known under the name petrolatum in Japan, is a paste-like component obtained by solvent fractionation of petroleum crude oil vacuum distillation residue, so it has a high molecular weight and high melting point compared to liquid paraffin and paraffin wax. It is known to contain components that cannot be identified as sulfur components or structures derived from common compounds or crude oil. Furthermore, it is known that even refined petrolatum has different high melting point and high molecular components depending on the production area of crude oil, and the viscosity and melting point are different.

  Cosmetics are generally designed with a precise blending of many ingredients, and it is known that sometimes the difference between the high melting point and high molecular weight components greatly affects the stability of the cosmetics. For example, when petrolatum is blended in a lipstick among cosmetics, it is often used mainly as a gloss imparting agent. However, since petrolatum contains a very high melting point polymer component as described above, when the lipstick blended with petrolatum is applied to the lips, the high melting point polymer component does not melt at the temperature of the coated surface, Since visible light scattering occurs, the improvement of gloss, which is the original purpose, is hindered. Furthermore, when petrolatum is used as a cosmetic feel improving agent, it is known that the difference in ingredients due to the difference in production area described above affects the coefficient of static friction and the coefficient of dynamic friction, giving a large difference in the feeling of use. .

  When petrolatum is used as an industrial lubricant or mold release agent, as described above, there are differences in the viscosity and temperature dependence among the refined products, and these differences are related to the static friction coefficient, dynamic friction coefficient, release It is known to have a great influence on formability.

  In addition, when liquid paraffin, paraffin wax and petrolatum originating from crude oil are used as ointment bases in cosmetics and pharmaceuticals, the structure derived from crude oil is identified in addition to the difference in usability as with cosmetics. It is known that a group of ingredients that cannot be adversely affected. In particular, discoloration and odor generation due to exposure not only affects the feeling of use, but also may cause irritation to the application site of the human body or affect the active ingredient body of the pharmaceutical product.

  On the other hand, industrial materials using these hydrocarbon materials are also required to have a low environmental impact in the production process as a recent global trend. For example, industrial materials using these hydrocarbon materials have less carbon dioxide emissions and less environmental impact when the raw material is derived from plants or microbial fermentation than from fossil fuels. It is believed that. In addition, when the industrial materials are discharged after use, if the raw materials of the industrial materials are derived from plants or from microbial fermentation, it is considered that they are easily decomposed by microorganisms in rivers and soils and have a low environmental load. Yes. Furthermore, carbon contained in industrial resources originating from constituents of living organisms such as plants and microorganisms is different from carbon contained in fossil fuels, and the living organisms absorb from the atmosphere by photosynthesis during the growth process. Derived from carbon dioxide. Therefore, even if these industrial resources are used, it is considered that there is no effect on the increase or decrease in the total amount of carbon dioxide in the atmosphere (hereinafter, sometimes referred to as the concept of carbon neutral). From the above, it is considered that when the raw material is derived from animals or plants or microbial fermentation, the environmental load is less when industrial materials are discharged into the environment after use than those derived from crude oil.

  Thus, several methods for producing a hydrocarbon material with less environmental load are disclosed. For example, Patent Document 1 discloses a method for producing a hydrocarbon-based oil by ketonization, hydrodeoxygenation, and isomerization of a raw material oil derived from a living body such as vegetable oil. Patent Document 2 discloses a method for obtaining a hydrocarbon mixture by reductive dehydroxymethylation of vegetable fatty alcohol.

Special table 2009-518530 gazette Special table 2010-531809 gazette

  However, the biological hydrocarbon compositions produced in Patent Documents 1 and 2 are all liquid compositions, and it is very difficult to produce a paste-like composition that can be used as a petrolatum substitute. there were.

  The present invention has been made in view of the above circumstances, and compared with existing hydrocarbon compositions, the content of contaminants other than the intended components is reduced, storage stability, and smoothness during application. Provided are a hydrocarbon composition having excellent properties (smoothness), gloss after application, stability under light irradiation, lubricity, and releasability, and a reduced environmental load, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have used a fatty acid composition having a specific fatty acid composition as a raw material, and performed a decarboxylative dimerization reaction on the fatty acid composition. Later, it was found that a paste-like hydrocarbon composition was obtained by performing a hydrodeoxygenation reaction on the obtained aliphatic ketone, and the present invention was completed.

That is, the manufacturing method of the paste-like composition of the present invention, the paste-like composition, and the method of using the paste-like composition are the following [1] to [22].
[1] Fatty acid composition is
(1) The content of the branched chain fatty acid is 70% by mass or more,
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less, and (3) at 25 ° C. having 2 or 3 carboxylic acids relative to the branched chain fatty acid. The content of the liquid branched chain fatty acid is 10% by mass or more,
Production of a paste-like composition characterized in that after a decarboxylative dimerization reaction is performed on a fatty acid composition, a hydrodeoxygenation reaction is performed on the resulting composition containing an aliphatic ketone. Method.
[2] The fatty acid composition is selected from the group consisting of isostearic acid, a branched chain fatty acid having 36 carbon atoms having two carboxylic acids, and a branched chain fatty acid having 54 carbon atoms having three carboxylic acids. The manufacturing method of the paste-like composition of said [1] containing the above.
[3] The method for producing a paste composition according to [1] or [2], wherein the fatty acid composition further contains a linear fatty acid having one or two carboxylic acids.
[4] The method for producing a paste-like composition according to any one of [1] to [3], wherein the branched chain fatty acid having one carboxylic acid at 25 ° C. is isostearic acid.
[5] The branched chain fatty acid having 2 or 3 carboxylic acids which is liquid at 25 ° C. has a branched chain fatty acid having 36 carbon atoms having 2 carboxylic acids and a branched chain having 54 carbon atoms having 3 carboxylic acids. The manufacturing method of the paste-like composition in any one of said [1]-[4] which is 1 or more selected from the group which consists of a chain fatty acid.
[6] The linear fatty acid in the fatty acid composition is composed of a linear fatty acid having 10 to 22 carbon atoms having one carboxylic acid and a linear fatty acid having 4 to 10 carbon atoms having two carboxylic acids. The manufacturing method of the paste-like composition in any one of said [3]-[5] which is 1 or more types selected from a group.
[7] Any of the above [1] to [6], wherein the decarboxylation dimerization reaction is performed in the presence of one or more selected from the group consisting of Group II, Group VII to XII metal atoms A method for producing a paste-like composition.
[8] The decarboxylation dimerization reaction is performed in the presence of one or more metals selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn. -The manufacturing method of the paste-like composition in any one of [7].
[9] The method for producing a paste-like composition according to [8], wherein the metal is an oxide or a hydroxide.
[10] The fatty acid composition is
(1) The content of the branched chain fatty acid is 70% by mass or more,
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less, and (3) at 25 ° C. having 2 or 3 carboxylic acids relative to the branched chain fatty acid. The content of the liquid branched chain fatty acid is 10% by mass or more,
Including a fatty ketone obtained after decarboxylation of a metal soap synthesized from a fatty acid composition and one or more selected from the group consisting of Group II and Group VII to XII metal atoms A method for producing a paste-like composition, wherein a hydrodeoxygenation reaction is performed on the composition.
[11] The hydrodeoxygenation reaction is a reaction in which a ketone group is reduced to a methylene group, and is performed in the presence of hydrazine or zinc amalgam. A method for producing the composition.
[12] The hydrodeoxygenation reaction is
A reduction reaction of the ketone for reducing the aliphatic ketone and synthesizing the aliphatic alcohol;
Intramolecular dehydration reaction in which the obtained aliphatic alcohol is dehydrated intramolecularly to form an unsaturated bond;
A reduction reaction of the unsaturated bond to obtain a saturated hydrocarbon by reducing the hydrocarbon in which the unsaturated bond is formed by the intramolecular dehydration reaction;
A method for producing a paste-like composition according to any one of the above [1] to [10].
[13] At least one of the reduction reaction of the ketone and the reduction reaction of the unsaturated bond is selected from the group consisting of Pt, Pd, Ni, Cu, Cr, Ru, Rh, Li, Al, B, and Zn. The method for producing a paste-like composition according to [12], which is performed in the presence of one or more.
[14] The method for producing a paste-like composition according to [12], wherein the intramolecular dehydration reaction is performed in the presence of a Bronsted acid and / or a Bronsted base.
[15] Any of [1] to [14] above, wherein a ratio of ¹⁴ C isotope to ¹² C isotope in the fatty acid composition is in the range of 6 × 10 ^{−13 to} 1.2 × 10 ⁻¹² . A method for producing a paste-like composition.
[16] Manufactured by the method for producing a paste composition according to any one of [1] to [15], wherein the ratio of ¹⁴ C isotope to ¹² C isotope is 6 × 10 ^{−13 to} 1.2 × 10 A pasty composition characterized by being in the range of ^-12 .
[17] The pasty composition according to [16], which is used as a substitute for petrolatum.
[18] The pasty composition according to [16], which is used as a lubricity improver.
[19] The pasty composition according to [16], which is used as a mold release improver.
[20] The pasty composition according to [16], which is used as an ointment base for pharmaceuticals or quasi drugs.
[21] The pasty composition of [16] used for cosmetics.
[22] The fatty acid composition is
(1) The content of the branched chain fatty acid is 70% by mass or more,
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less, and (3) at 25 ° C. having 2 or 3 carboxylic acids relative to the branched chain fatty acid. The content of the liquid branched chain fatty acid is 10% by mass or more,
A paste-like composition obtained by subjecting a fatty acid composition to a decarboxylative dimerization reaction and then subjecting the resulting composition containing an aliphatic ketone to a hydrodeoxygenation reaction, A method for using a paste-like composition, characterized by being used as an alternative to the above.

  By the method for producing a paste-like composition of the present invention, a paste-like hydrocarbon composition suitable for various industrial materials can be obtained from a fatty acid composition having a specific fatty acid composition. The paste-like composition obtained by this method can significantly reduce the content of impurities and impurities as compared to a paste-like hydrocarbon composition refined from crude oil, and has storage stability, It has excellent lubricity (smoothness), gloss after application, stability under light irradiation, lubricity, and releasability. Furthermore, a paste-like hydrocarbon composition with reduced environmental load can be obtained by using a biological fatty acid composition as a raw material. For this reason, the paste-like composition obtained by the said method is suitable mainly as a substitute of petrolatum, and can be used widely for various industrial materials.

<Method for producing paste-like composition>
The process for producing a paste-like composition of the present invention is carried out by subjecting a fatty acid composition comprising a specific fatty acid composition to hydrogenation for a composition containing an aliphatic ketone obtained after decarboxylation dimerization reaction. It is characterized by performing a deoxygenation reaction. By using a fatty acid composition having a specific fatty acid composition as a raw material, a paste-like composition can be obtained.

[Fatty acid composition]
The fatty acid composition used as a raw material has a fatty acid composition having the following characteristics (1) to (3).
(1) The content of the branched chain fatty acid is 70% by mass or more.
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less.
(3) The content ratio of the branched chain fatty acid which is liquid at 25 ° C. having 2 or 3 carboxylic acids with respect to the branched chain fatty acid is 10% by mass or more.
Each characteristic will be described below.

  The fatty acid composition has a branched chain fatty acid content of 70% by mass or more. The content of the branched chain fatty acid in the fatty acid composition may be 70% by mass or more, preferably 74% by mass or more, and more preferably 78% by mass or more. When the content of the branched chain fatty acid in the fatty acid composition is 70% by mass or more, the obtained hydrocarbon composition can be made into a paste. When the content of the branched chain fatty acid is low, the produced hydrocarbon composition is likely to be solid even if the above-mentioned characteristics (2) and (3) are provided, and a paste-like composition is produced. It is difficult.

  In addition, in this invention and this-application specification, a branched chain fatty acid means the compound (compound which consists of carbon and hydrogen) which has a branched chain, Comprising: One or several carboxylic acid. That is, it is a compound in which one or more hydrogen atoms of a branched hydrocarbon are substituted with a carboxyl group.

  The number of carbon atoms and the number of carboxylic acids of the branched chain fatty acid contained in the fatty acid composition are not particularly limited. For example, the branched chain has 5 to 54 carbon atoms and has 1 to 3 carboxylic acids. Fatty acids are mentioned. The fatty acid composition contains at least two kinds of branched chain fatty acids.

  Moreover, in this invention and this-application specification, both saturated fatty acid and unsaturated fatty acid are contained in branched chain fatty acid. The branched chain fatty acid contained in the fatty acid composition may be a saturated fatty acid only, an unsaturated fatty acid only, or both a saturated fatty acid and an unsaturated fatty acid. In the method for producing a paste-like composition of the present invention, as will be described later, the unsaturated bond in the reaction composition is finally converted into a saturated bond by a reduction reaction, so that the saturated fatty acid in the fatty acid composition as a raw material and Regardless of the content ratio of the unsaturated fatty acid, a paste-like composition containing a saturated hydrocarbon as a main component can be obtained.

  The fatty acid composition contains 65% by mass or less of a branched chain fatty acid having one carboxylic acid at 25 ° C. (hereinafter sometimes referred to as “liquid branched chain monomeric acid”). The content of the liquid branched monomeric acid in the fatty acid composition may be 65% by mass or less, preferably 60% by mass or less, and more preferably 40-60% by mass. When the content of the liquid branched monomeric acid in the fatty acid composition is 65% by mass or less, the obtained hydrocarbon composition can be made into a paste. When the content of the monomeric acid in the liquid branched chain is too large, the produced hydrocarbon composition is more liable to be liquid than the paste, even if the characteristics (1) and (3) are provided. It is difficult to produce a paste-like composition with favorable viscosity characteristics.

  Examples of the liquid branched monomer acid include branched chain fatty acids having one carboxylic acid having 5 to 20 carbon atoms. Specifically, isovaleric acid (isopentanoic acid), isocaproic acid (isohexanoic acid), isoenanthic acid (isoheptanoic acid), isocaprilic acid (isooctanoic acid), isoperargonic acid (isononanoic acid), isocapriic acid (isodecanoic acid), iso Undecanoic acid, isolauric acid (isododecanoic acid), isotridecylic acid (isotridecanoic acid), isomyristic acid (isotetradecanoic acid), isopentadecyl acid (isopentadecanoic acid), isopalmitic acid (isohexadecanoic acid), isomalagic acid (isoheptadecanoic acid) ), Isostearic acid (isooctadecanoic acid, 2-heptylundecanoic acid), isononadecylic acid (isonononadecanoic acid), and isoarachidic acid (isoicosanoic acid) are preferred, and isostearic acid is preferred. Preferred. The fatty acid composition may contain only one type of liquid branched-chain monomer acid, or may contain two or more types.

  The fatty acid composition is a branched-chain fatty acid having 2 or 3 carboxylic acids with respect to the branched-chain fatty acid, which is liquid at 25 ° C. (hereinafter sometimes referred to as “liquid branched-chain dimer acid or trimer acid”). The content ratio is 10% by mass or more (10 ≦ [content of branched liquid dimer or trimer acid] / [content of branched chain fatty acid] × 100). When the fatty acid composition contains liquid branched dimer acid or trimer acid, the obtained hydrocarbon composition can be made into a paste. In the fatty acid composition, when the content ratio of the dimer acid or trimer acid of the liquid branched chain with respect to the branched chain fatty acid is too low, the carbonized product produced even if the characteristics (1) and (2) are provided. The hydrogen composition is liable to be more liquid than the paste, and it is difficult to produce a paste composition having preferable viscosity characteristics.

  Examples of the liquid branched dimer acid or trimer acid include branched chain fatty acids having 2 or 3 carboxylic acids having 10 to 54 carbon atoms. Specifically, the compound obtained by the intermolecular polymerization reaction by 2 molecule | numerator or 3 molecule | numerator of the unsaturated fatty acid which has one C6-C20 carboxylic acid is mentioned. The liquid branched dimer acid or trimer acid may be any fatty acid that is a liquid fatty acid at 25 ° C. having at least one branched chain structure, and a molecule in which linear unsaturated fatty acids form a branched chain structure. The compound obtained by carrying out interpolymerization reaction may be sufficient, and the compound obtained by carrying out intermolecular polymerization reaction of branched chain unsaturated fatty acids may be sufficient. Specifically, a dibasic acid having 36 carbon atoms (branched fatty acid having two carboxylic acids) obtained by two molecules of isostearic acid undergoing an intermolecular polymerization reaction, and three molecules of isostearic acid being subjected to an intermolecular polymerization reaction. C54 tribasic acid (branched fatty acid having three carboxylic acids) and the like obtained by doing so.

  The fatty acid composition may contain other fatty acids as long as the fatty acid compositions (1) to (3) are satisfied. For example, the fatty acid composition may contain one or more linear fatty acids. In addition, in this invention and this-application specification, a linear fatty acid is a linear hydrocarbon and means the compound which has 1 or 2 carboxylic acid. That is, a straight-chain fatty acid having one carboxylic acid is a compound in which one of the hydrogen atoms bonded to the carbon atom at one end of the straight-chain hydrocarbon is substituted with a carboxyl group. . In the linear fatty acid having two carboxylic acids, the carbon atoms at both ends of the linear hydrocarbon are each substituted with one hydrogen atom bonded to the carbon atom by a carboxyl group.

The linear fatty acid contained in the fatty acid composition may be liquid at 25 ° C. or may be solid. Further, it may be a saturated fatty acid or an unsaturated fatty acid. Furthermore, you may have one carboxylic acid and may have two. Among these, linear fatty acids having one carboxylic acid having 8 to 22 carbon atoms and linear fatty acids having two carboxylic acids having 4 to 10 carbon atoms are preferable.
Specifically, as the linear fatty acid having one carboxylic acid, caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecane) Acid), oleic acid (cis-9-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (octadecanetrienoic acid), arachidic acid (eicosanoic acid), erucic acid (docosenoic acid), behenic acid (docosanoic acid) ) And the like. Examples of the linear fatty acid having two carboxylic acids include sebacic acid having 10 carbon atoms. In the present invention, the fatty acid composition may include both a linear fatty acid having one carboxylic acid having 10 to 22 carbon atoms and a linear fatty acid having two carboxylic acids having 4 to 10 carbon atoms. Preferably, it contains a linear fatty acid having one carboxylic acid having 10 to 22 carbon atoms and sebacic acid.

  In the present invention, the content of the linear fatty acid having one carboxylic acid contained in the fatty acid composition is preferably 26% by mass or less, and more preferably 20% by mass or less.

  The fatty acid composition preferably contains a linear fatty acid having two carboxylic acids, and more preferably contains sebacic acid. When it contains sebacic acid, the content is preferably 1% by mass or more, and more preferably 2 to 4% by mass.

Each fatty acid in the fatty acid composition may be refined from crude oil, synthesized from hydrogen gas and carbon dioxide gas, or derived from a living organism (derived from animals or plants or yeast fermentation) May be). A synthetic product or a biological one is preferable because contamination with unexpected impurities or the like can be suppressed, and a biological one is more preferable from the viewpoint of reducing environmental burden. Although ^{not, 14 C,} isotopes are included in the fatty acid-derived oil, the fatty acids derived from synthetic or biological in which the gas and raw material are ^{included, 14 C,} isotopes, for ^{12 C} isotope ¹⁴ The ratio of C isotopes is in the range of 6 × 10 ^{−13 to} 1.2 × 10 ⁻¹² .

The ¹⁴ C content of the sample can be measured in a liquid scintillation spectrometer by counting ¹⁴ C isotopes that decompose in the counter (Libby counter method) or by accelerator mass spectrometry. Accelerator mass spectrometry (abbreviation: AMS) uses nuclear physics analysis to analyze ¹⁴ C isotopes in very small samples (milligram range) in the range of ppt to ppq (10 ⁻¹² to 10 ⁻¹⁶ ). It can be detected.

  Moreover, when adjusting a fatty acid composition, a fatty acid may be added as it is, and may be added in the state of various salts, such as an alkali metal salt.

[Decarboxylative dimerization reaction]
In the method for producing a paste-like composition of the present invention, first, a fatty acid in the fatty acid composition is subjected to a decarboxylation dimerization reaction to obtain an aliphatic ketone. In the present invention, the method of decarboxylating and dimerizing each carboxylic acid of two molecules of fatty acid is not particularly limited, and can be performed using a known chemical reaction.

For example, after synthesizing a metal soap having a carbon number of [2n] from two fatty acid molecules having a carbon number of [n], the fatty acid having a carbon number of [2n-1] is obtained by decarboxylation by thermal decomposition. A ketone is obtained.
The synthesis of the metal soap can be performed, for example, by a saponification reaction using an alkaline earth metal or a metal. As the metal, for example, one or more selected from the group consisting of Group II, Group VII to XII metal atoms can be used, and it consists of Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn. One or more metals selected from the group are preferred. The metal is more preferably used as an oxide or a hydroxide. In the present invention, it is particularly preferable to use magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide or the like.
The thermal decomposition temperature and reaction time of the metal soap are not particularly limited as long as the temperature and time are sufficient for the decarboxylation reaction to occur. For example, the metal soap can be decarboxylated by heating at 140 to 400 ° C., preferably 160 to 340 ° C. for 5 to 30 hours, preferably 10 to 24 hours.

  In addition, in the manufacturing method of the paste-like composition of this invention, the process of synthesize | combining metal soap from the said fatty acid composition can also be abbreviate | omitted. That is, instead of performing the decarboxylation dimerization reaction using the fatty acid composition as a raw material, a metal soap is used as a raw material, and the metal soap is decarboxylated by thermal decomposition to be used for a subsequent hydrodeoxygenation reaction. Aliphatic ketones may be obtained. As the metal soap used as a raw material, one having a fatty acid residue composition similar to that obtained by saponifying the fatty acid composition is used. Specific examples include metal soaps synthesized from the fatty acid composition and one or more selected from the group consisting of Group II and Group VII to XII metal atoms.

[Hydrodeoxygenation reaction]
A hydrodeoxygenation reaction is performed on the composition containing the aliphatic ketone obtained by the decarboxylation dimerization reaction to obtain a paste-like composition containing saturated hydrocarbon as a main component. The hydrodeoxygenation reaction is not particularly limited as long as it is a reaction that can convert the ketone group of the aliphatic ketone to a methylene group, and can be performed by appropriately combining known chemical reactions.

  The hydrodeoxygenation reaction may be a reduction reaction in which a ketone group in an aliphatic ketone is directly reduced to a methylene group, such as Wolf-Kishner reduction or Clementen reduction. The Wolf Kishner reduction and the Clementen reduction can be performed by a conventional method. For example, in Wolf Kishner reduction, hydrazine and a base (for example, sodium hydroxide) are added to an aliphatic ketone dissolved in a solvent such as dimethyl sulfoxide or diethylene glycol, and reacted at room temperature to 200 ° C. In the Clementen reduction, zinc amalgam is added to and reacted with an aliphatic ketone dissolved in a strongly acidic solvent such as hydrochloric acid. In addition, the aliphatic ketone can be directly reduced by catalytic hydrogenation using a palladium catalyst in the presence of hydrogen gas.

  The hydrodeoxygenation reaction includes a reduction reaction of a ketone that reduces the aliphatic ketone and synthesizes an aliphatic alcohol, and an intramolecular dehydration reaction that forms an unsaturated bond by intramolecular dehydration of the obtained aliphatic alcohol. And a reduction reaction of the unsaturated bond in which unsaturated hydrocarbons are formed by the intramolecular dehydration reaction to obtain saturated hydrocarbons. The reaction at each stage can be performed by a conventionally known chemical reaction. These three-stage reactions can all be carried out continuously in one reaction system, or only two of these reactions can be carried out simultaneously in one reaction system. It can also be performed sequentially in the reaction system.

  For example, a reduction reaction of a ketone that synthesizes an aliphatic alcohol (that is, a reaction that converts a carbon-oxygen double bond of a carbonyl group to a hydroxyl group), or a reduction reaction that converts an unsaturated bond to a saturated bond (that is, a fatty acid) The reaction of reducing the carbon-carbon double bond therein to convert it into a carbon-carbon single bond) can be performed by a known reduction reaction. Further, both the reduction reactions may be carried out by a reduction reaction using the same catalyst, or may be carried out by a reduction reaction using different catalysts. In the present invention, at least one selected from the group consisting of Pt, Pd, Ni, Cu, Cr, Ru, Rh, Li, Al, B, and Zn is used as a catalyst, and reduction is performed in an environment in which hydrogen gas is introduced. It is preferable to carry out the reaction. In addition, Birch reduction using Li as a catalyst can be performed in the presence of liquid ammonia.

  The intramolecular dehydration reaction is not particularly limited as long as it is a reaction in which an aliphatic alcohol is dehydrated and condensed in the molecule. For example, a dehydration condensation reaction can be performed by using a Bronsted acid and / or Bronsted base as a catalyst and heating in the presence of these. The reaction temperature and time can be appropriately adjusted in consideration of the type of catalyst used, the amount of aliphatic alcohol used in the reaction, and the like. For example, the reaction can be performed at 80 to 250 ° C. for 1 to 10 hours.

  Examples of the Bronsted acid include acid catalysts such as activated clay, zeolite, and alumina. Examples of the Bronsted base include aluminum hydroxide and sodium hydroxide.

  The unsaturated bond formed by the intramolecular dehydration reaction by the reduction reaction of the unsaturated bond to the saturated bond, the unsaturated bond originally possessed by the fatty acid used as the raw material, and the unsaturated bond formed by the previous reaction. Saturated bonds are also reduced. For this reason, by sufficiently carrying out the reduction reaction, the content of unsaturated hydrocarbons is extremely small or consists only of saturated hydrocarbons (that is, the content of unsaturated hydrocarbons in a normal detection method). A composition (below the detection limit) is obtained.

[Paste-like composition]
The composition obtained by the method for producing a paste-like composition of the present invention is in a paste form (a fluid and highly viscous state) containing saturated hydrocarbon as a main component. In particular, the paste composition has a very low content of high-molecular-weight / high-melting impurities, impurities of unknown structure, etc., compared to conventional petroleum jelly manufactured from crude oil. Excellent lubricity (smoothness), gloss after application, stability under light irradiation, lubricity, and releasability.

  The paste composition can be suitably used as a raw material for various products, particularly as a substitute for petrolatum. For example, the paste-like composition can be suitably used as an ointment base for a lubricity improver, a mold release improver, a pharmaceutical product or a quasi-drug.

  Moreover, the said paste-form composition can also be used as it is as a raw material of cosmetics, a pharmaceutical, and a quasi-drug. When using the said paste-like composition as 1 type of raw materials, such as cosmetics, content of the said paste-like composition in cosmetics etc. can be 0.1-95 mass%, 0.5- 90 mass% is preferable and 1-80 mass% is more preferable.

  Cosmetic forms containing the paste composition include oil-dissolving types; O / W type, W / O type, W / O / W type, O / W / O type and other emulsifying types; It can take a desired form such as a solid type; In addition, the types of such cosmetics include cleansing oils, emulsions, creams, serums, emollient creams, lip care sticks and other skin care cosmetics, makeup bases, lipsticks, foundations, eye shadows and other makeup cosmetics, hair waxes, Examples include hair care cosmetics such as hair sprays and hair conditioners.

  The cosmetics, pharmaceuticals, and quasi-drugs containing the paste-like composition can be produced by blending various components generally used in cosmetics and the like, if necessary, by a conventionally known method. For example, anionic surfactant, cationic surfactant, amphoteric surfactant, lipophilic nonionic surfactant, hydrophilic nonionic surfactant, silicone surfactant, natural surfactant, liquid fat, solid fat Waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, powders, humectants, natural water-soluble polymers, semi-synthetic water-soluble polymers, synthetic water-soluble polymers, inorganic Water-soluble polymer, thickener, ultraviolet absorber, sequestering agent, lower alcohol, polyhydric alcohol, monosaccharide, oligosaccharide, polysaccharide, amino acid, organic amine, synthetic resin emulsion, pH adjuster, vitamins, oxidation An inhibitor, an antioxidant assistant, a fragrance, water, and the like can be appropriately blended as necessary.

  Hereinafter, the present invention will be described in more detail based on specific examples. In addition, this invention is not limited to the content of the Example shown below at all.

Example 1 Synthesis of Pasty Hydrocarbon Composition
In a 2 L pressure-resistant metal container equipped with a stirrer, thermometer, nitrogen gas inlet tube and moisture separator, 8 g of lauric acid [Product name: PALMAC98-12 (manufactured by ACIDCHEM)], myristic acid [Product name: PALMAC98-14] (Product of ACIDCHEM)] 20 g, palmitic acid [product name: PALMAC98-16 (manufactured by ACIDCHEM)] 34 g, stearic acid [product name: PALMAC98-18 (manufactured by ACIDCHEM)] 41 g, mixture of arachidic acid / behenic acid [ Product name: EDENOR C20-22 (manufactured by Cognis)] 45 g, sebacic acid [product name: sebacic acid (manufactured by Ogura Gosei Kogyo)], purified dimer acid [product name: EMPOL1012 (manufactured by Cognis)] 304 g, isostearin Acid [Product name: PRISORINE 3505 (manufactured by Croda)] 51 8 g and 152 g of zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and reacted at 320 ° C. under a nitrogen stream for 12 hours. After the reaction, 5 wt% of Ru / C (manufactured by Wako Pure Chemical Industries) and p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries) 500 ppm are added to the total amount of raw fatty acids (1000 g), After removing the air under reduced pressure, hydrogen gas was continuously introduced at a pressure of 3 MPa and reacted at 240 ° C. for 3 hours. Subsequently, 3 wt% aluminum hydroxide [product name: KYOWARD 200B (manufactured by Kyowa Chemical Industry Co., Ltd.)] was added to the total amount of raw fatty acids, and the mixture was stirred at 105 ° C. for 2 hours under reduced pressure. Ru / C, zinc oxide, and aluminum hydroxide were removed by filtration to obtain 650 g of a white paste-like hydrocarbon composition.

  The purified dimer acid and isostearic acid used were analyzed by GPC (Gel Permeation Chromatography), and no peak was detected on the left side of the dimer acid in the chromatograph. That is, it was confirmed that the purified dimer acid and isostearic acid used did not contain trimer acid at a level detectable by GPC.

[Examples 2 to 9, Comparative Examples 1 to 7]
A hydrocarbon composition was obtained in the same manner as in Example 1 except that the raw fatty acid composition was changed to the fatty acid composition shown in Tables 1 and 2. In Tables 1 and 2, “C10” is capric acid [product name: PALMAC 99-10 (manufactured by ACIDCHEM)], “C12” is lauric acid [product name: PALMAC98-12 (manufactured by ACIDCHEM)], “C14”. Is myristic acid [Product name: PALMAC98-14 (manufactured by ACIDCHEM)] “C16” is palmitic acid [Product name: PALMAC98-16 (manufactured by ACIDCHEM)], “C18” is stearic acid [Product name: PALMAC98-18 ( ACIDCHEM)], “C20” is arachidic acid, “C22” is behenic acid (a mixture of arachidic acid / behenic acid [product name: EDENOR C20-22 (manufactured by Cognis)]), “SLFA” is 1 carvone Total amount of linear fatty acids with acid, “C10DA” is sebacic acid [Product name: Sebacic acid (Ogura Synthesis) "Dimer" is a purified dimer acid [product name: EMPOL1012 (manufactured by Cognis)], "iC18" is isostearic acid [product name: PRISOLINE 3505 (manufactured by Croda)], and "iFA" is a branched chain. Indicates the total amount of fatty acids. “Dimer / iFA” indicates the content of the purified dimer acid relative to the total amount of branched chain fatty acids.

  About the hydrocarbon compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 7, storage stability, lubricity at the time of application (smoothness), gloss after application, stability under light irradiation, friction characteristics ( Lubricity) and moisture permeability were evaluated. In addition, Nomcoat W (manufactured by Nisshin Oillio Group) was used as Comparative Example 8, and pharmacopeia white petrolatum (manufactured by Kosuge Pharmaceutical Co., Ltd.) was also used as Comparative Example 9.

<Evaluation of lubricity during application>
The lubricity at the time of application was evaluated by a sensory test when about 100 μg of each hydrocarbon composition was taken and applied to the inside of the arm. Judgment criteria are shown below.
Evaluation criteria;
○: It can be applied smoothly without feeling solid at the time of application.
(Triangle | delta): Although a slight solid feeling is felt at the time of application | coating, it can apply | coat smoothly.
X: A solid feeling is clearly felt at the time of application and lacks smoothness.

<Storage stability evaluation>
(Evaluation method)
After putting each hydrocarbon composition into a 50 mL glass bottle with a lid and sealing the lid, the chamber temperature is left at 48 ° C. for 48 hours, and the chamber temperature is 40 ° C. At the point of time, the sample was taken out from the chamber. About 100 μg of each sample was taken immediately after removal and confirmed by a sensory test when applied to the inside of the arm, and evaluated according to the following criteria.
Evaluation criteria;
○: No change before and after the stability test.
(Triangle | delta): A slight change is recognized by the lubricity at the time of application | coating before and after a stability test.
X: A remarkable change is observed in the lubricity at the time of application before and after the stability test.

<Gloss evaluation during application>
The gloss after application was evaluated by visual evaluation and the degree of increase in glossiness.
As for the gloss after the visual application, first, the inside of the paneler's arm was cleaned with running water and a hand washing detergent, and then excess oil was removed with ethanol. After drying the clean spot, about 100 μg of each hydrocarbon composition was placed on the clean spot, and the gloss after spreading was visually evaluated.
Evaluation criteria;
○: Gloss and glossiness are observed on the coated surface.
Δ: The coated surface slightly lacks gloss and gloss.
X: Gloss and glossiness are not recognized on the coated surface.

<Gloss evaluation of coated surface>
The gloss of the coated surface was evaluated by the “degree of increase in glossiness (hereinafter referred to as ΔGs)” when each hydrocarbon composition was coated on the rough surface with a constant film thickness. The glossiness was measured with reference to Method 1 “85 degree specular gloss” described in JIS Z 8741. For measurement, a PG-1M type handy gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. was used, and a fixed film thickness type applicator [Product name: Doctor Blade (manufactured by Tester Sangyo Co., Ltd.)] ] Was used to prepare a coating film with a film thickness of 10 μm. The glossiness was obtained by measuring the glossiness at an incident angle of 85 ° (hereinafter referred to as Gs85 °) at n = 2 and calculating ΔGs85 ° by the following formula.
Formula: [Glossiness increase degree (ΔGs85 °)] = [Average value of Gs85 ° of sample] − [Average value of Gs85 ° of rough surface]

<Evaluation of stability of hue and odor under light irradiation>
Each hydrocarbon composition was put into a 30 mL glass bottle that can be sealed and left in a place exposed to sunlight to perform an exposure test. In each sample, a sample shielded with aluminum foil was evaluated as a control sample. About each sample after three-day progress, the change of the hue and the change of the odor were respectively compared with the control sample, and evaluated according to the following criteria.
[Hue change]
A: There is no change in hue as compared with the control sample.
○: Slight yellowing is observed compared to the control sample.
Δ: Significant yellowing is observed compared to the control sample.
[Change in odor]
A: There is no change in odor compared to the control sample.
○: Slightly deteriorated odor is observed compared to the control sample.
(Triangle | delta): The remarkable deterioration odor is recognized compared with a control sample.

<Evaluation of friction characteristics>
Lubricity was evaluated by measuring the static friction coefficient and dynamic friction coefficient. The static friction coefficient and the dynamic friction coefficient are measured using a static friction measuring machine [model: Handy Tribomaster TS201Ts (manufactured by Trinity Labs)], and a protein particle-woven artificial leather [product name: Supplare (manufactured by Idemitsu Technofine)]. Measurements were performed on the surface using the following conditions. The static friction coefficient was evaluated by calculating an average value in 10 reciprocations.
Measurement load: 300g
Sample amount: 100 μg
Mounting platform moving speed: 10 reciprocations at a speed of 0.5 cm / sec Mounting platform moving distance: 6 cm

<Evaluation of moisture permeability>
A Φ70 mm filter paper (manufactured by ADVANTEC Co., Ltd .; No. 1) was prepared by accurately weighing each hydrocarbon composition dissolved and dried in a thermostat at 105 ° C. for 12 hours. 5C] (assumed to be weight (A)), the weight (B) of the filter paper impregnated with each hydrocarbon composition was accurately measured. The impregnation amount of the sample (hydrocarbon composition) was adjusted so that the sample coating amount was 6 to 8 mg / cm ² using the following calculation formula.
Formula: [Sample coating amount (mg / cm ² )] = ([Weight (B) (mg)] − [Weight (A) (mg)]) / [38.47 (cm ² ) (area of filter paper) ]

The filter paper coated with the sample was placed in a moisture permeable cup (JIS-Z0208) containing glycerin (about 15 g), and fixed with a dissolved wax sealant (beeswax / paraffin wax mixture, weight ratio: 6: 4). After the sealant solidified, the weight (weight (C)) of the moisture permeable cup on which the filter paper was set was accurately measured.
Place the moisture permeable cup with the filter paper fixed in a desiccator saturated with water vapor (saturated ammonium chloride aqueous solution, humidity: 80%), leave the desiccator at 25 ° C for 3 hours, and then accurately measure the weight of the moisture permeable cup. And weight (D).
Using the following calculation formula, the water permeation amount and water permeation rate that permeated from the outside to the inside of the filter paper coated with each hydrocarbon composition and dissolved in glycerin were calculated.
Formula: [moisture permeation amount (mg / cm ² )] = ([weight (D) (mg)] − [weight (C) (mg)]) / [28.26 (cm ² ) (permeation of moisture permeable cup area)]
Formula: [moisture permeability (%)] = [moisture permeability of sample (mg)] / [moisture permeability of blank (mg)] × 100

  The evaluation results of each hydrocarbon composition are shown in Tables 1 and 2. As a result, the hydrocarbon compositions of Examples 1 to 9 have the storage stability, the slipperiness (smoothness) at the time of application, the gloss after application, and the stability under light irradiation as compared with those of Comparative Examples 8 and 9. And the friction properties (lubricity) and moisture permeability were superior to those of the hydrocarbon composition formulations of Comparative Examples 8 and 9. On the other hand, the hydrocarbon composition of Comparative Example 1 in which the content of the liquid branched-chain monomer acid in the raw fatty acid composition is more than 65% by mass is close to liquid rather than pasty and has storage stability. The slipperiness (smoothness) at the time of application, the gloss after application, and the stability under light irradiation were all inferior to the hydrocarbon compositions of Examples 1-9. The hydrocarbon compositions of Comparative Examples 2 and 3 that did not contain dimer acid and the hydrocarbon compositions of Comparative Examples 4 to 7 in which the content of branched chain fatty acids was less than 70% by mass were all solid. Yes, all of storage stability, lubricity (smoothness) during coating, gloss after coating, and stability under light irradiation were inferior to the hydrocarbon compositions of Examples 1-9.

  The paste-like composition obtained by the method for producing a paste-like composition of the present invention has storage stability, lubricity (smoothness) during application, gloss after application, stability under light irradiation, lubricity, and Since it has excellent releasability and is suitable as a substitute for petrolatum, it is useful as an industrial base material in various industrial products such as cosmetics, ointment bases in pharmaceuticals, industrial lubricants and mold release agents.

Claims (22)

Fatty acid composition
(1) The content of the branched chain fatty acid is 70% by mass or more,
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less, and (3) at 25 ° C. having 2 or 3 carboxylic acids relative to the branched chain fatty acid. The content of the liquid branched chain fatty acid is 10% by mass or more,
Production of a paste-like composition characterized in that after a decarboxylative dimerization reaction is performed on a fatty acid composition, a hydrodeoxygenation reaction is performed on the resulting composition containing an aliphatic ketone. Method.   The fatty acid composition contains at least one selected from the group consisting of isostearic acid, a branched chain fatty acid having 36 carbon atoms having two carboxylic acids, and a branched chain fatty acid having 54 carbon atoms having three carboxylic acids. The method for producing a paste-like composition according to claim 1.   The manufacturing method of the paste-form composition of Claim 1 or 2 in which the said fatty acid composition contains the linear fatty acid which further has 1 or 2 carboxylic acid.   The manufacturing method of the paste-form composition as described in any one of Claims 1-3 whose liquid branched chain fatty acid which has the said 1 carboxylic acid at 25 degreeC is isostearic acid.   The branched fatty acid in liquid form at 25 ° C. having 2 or 3 carboxylic acids is a branched chain fatty acid having 36 carbon atoms having 2 carboxylic acids and a branched chain fatty acid having 54 carbon atoms having 3 carboxylic acids. The manufacturing method of the paste-form composition as described in any one of Claims 1-4 which is 1 or more selected from the group which consists of.   The linear fatty acid in the fatty acid composition is selected from the group consisting of a linear fatty acid having 10 to 22 carbon atoms having one carboxylic acid and a linear fatty acid having 4 to 10 carbon atoms having two carboxylic acids. The manufacturing method of the paste-form composition as described in any one of Claims 3-5 which is 1 or more types.   The paste form according to any one of claims 1 to 6, wherein the decarboxylation dimerization reaction is performed in the presence of one or more selected from the group consisting of Group II, Group VII to XII metal atoms. A method for producing the composition.   The decarboxylation dimerization reaction is performed in the presence of one or more metals selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn. A method for producing a paste-like composition according to claim 1.   The manufacturing method of the paste-form composition of Claim 8 whose said metal is an oxide or a hydroxide. Fatty acid composition
(1) The content of the branched chain fatty acid is 70% by mass or more,
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less, and (3) at 25 ° C. having 2 or 3 carboxylic acids relative to the branched chain fatty acid. The content of the liquid branched chain fatty acid is 10% by mass or more,
Including a fatty ketone obtained after decarboxylation of a metal soap synthesized from a fatty acid composition and one or more selected from the group consisting of Group II and Group VII to XII metal atoms A method for producing a paste-like composition, wherein a hydrodeoxygenation reaction is performed on the composition.   The said hydrodeoxygenation reaction is reaction which reduces a ketone group to a methylene group, and is performed in presence of hydrazine or zinc amalgam, The paste-form composition as described in any one of Claims 1-10. Manufacturing method. The hydrodeoxygenation reaction is
A reduction reaction of the ketone for reducing the aliphatic ketone and synthesizing the aliphatic alcohol;
Intramolecular dehydration reaction in which the obtained aliphatic alcohol is dehydrated intramolecularly to form an unsaturated bond;
A reduction reaction of the unsaturated bond to obtain a saturated hydrocarbon by reducing the hydrocarbon in which the unsaturated bond is formed by the intramolecular dehydration reaction;
The manufacturing method of the paste-form composition as described in any one of Claims 1-10 which has these.   At least one of the reduction reaction of the ketone and the reduction reaction of the unsaturated bond is one or more selected from the group consisting of Pt, Pd, Ni, Cu, Cr, Ru, Rh, Li, Al, B, and Zn The manufacturing method of the paste-form composition of Claim 12 performed in presence.   The method for producing a paste-like composition according to claim 12, wherein the intramolecular dehydration reaction is performed in the presence of a Bronsted acid and / or a Bronsted base. The paste according to any one of claims 1 to 14, wherein a ratio of ¹⁴ C isotope to ¹² C isotope in the fatty acid composition is in a range of 6 × 10 ^{−13 to} 1.2 × 10 ^−12. A method for producing a composition. It manufactures by the manufacturing method of the paste-form composition as described in any one of Claims 1-15, and the ratio of ¹⁴ C isotope with respect to ¹² C isotope is 6 * 10 < ^-13 > -1.2 * 10 < ^-12 >. A paste-like composition characterized by being in the range.   The paste-like composition according to claim 16, which is used as a substitute for petrolatum.   The paste-like composition according to claim 16, which is used as a lubricity improver.   The paste-like composition of Claim 16 used as a mold release improvement agent.   The paste-like composition according to claim 16, which is used as an ointment base for pharmaceuticals or quasi drugs.   The paste-like composition of Claim 16 used for cosmetics. Fatty acid composition
(1) The content of the branched chain fatty acid is 70% by mass or more,
(2) The content of branched fatty acid that is liquid at 25 ° C. having one carboxylic acid is 65% by mass or less, and (3) at 25 ° C. having 2 or 3 carboxylic acids relative to the branched chain fatty acid. The content of the liquid branched chain fatty acid is 10% by mass or more,
A paste-like composition obtained by subjecting a fatty acid composition to a decarboxylative dimerization reaction and then subjecting the resulting composition containing an aliphatic ketone to a hydrodeoxygenation reaction, A method for using a paste-like composition, characterized by being used as an alternative to the above.