Surfactant composition and method for producing the same

Abstract

An object of the present invention is to provide a novel surfactant composition which can improve detergency, does not gel or is unlikely to gel during handling, and has suppressed odor. The problem is solved by a surfactant composition, which comprises: a C12 body represented by the following formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 9; a C13 body represented by the above formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 10; a C14 body represented by the above formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 11; and a Y body represented by the above formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is at least one of 8 or less and 12 or more, the content of the C12 body is 10 to 25% by mass, the content of the C13 body is 40 to 65% by mass, the content of the C14 body is 20 to 49.9% by mass, and the content of the Y body is 0.1% by mass or more and less than 5% by mass.

Description

Technical Field

[0001] The present invention relates to surfactant compositions and methods for making the same. Background Art

[0002] Higher secondary alcohol ethoxylates are widely used as nonionic surfactants due to their low pour point and easy handling. As a known example, there is a detergent composition containing a nonionic surfactant and a primary alcohol alkoxylate, an anionic surfactant or a cationic surfactant for the purpose of improving cleaning power, wherein the nonionic surfactant contains a higher secondary alcohol alkoxylate adduct represented by a specific chemical formula (for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 11-349984 Summary of the invention

[0006] [Problems to be solved by the invention]

[0007] On the other hand, since the aqueous composition containing a surfactant is used in a flowing state, the gelation range must be properly controlled. In addition, the inventors have found that in modern society, there are not only basic performance issues such as the cleaning power of the surfactant composition, but also new issues such as reducing odor. Therefore, the object of the present invention is to provide a novel surfactant composition that can improve cleaning power, does not gel or is not easy to gel, and has suppressed odor.

[0008] [Technical solutions to solve the problem]

[0009] The above-mentioned problems can be solved by the following invention.

[0010] A surfactant composition comprising a C12 body represented by the following formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 9;

[0011] [Chemical formula 1]

[0012]

[0013] A C13 body represented by the above formula (1), in which A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 10; a C14 body represented by the above formula (1), in which A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 11; and a Y body represented by the above formula (1), in which A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is at least one of 8 or less and 12 or more; the content of the C12 body is 10 to 25% by mass, the content of the C13 body is 40 to 65% by mass, the content of the C14 body is 20 to 49.9% by mass, and the content of the Y body is 0.1% by mass or more and less than 5% by mass.

[0014] [Effects of the invention]

[0015] According to the present invention, it is possible to provide a novel surfactant composition which can improve detergency, does not gel or is unlikely to gel, and has suppressed odor. DETAILED DESCRIPTION

[0016] The present invention is described below. It should be noted that the present invention is not limited to the following embodiments. In addition, unless otherwise specified, the operation and the measurement of physical properties are measured at room temperature (20 to 25° C.). In addition, the description of "content" can be interpreted as "content ratio" according to the context.

[0017] [First Invention]

[0018] <Surfactant composition>

[0019] A surfactant composition according to one embodiment of the present invention includes:

[0020] A C12 compound represented by the following formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 9;

[0021] [Chemical formula 2]

[0022]

[0023] A C13 body represented by the above formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 10; a C14 body represented by the above formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is 11; and a Y body represented by the above formula (1), wherein A is an alkylene group having 1 to 3 carbon atoms, x is 1 to 50, and m+n is at least one of 8 or less and 12 or more; the content of the C12 body is 10 to 25% by mass, the content of the C13 body is 40 to 65% by mass, the content of the C14 body is 20 to 49.9% by mass, and the content of the Y body is 0.1% or more and less than 5% by mass. The surfactant composition (sometimes also referred to as a "cleaning agent composition") can improve cleaning power, does not gel or is not easy to gel (during treatment), and has suppressed odor.

[0024] In one embodiment of the present invention, the alkylene group having 1 to 3 carbon atoms is preferably an ethylene group or a propylene group, and more preferably an ethylene group. According to this embodiment, a surfactant composition having high detergency can be obtained at low cost.

[0025] In one embodiment of the present invention, x is preferably 5 to 50, more preferably 6 to 30, further preferably 7 to 15, and further preferably 9 to 12. This embodiment can impart solubility in water and affinity for oil, and exert excellent cleaning power. It should be noted that A and x of the C12 body, C13 body, C14 body, and Y body may be different.

[0026] In one embodiment of the present invention, the content of the C12 body is 10% by mass or more and 25% by mass or less, preferably 15 to 24% by mass, more preferably 16 to 23% by mass, further preferably 17 to 22% by mass, further preferably 18 to 22% by mass, and further preferably 19 to 22% by mass. In this manner, the fluidity and cleaning power of the liquid detergent can be taken into account. If it is less than 10% by mass, the aqueous solution may gel. If it exceeds 25% by mass, the cleaning power may be reduced.

[0027] In one embodiment of the present invention, the content of the C13 body is 40 to 65% by mass, preferably 45 to 65% by mass, more preferably 48 to 63% by mass, further preferably 50 to 60% by mass, further preferably 50 to 58% by mass, further preferably 50 to 56% by mass, further preferably 50% by mass or more and less than 55% by mass, and may be 51 to 53% by mass. In this manner, there is a technical effect of improving the fluidity of the liquid detergent. If it is less than 40% by mass, the aqueous solution may gel. If it is 55% by mass or more (or more than 65% by mass), the aqueous solution may gel. Or the odor level sometimes deteriorates.

[0028] In one embodiment of the present invention, the content of the C14 body is 20 to 49.9% by mass, preferably 21 to 30% by mass, more preferably 22 to 29% by mass, further preferably 23 to 28% by mass, and further preferably 24 to 26% by mass. In this manner, there is a technical effect of inhibiting gelation and improving cleaning power. If it is less than 20% by mass, the cleaning power may be reduced. If it exceeds 49.9% by mass, gelation is likely.

[0029] In one embodiment of the present invention, the content of the Y body is 0.1% by mass or more and less than 5% by mass, preferably 0.2-4.5% by mass, more preferably 0.4-4.0% by mass, 0.8-3.8% by mass, 1.0-3.6% by mass, 1.2-3.5% by mass, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.6% by mass or more, 1.8% by mass or more, 2.0% by mass or more, 2.2% by mass or more, 2.4% by mass or more, 2.6% by mass or more, or 2.8% by mass or more. In this way, there is a technical effect of suppressing the gelation of the detergent and further improving the cleaning power. If it is less than 0.1% by mass, the desired effect of the present invention cannot be exerted. If it is 5% by mass or more, the odor may deteriorate. It should be noted that, as described later, from the viewpoint of suppressing odor, the content of the C15 body is preferably 2.0% by mass or less.

[0030] According to one embodiment of the present invention, the content (containing ratio) of at least one of the C9 body, C10 body and C11 body is preferably the same as or more than the content (containing ratio) of at least one of the C15 body, C16 body and C17 body. Through this embodiment, the cleaning power is further improved. According to one embodiment of the present invention, the content (containing ratio) of at least one of the C9 body, C10 body and C11 body relative to the content (containing ratio) of at least one of the C15 body, C16 body and C17 body is 1 or more, 1.1 or more or 1.2 or more. Through this embodiment, the cleaning power is further improved. According to one embodiment of the present invention, the content (containing ratio) of at least one of the C9 body, C10 body and C11 body relative to the content (containing ratio) of at least one of the C15 body, C16 body and C17 body is 10 or less, 7 or less, 5 or less, less than 5, 4 or less, 3 or less, 2 or less, 1.8 or less, 1.6 or less or 1.5 or less. Through this embodiment, the cleaning power is further improved.

[0031] In one embodiment of the present invention, in the above-mentioned Y body, m+n is at least one selected from 7, 8, 12 and 13. That is, by the above-mentioned Y body being at least one selected from C10 body, C11 body, C15 body and C16 body, it has the technical effect of being able to inhibit the gelation of the aqueous solution and further improve the cleaning power. Although the cleaning power of C10 body and C11 body is slightly poor, they have the characteristics of inhibiting gelation and excellent penetration into the fiber. Although the C15 body and C16 body maintain the characteristics of fluidity and have slightly poor penetration into the fiber, they have the characteristics of very excellent cleaning power. Therefore, in each use, by appropriately selecting from the group consisting of C10 body, C11 body, C15 body and C16 body, a surfactant composition having both fluidity, penetration and cleaning power can be obtained. In this embodiment, it is preferred that m+n is at least one selected from 8 and 12. That is, by making the Y form at least one selected from the C11 form and the C15 form, there is a technical effect that appropriate fluidity, penetration and cleaning power can be achieved in various applications as described above.

[0032] Furthermore, since saturated aliphatic hydrocarbons having m+n of 7, 8, 12, or 13 can be further included in the saturated aliphatic hydrocarbons having m+n of 9, 10, or 11 as the main raw material of the surfactant containing the Y-form, precise distillation purification is not required when producing the saturated aliphatic hydrocarbons. Therefore, equipment for precise distillation is not required, and the distillation operation can be easily performed within the distillation time, so the productivity of the saturated aliphatic hydrocarbons is improved, and as a result, there is an economic effect that the production cost of the surfactant composition can be unexpectedly reduced.

[0033] In one embodiment of the present invention, the content of C10 body is 0.2 mass % or less, 0.1 mass % or less, or 0.05 mass % or less. This embodiment has a technical effect of improving the fluidity of the detergent.

[0034] In one embodiment of the present invention, the content of C11 body is 0.3 mass % or more, more than 0.3 mass %, 0.35 mass % or more, 0.4 mass % or more, 0.45 mass % or more, 0.5 mass % or more, 0.6 mass % or more, 0.7 mass % or more, 0.8 mass % or more, 0.9 mass % or more, 1.0 mass % or more, more than 1.0 mass %, 1.2 mass % or more, 1.4 mass % or more, 1.6 mass % or more, or 1.8 mass % or more. This embodiment has the technical effect of improving the fluidity of the detergent.

[0035] In one embodiment of the present invention, the content of C11 body is 3.0 mass %, 2.4 mass %, 2.2 mass %, 2.1 mass %, 2.0 mass %, 1.8 mass %, 1.6 mass %, 1.5 mass %, 1.4 mass %, 1.2 mass %, 1.0 mass %, 0.8 mass %, 0.6 mass %, or 0.5 mass %. In this way, there is a technical effect that the cleaning power of the cleaning agent can be suppressed. Therefore, one embodiment of the present invention is that the content of C11 body exceeds 0.3 mass % and is 3.0 mass %.

[0036] In one embodiment of the present invention, the content of C15 body is 2.0 mass % or less, 1.9 mass % or less, 1.8 mass % or less, 1.7 mass % or less, 1.6 mass % or less, less than 1.6 mass %, 1.5 mass % or less, 1.4 mass % or less, 1.2 mass % or less, 1.0 mass % or less, or 0.05 mass % or less. This embodiment has the technical effect of being able to suppress the gelation of the detergent.

[0037] Here, as shown in the examples, if the C15 body is greater than 2% by mass, it is possible to become the cause of the odor of the detergent composition, so it is not preferred. On the other hand, in one embodiment of the present invention, the content of the C15 body exceeds 0% by mass, 0.5% by mass or more, 0.6% by mass or more, 0.8% by mass or more, 1.0% by mass or more, 1.2% by mass or more, 1.4% by mass or more, 1.5% by mass or more, 1.6% by mass or more, more than 1.6% by mass, or 1.8% by mass or more. In this way, there is a technical effect of improving the cleaning power of the detergent.

[0038] In one embodiment of the present invention, the content of C11 body with m+n of 8 exceeds 0.3 mass % (0.6 mass % or more, 0.7 mass % or more, 0.8 mass % or more, or 0.9 mass % or more) and is 3.0 mass % or less, and the content of C15 body with m+n of 12 is less than 1.6 mass %. This embodiment provides a technical effect of excellent fluidity, penetration and cleaning power as a cleaning agent.

[0039] In one embodiment of the present invention, the total content of the C12 form, the C13 form, the C14 form, and the Y form is 100% by mass.

[0040] It should be noted that, in this specification, the upper limit, lower limit, and range of various contents (content ratios) are disclosed, and in this specification, all upper limit, lower limit, and range or combinations thereof are disclosed, which becomes the basis for the legality of the modification.

[0041] <Method for producing surfactant composition>

[0042] In one embodiment of the present invention, a method for producing a surfactant composition includes the step of adding an alkylene oxide to a secondary alcohol mixture, wherein the secondary alcohol mixture contains 10 to 25% by mass of a C12 precursor represented by the following formula (2) where m+n is 9;

[0043] [Chemical formula 3]

[0044]

[0045] 40 to 65% by mass of a C13 precursor represented by the above formula (2) and having m+n of 10; 20 to 49.9% by mass of a C14 precursor represented by the above formula (2) and having m+n of 11; and 0.1% by mass or more and less than 5% by mass of a Y precursor represented by the above formula (2) and having m+n of at least one of 8 or less and 12 or more. According to this production method, a surfactant composition can be produced that has improved cleaning power and does not gel or is not easily gelled during handling.

[0046] (Preparation of secondary alcohol mixture)

[0047] In one embodiment of the present invention, the secondary alcohol mixture represented by the above formula (2) can be obtained by subjecting the raw material saturated aliphatic hydrocarbon mixture to an oxidation step and an alcoholation step.

[0048] In one embodiment of the present invention, the oxidation process can be carried out by referring to or combining with conventionally known knowledge. For example, the description of the oxidation process in Japanese Patent Publication No. 48-34807 and Oil Chemistry, 24, 7, pp427-434 (1975) can be appropriately referred to or combined, but it is not limited to these methods. If an example is given for illustration, the oxidation reaction is carried out by blowing a gas containing oxygen and nitrogen into the raw material saturated aliphatic hydrocarbon mixture in the presence of a boron compound. As the boron compound, metaboric acid, orthoboric acid, etc. are preferred. Next, orthoboric acid esterification of the alcohol produced by hydrolysis such as hot water treatment is carried out. It is preferred to react the alcohol with boric acid under the conditions of 10 to 300 hPa and 150 to 190° C. to carry out orthoboric acid esterification. Unreacted saturated aliphatic hydrocarbons can be removed by flashing the mixture containing the orthoboric acid ester, preferably at 1 to 100 hPa. Next, the distillation residue is hydrolyzed to separate into boric acid and an organic layer through a hydrolysis step, the separated organic layer is saponified with an alkali, the alkaline aqueous solution layer and the crude alcohol layer are saponified, and washed with water to remove organic acids and organic acid esters. Then, fractional distillation is performed to obtain a secondary alcohol mixture.

[0049] As described above, in one embodiment of the present invention, the oxidation step includes: adding a gas containing oxygen and nitrogen in the presence of a boron compound to subject the raw material saturated aliphatic hydrocarbon mixture of the present invention to an oxidation reaction. In addition, in one embodiment of the present invention, a step of preparing a mixture containing orthoboric esters by esterifying the alcohol generated in the oxidation reaction. In addition, in one embodiment of the present invention, a step of distilling the mixture containing the orthoboric esters to remove unreacted saturated aliphatic hydrocarbons. In addition, in one embodiment of the present invention, a hydrolysis step of hydrolyzing the distillation residue to separate into boric acid and an organic layer. In addition, in one embodiment of the present invention, a step of saponifying the separated organic layer with alkali, more specifically, a step of saponifying the separated organic layer into an alkaline aqueous solution layer and a crude alcohol layer, and washing with water is included. In one embodiment of the present invention, a step of fractionating after removing the organic acid and the organic acid ester to obtain a secondary alcohol mixture is included.

[0050] [Raw material: saturated aliphatic hydrocarbon mixture]

[0051] Here, the raw material saturated aliphatic hydrocarbon mixture is a raw material for obtaining the secondary alcohol mixture represented by the above formula (2). In one embodiment of the present invention, the raw material saturated aliphatic hydrocarbon mixture contains saturated aliphatic hydrocarbons having 12 carbon atoms (equivalent to C12 body), saturated aliphatic hydrocarbons having 13 carbon atoms (equivalent to C13 body), saturated aliphatic hydrocarbons having 14 carbon atoms (equivalent to C14 body), and saturated aliphatic hydrocarbons having 11 or less carbon atoms and 15 or more carbon atoms (equivalent to Y body) in a predetermined ratio.

[0052] That is, the raw material saturated aliphatic hydrocarbon mixture contains saturated aliphatic hydrocarbons having 12 carbon atoms, saturated aliphatic hydrocarbons having 13 carbon atoms, saturated aliphatic hydrocarbons having 14 carbon atoms, and saturated aliphatic hydrocarbons having 11 or less carbon atoms and 15 or more carbon atoms at contents of 10 to 25 mass%, 40 to 65 mass%, 20 to 49.9 mass%, 0.1 mass% or more and less than 5 mass%, respectively. It should be noted that the preferred contents (content ratio, (mass %)) of saturated aliphatic hydrocarbons of various carbon numbers in the raw material saturated aliphatic hydrocarbon mixture and their ranges, upper limits and lower limits are similar to those described in the above-mentioned <Surfactant composition>, and therefore, the description thereof is omitted here. More specifically, the description of the C12 body can be replaced with the description of saturated aliphatic hydrocarbons having 12 carbon atoms, the description of the C13 body can be replaced with the description of saturated aliphatic hydrocarbons having 13 carbon atoms, the description of the C14 body can be replaced with the description of saturated aliphatic hydrocarbons having 14 carbon atoms, and the description of the Y body can be replaced with the description of saturated aliphatic hydrocarbons having 11 or less carbon atoms and 15 or more carbon atoms.

[0053] As a specific example, the above-mentioned “In one embodiment of the present invention, the content of the Y body is 0.1 mass% or more and less than 5 mass%, preferably 0.2 to 4.5 mass%, more preferably 0.4 to 4.0 mass%, can be 0.8 to 3.8 mass%, can also be 1.0 to 3.6 mass%, can also be 1.2 to 3.5 mass%, can be 1.2 mass% or more, 1.3 mass% or more, 1.4 mass% or more, 1.6 mass% or more, 1.8 mass% or more, 2.0 mass% or more, 2.2 mass% or more, 2.4 mass% or more, 2.6 mass% or more, or 2.8 mass% or more.” can be replaced by “In one embodiment of the present invention, The content of saturated aliphatic hydrocarbons with a carbon number of 11 or less and 15 or more in the raw material saturated aliphatic hydrocarbon mixture is 0.1 mass% or more and less than 5 mass%, preferably 0.2 to 4.5 mass%, more preferably 0.4 to 4.0 mass%, 0.8 to 3.8 mass%, 1.0 to 3.6 mass%, 1.2 to 3.5 mass%, 1.2 mass% or more, 1.3 mass% or more, 1.4 mass% or more, 1.6 mass% or more, 1.8 mass% or more, 2.0 mass% or more, 2.2 mass% or more, 2.4 mass% or more, 2.6 mass% or more, or 2.8 mass% or more. ".

[0054] In one embodiment of the present invention, the preparation of the raw material saturated aliphatic hydrocarbon mixture containing saturated aliphatic hydrocarbons with a carbon number of 12, saturated aliphatic hydrocarbons with a carbon number of 13, saturated aliphatic hydrocarbons with a carbon number of 14, and saturated aliphatic hydrocarbons with a carbon number of less than 11 and a carbon number of more than 15 in a specified proportion can also be carried out by referring to or combining previously known insights, for example, by performing separation operations using conventional methods (such as distillation).

[0055] According to one embodiment of the present invention, a secondary alcohol mixture to which alkylene oxide is added is prepared by subjecting a raw material saturated aliphatic hydrocarbon mixture to an oxidation step, wherein the raw material saturated aliphatic hydrocarbon mixture contains saturated aliphatic hydrocarbons having 12 carbon atoms, saturated aliphatic hydrocarbons having 13 carbon atoms, saturated aliphatic hydrocarbons having 14 carbon atoms, and saturated aliphatic hydrocarbons having 11 or less carbon atoms and 15 or more carbon atoms at 10 to 25 mass%, 40 to 65 mass%, 20 to 49.9 mass%, 0.1 mass% or more and less than 5 mass%, respectively. Alkylene oxide can be added to the secondary alcohol mixture prepared in this way to produce a surfactant composition.

[0056] (Alkylene oxide addition)

[0057] In one embodiment of the present invention, a method for producing a surfactant composition, for example, comprises a step of adding alkylene oxide to a secondary alcohol mixture prepared by the above method, wherein the secondary alcohol mixture contains 10 to 25% by mass of a C12 precursor represented by the following formula (2) where m+n is 9;

[0058] [Chemical formula 4]

[0059]

[0060] 40 to 65% by mass of a C13 precursor represented by the above formula (2) and having m+n of 10; 20 to 49.9% by mass of a C14 precursor represented by the above formula (2) and having m+n of 11; and 0.1% by mass or more and less than 5% by mass of a Y precursor represented by the above formula (2) and having m+n of at least one of 8 or less and 12 or more. According to this production method, a surfactant composition that has improved cleaning power and does not gel or is not easily gelled during handling can be produced.

[0061] It should be noted that the preferred content (content ratio (mass %)) of each precursor in the secondary alcohol mixture and its range, upper limit and lower limit are equally appropriate as described in the above-mentioned <Surfactant composition>, so the description is omitted here. More specifically, the description of the C12 body can be replaced by the description of the C12 precursor, the description of the C13 body can be replaced by the description of the C13 precursor, the description of the C14 body can be replaced by the description of the C14 precursor, and the description of the Y body can be replaced by the description of the Y precursor. More specifically, in the specific example described in [Raw saturated aliphatic hydrocarbon mixture], the raw material saturated aliphatic hydrocarbon mixture can be replaced by a secondary alcohol mixture for application.

[0062] In one embodiment of the present invention, the addition of the alkylene oxide can be performed by referring to or combining conventionally known knowledge. Conventionally known examples include methods described in Japanese Patent Application Publication No. 2003-221593, Japanese Patent Application Publication No. 48-34807, and Oil Chemistry, 24, 7, pp427-434 (1975). The addition of the alkylene oxide is described below by giving specific examples, but is not limited to the following.

[0063] In one embodiment of the present invention, as alkylene oxide, ethylene oxide, propylene oxide, etc. are preferred. In one embodiment of the present invention, when adding alkylene oxide, nitrogen substitution is performed in advance. The initial nitrogen pressure during nitrogen substitution is preferably 0.05-1.0 MPa, more preferably 0.05-0.4 MPa. In one embodiment of the present invention, as the reaction temperature, it is preferably 40-100°C, more preferably 40-70°C. In one embodiment of the present invention, the number of moles of alkylene oxide fed is preferably 1-5 moles, more preferably 2-4 moles, relative to 1 mole of hydroxyl groups in the secondary alcohol mixture. As a catalyst, acid catalysts such as boron trifluoride and tri(pentafluorophenyl)borane are preferred. After the reaction, the obtained oil layer is washed with an aqueous solution of sodium hydroxide, potassium hydroxide, etc., thereby removing the catalyst and by-products, and an alkylene oxide adduct can be obtained. In order to further improve the purity, it is preferred to remove the unreacted alcohol by distillation. Alkaline compounds such as sodium hydroxide and potassium hydroxide are added to the obtained alkylene oxide adduct, and alkylene oxide is added again, thereby obtaining an alkylene oxide adduct suitable for use in a detergent composition. The average number of added moles is preferably 5 to 50, more preferably 6 to 30, further preferably 7 to 15, and further preferably 9 to 12 per 1 mol of hydroxyl groups.

[0064] <Application of surfactant composition>

[0065] In one embodiment of the present invention, as the use of the surfactant composition, the surfactant composition of the present invention is preferably used as a detergent because it does not gel or is unlikely to gel, has excellent detergency, and has suppressed odor.

[0066] In one embodiment of the present invention, the surfactant composition may be used alone or in combination with other conventionally known surfactants. Examples of such surfactants include anionic surfactants such as alkylbenzene sulfonates, alkyl sulfate ester salts, α-olefin sulfonates, alkyl sulfonates, aliphatic amide sulfonates, dialkyl sulfosuccinates, and alkyl ether sulfate ester salts, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and zwitterionic surfactants such as alkyl betaines.

[0067] In one embodiment of the present invention, various additives may be added to the surfactant composition. Examples of such additives include alkali agents, builders, fragrances, fluorescent brighteners, colorants, foaming agents, foam stabilizers, polishing agents, bactericides, bleaching agents, enzymes, preservatives, dyes, solvents, and the like.

[0068] In one embodiment of the present invention, when the surfactant composition is used as a detergent, it can be effectively used as a detergent, shampoo, shower gel, etc. for clothing, fiber products, tableware, containers, sundry goods, foods, building maintenance products, houses, furniture, automobiles, airplanes, metal products, etc.

[0069] In one embodiment of the present invention, a surfactant composition can be used as an emulsifier. There is no particular limitation on the oily substance that can use the emulsifier, and mineral oil, animal and vegetable oil, synthetic oil, etc. can be used. They can be used alone, or two or more kinds can be mixed. Examples of mineral oils include spindle oil, engine oil, liquid paraffin oil, etc. Examples of animal and vegetable oils include tallow, lard, fish oil, whale oil, rapeseed oil, sesame oil, coconut oil, soybean oil, palm oil, camellia oil, castor oil, etc. In one embodiment of the present invention, the emulsifier can be used for pesticides, metalworking oils, coatings, and emulsifiers for emulsion polymerization, etc.

[0070] [Example]

[0071] The present invention will be described in more detail below by way of Examples and Comparative Examples. However, the present invention should not be construed as being limited to these Examples and Comparative Examples. Examples obtained by appropriately combining the technical means disclosed in the Examples are also within the scope of the present invention.

[0072] <Example 1>

[0073] (Oxidation process, alcoholization process)

[0074] 1000 g of a mixture of saturated aliphatic hydrocarbons having a carbon atom distribution as shown in the following Table 1 and 25 g of metaboric acid are added to a 3 L cylindrical reactor, and a gas having an oxygen concentration of 3.5 vol% and a nitrogen concentration of 96.5 vol% is blown into the reactor at a rate of 430 L per hour, and an oxidation reaction is carried out at normal pressure and 170°C for 2 hours.

[0075] 50% by mass of the oxidation reaction mixture is hydrolyzed with a large amount of hot water (95°C) to separate the oil layer containing the generated alcohol. The remaining 50% of the oxidation reaction liquid is mixed with the oil layer to adjust the presence of 1.04 equivalents of borate-forming compounds in terms of orthoborate equivalents. It is treated at 200 hPa and 170°C to orthoborate the alcohol contained therein. The mixture containing the orthoborate is flashed at 7 hPa to remove unreacted saturated aliphatic hydrocarbons until the temperature of the residual liquid reaches 170°C. Next, the residual liquid is hydrolyzed with a large amount of hot water at 95°C, and the boric acid is removed into the aqueous phase. The obtained oil layer is saponified and washed with water to remove organic acids and organic acid esters. The oil phase is fractionated at 7 hPa, and the first fraction having a boiling point range of 95°C or more and less than 120°C is a mixture of a small amount of paraffin, carbonyl compounds and monohydric primary alcohols. The second fraction (the fraction with a boiling point range of 120 to 150° C.) also yielded a small amount of carbonyl compounds and polyhydric secondary alcohols, but most of them were monohydric secondary alcohols. As the second fraction, monohydric secondary alcohols were obtained. A secondary alcohol mixture was obtained in the above manner.

[0076] (Alkylene oxide addition step)

[0077] 1 kg of the secondary alcohol mixture obtained above was placed in a 3 L SUS autoclave equipped with a stirrer, a thermometer, and an inlet tube for introducing ethylene oxide (EO), and the autoclave was purged with nitrogen. Then, 1.68 g of BF 3 -Et catalyst (BF 3 :46-49%), 1.7 mol of ethylene oxide (EO) was added to 1 mol of hydroxyl groups at an initial nitrogen pressure of 0.05 MPa and 55±5℃. Then, NaOH solution was added, and the reaction solution was washed at 90℃, and further washed with water until the pH became below 7. Next, the oil phase was put into a 3L glass three-necked flask, and a distillation tower (filler Dixon packing inner diameter 40mm, length 200mm, theoretical plate number 3 stages) was installed to distill, thereby obtaining 3 mols of ethoxylate adduct relative to 1 mol of hydroxyl groups with an average addition mole number. Next, 558g of the obtained ethoxylate adduct and 1g of potassium hydroxide were put into the same autoclave as above, and after nitrogen substitution, the pressure in the reactor was set to 15kPa with nitrogen, and heated to 150℃ to react 442g of ethylene oxide. After the reaction, it was neutralized with acetic acid to obtain a surfactant as an ethylene oxide adduct. It should be noted that it was confirmed that the obtained surfactant composition can be represented by the above formula (1), and the contents of C11 body (i.e., Y body) with m+n being 8, C12 body (i.e., m+n being 9), C13 body (i.e., m+n being 10), C14 body (i.e., m+n being 11), and C15 body (i.e., Y body) with m+n being 12 (hereinafter referred to as the distribution of the number of carbon atoms) are shown in Table 1. The average number of moles of EO added was confirmed to be 9.0 by the following hydroxyl value measurement method.

[0078] <Examples 2, 3, 4, 5, Comparative Examples 1 to 4>

[0079] The same operation as in Example 1 was carried out except that the mixture of saturated aliphatic hydrocarbons in Example 1 was changed to that shown in the following Table 1, thereby obtaining a surfactant composition as an ethoxylate adduct. It is to be noted that it was confirmed that the obtained surfactant composition can be represented by the above formula (1), and the distribution of the number of carbon atoms of the surfactant compositions of Examples 2 to 5 and Comparative Examples 1 to 4 is shown in Table 1. The average number of moles of EO added was confirmed by the following hydroxyl value measurement method to be 9.0, 9.0, 9.0, 9.0, 9.0, 8.6, 9.4, and 9.0, respectively.

[0080] The carbon atom distribution of the raw material paraffin (mixture of saturated aliphatic hydrocarbons), the carbon atom distribution of the secondary alcohol (mixture of secondary alcohols), and the carbon atom distribution of the alkoxylate (ethoxylate adduct) are the same.

[0081] <Evaluation Method>

[0082] (Hydroxy value determination method)

[0083] Take 444g of special grade phthalic anhydride reagent, dissolve it in special grade pyridine reagent, and make a total of 3L of phthalic acid reagent. Accurately weigh about 1g of the sample in a Teflon flask, add 9mL of phthalic acid reagent, and cover it with a Teflon cover. At this time, the test without the sample is regarded as a blank test. Place the flask on a hot plate with the surface temperature adjusted to 120°C and heat for 90 minutes. It should be noted that during heating, the flask is gently shaken and stirred at a ratio of once every 15 minutes. After heating, add 15mL of pure water, cool it for 10 minutes, add 50mL of pure water, and stir gently. Set the flask in an automatic titration device (AT-610 manufactured by Kyoto Electronics Co., Ltd.) and perform neutralization titration with 0.5mol / L potassium hydroxide solution (manufactured by Kanto Chemical Co., Ltd., volumetric analysis titrant). Perform 3 measurements on each sample, and calculate the hydroxyl value according to the following formula.

[0084] HV={(VB-VS)×N×F×56.11} / S

[0085] HV: Hydroxyl value (mgKOH / g)

[0086] VB: Titration of 0.5 mol / L potassium hydroxide aqueous solution in blank test (mL)

[0087] VS: Titration of 0.5 mol / L potassium hydroxide aqueous solution of the sample (mL)

[0088] N: 0.5 (concentration of potassium hydroxide aqueous solution (mol / L))

[0089] F: Factor of 0.5 mol / L potassium hydroxide aqueous solution

[0090] S: sample collection amount (g).

[0091] The average molecular weight was calculated from the obtained hydroxyl value, and the average number of added mols of EO was calculated from the difference from the average molecular weight of the secondary alcohol.

[0092] n=(56110 / HV-Mw) / 44.05

[0093] Mw: average molecular weight of secondary alcohol.

[0094] (Method for measuring the distribution of carbon atoms in saturated aliphatic hydrocarbons)

[0095] The distribution of the number of carbon atoms of saturated aliphatic hydrocarbons was measured using the following apparatus and under the following conditions.

[0096] Device: GC-2010 (SHIMAZU)

[0097] Conditions: Column: UA1(MS / HT)-30M-0.25F(GL Science)

[0098] Injection volume: 0.5ml

[0099] Injection method: No split

[0100] Injection temperature: 400℃

[0101] Column temperature: 50℃(10min)~5℃ / min-400℃(30min)

[0102] Carrier gas: He, 1ml / min

[0103] Detector: FID (400℃, H 2 50ml / min, Air 400ml / min, N 2 20ml / min).

[0104] (Method for measuring the distribution of carbon atoms in surfactant composition)

[0105] Equipment: Alliance 2695HPLC (Waters)

[0106] Column: Intersil ODS-2, inner diameter 3.0 mm, length 150 mm (GL Science)

[0107] Column temperature: 40°C

[0108] Injection volume: 100 μl

[0109] Sample concentration: 2%

[0110] Eluent: acetonitrile / water = 65 / 35 (vol%)

[0111] Flow rate: 1ml / min

[0112] Detector: RI.

[0113] (HLB)

[0114] The HLB of the surfactant compositions of Examples and Comparative Examples is shown in Table 1. It should be noted that HLB is a value obtained by the Griffin method. According to one embodiment of the present invention, the HLB of the surfactant composition is preferably 10.0 to 16.0, more preferably 11.0 to 15.0, and even more preferably 12.0 to 14.0.

[0115] (1) Gelation range

[0116] An aqueous solution (25° C.) of the surfactant composition having a predetermined concentration (40% to 50% by mass) shown in Table 1 was prepared. The solution was then heated to 40° C. over 60 minutes. The solution was then naturally cooled to 25° C. at room temperature of 25° C., and the presence or absence of fluidity was visually checked.

[0117] Therefore, according to one embodiment of the present invention, the gelation range is measured in an aqueous solution (25° C.) of 40% by mass to 50% by mass of the surfactant composition.

[0118] (2) Cleaning power

[0119] With reference to JIS K-3362:2008, a cleaning power test was conducted under the following conditions. That is, first, a pollutant was prepared. The composition of the pollutant was 28.3 mass % of oleic acid, 15.6 mass % of triolein, 12.2 mass % of cholesterol oleate, 2.5 mass % of liquid paraffin, 2.5 mass % of squalene, 1.6 mass % of cholesterol, 7.0 mass % of gelatin, 29.8 mass % of red loess, and 0.5 mass % of carbon black.

[0120] The contaminated material was applied to a cloth (5 cm×5 cm) to prepare a contaminated cloth. Five contaminated cloths were prepared in the same manner, and a total of six contaminated cloths were prepared.

[0121] A total of 6 pieces of soiled cloth and 30 g of cotton were immersed in 900 g of water (30° C.) containing 1.5 mmol / L of Ca and 1.0 mmol / L of Mg. Each surfactant composition was added to the water (30° C.) to a concentration of 0.05 wt %. Then, cleaning was performed for 20 minutes at a stirring speed of 120 rpm.

[0122] The reflectance of the contaminated cloth before and after cleaning was measured at 4 locations (front and back, 2 times each) for each test cloth, and the difference in reflectance (ΔZ) before and after cleaning was evaluated based on the average value (24 locations in total). The reflectance was measured using a colorimeter (Spectrocolorimeter SA5500 (manufactured by Nippon Denshoku Industries Co., Ltd.)).

[0123] <<Conditions>>

[0124] Measuring diameter: 28mm

[0125] Observation light source: D65

[0126] Observation conditions: 10 degree field of view

[0127] Measurement item: Z.

[0128] (3) Odor

[0129] The following sensory test was used to investigate whether the surfactant had an odor. The surfactant composition obtained in the Examples and Comparative Examples was placed in a 50 ml glass container, heated to 50°C in a hot water bath for 30 minutes, and then judged by 5 people whether there was an odor. If more than 2 people felt the odor, it was marked as ×, and if less than 1 person felt the odor, it was marked as 0.

[0130] [Table 1]

[0131]

[0132] This application is based on Japanese Patent Application No. 2019-173623, Japanese Patent Application No. 2019-173624, and Japanese Patent Application No. 2019-173625 filed on September 25, 2019, the entire disclosure of which is incorporated herein by reference.

Claims

1. A surfactant composition comprising a C12 body, a C13 body, a C14 body and a Y body, The C12 isomer is represented by the following formula (1), wherein A is ethylene, x is 1 to 50, and m+n is 9. The C13 isomer is represented by the above formula (1), wherein A is ethylene, x is 1 to 50, m+n is 10, The C14 isomer is represented by the above formula (1), wherein A is ethylene, x is 1 to 50, m+n is 11, The Y body is represented by the above formula (1), wherein A is ethylene, x is 1 to 50, m+n is 8 and / or 12, The content of the C12 body is 10% to 25% by mass. The content of the C13 body is 40% to 65% by mass. The content of the C14 body is 20% to 49.9% by mass. The Y form with m+n being 8 is 2.4% by mass or less, The Y form with m+n being 12 is 2.0 mass % or less, The total amount of the Y form in which m+n is 8 and the Y form in which m+n is 12 is 0.1% by mass or more.

2. The surfactant composition according to claim 1, wherein The content of Y-form where m+n is 8 is 2.2 mass % or less.

3. The surfactant composition according to claim 1, wherein The content of Y-form where m+n is 8 is 2.0 mass % or less.

4. The surfactant composition according to claim 1, wherein The content of Y-form where m+n is 8 is greater than 0.3 mass % and less than 2.0 mass %, The content of Y-form where m+n is 12 is less than 1.6 mass %.

5. A method for producing a surfactant composition, comprising the step of adding alkylene oxide to a secondary alcohol mixture, The secondary alcohol mixture comprises 10% to 25% by mass of a C12 precursor, 40% to 65% by mass of a C13 precursor, 20% to 49.9% by mass of a C14 precursor, 2.4% or less by mass of a Y precursor represented by the following formula (2) in which m+n is 8, and 2.0% or less by mass of a Y precursor represented by the following formula (2) in which m+n is 12, The C12 precursor is represented by the following formula (2) and m+n is 9, The C13 precursor is represented by the above formula (2) and m+n is 10, The C14 precursor is represented by the above formula (2) and m+n is 11.

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