JP2006104437A - Anionic surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surfactant excellent in balance of detergency against oily stains, rinsability, handleability and handling safety. <P>SOLUTION: The present invention relates to a secondary alkyl ether sulfate salt type anionic surfactant having an average chain length of polyalkylene ether of 1.5 to 2.5 and represented by chemical formula 1 (wherein R<SB>1</SB>and R<SB>2</SB>are each independently a straight-chain or branched 1 to 18C alkyl, with the total number of carbon atoms of both being 7 to 29; A is ≥2C alkylene group; n is the number of oxyalkylene repeating units and the average of n's is 1.5 to 2.5; M is an alkali metal, an alkaline earth metal, ammonium group, or a hydrogen atom-substituted ammonium group; and m is the valence of M) and a composition containing the surfactant. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an anionic surfactant having a specific chemical structure, and a composition containing such an anionic surfactant. Specifically, the average value of the polyalkylene ether chain length contained in the molecular structure is 1.5-2. And an anionic surfactant of the secondary alkyl ether sulfate type that is .5.

  In the field of household and industrial detergents and emulsifiers, various surfactants are used in accordance with the respective usage conditions. Surfactants are roughly classified into four types, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, based on their ionic properties. Of these, anionic surfactants are mainly used as the main component of clothes or kitchen detergents.

  Examples of the anionic surfactant include alkyl allyl sulfonate, alkyl sulfate ester salt, and alkyl ether sulfate ester salt. Of these, alkylallyl sulfonates, especially alkyl benzene sulfonates, were the most widely produced and consumed in the world in the past, but their use is restricted worldwide because of their poor biodegradability and adverse environmental impact. Be in the direction to be. Alkyl allyl sulfonates, alkyl sulfate esters, and the like are inherently poor in water solubility, and it is known that the surface activity decreases when the hardness of the water used is high.

  The alkyl ether sulfate ester type anionic surfactant includes an anionic surfactant having a primary alkyl ether sulfate salt type and a secondary alkyl ether sulfate type structure. Here, primary alkyl refers to primary alkyl when there is one carbon atom substituent (such as an alkyl group) bonded to oxygen of the oxyalkylene group, and secondary alkyl when there are two substituents. .

  The primary alkyl ether sulfate ester salt has a problem in handling operability such as high viscosity as an aqueous solution and easy gelation. In addition, surface activity such as surface tension and osmotic power is insufficient, and there is room for improvement in detergency and emulsification power.

  On the other hand, the secondary alkyl ether sulfate ester type is excellent in handling operability such as low viscosity of the blended aqueous solution and difficulty in gelation. Moreover, it is a useful active agent which is also excellent in surface tension and penetrating power, and further excellent in detergency and emulsifying power, and also has good foam loss (see, for example, Patent Documents 1 and 2).

  In Patent Document 2, as a method for producing a higher secondary alkyl ether sulfate, a crystalline aluminosilicate is used as a catalyst when monoethylene glycol (MEG) is added to a double bond of a long-chain olefin (OL). There has been proposed a method of sulfating the obtained higher secondary alcohol alkoxylate or the higher secondary alcohol alkoxylate obtained by further adding ethylene oxide (EO).

In such a production method, both the OL-added MEG and the EO-added sulfate, composition A containing 95% or more of an alkyl ether sulfate having a monoethoxylate structure, and polyalkylene There is provided a composition B comprising an EO adduct sulfate in a form in which the range of ether chain length is widely distributed.
JP 59-175463 A JP-A-10-251216

  However, in the invention described in JP-A-10-251216, although composition A has higher rinsing properties than composition B, it has low detergency. On the other hand, composition B is less rinsable than composition A, although the polyalkylene ether chain length is increased and the hydrophilicity is increased to increase the detergency. For this reason, it is currently impossible to provide a product with a good balance between the characteristics of rinsing properties and detergency.

  Accordingly, the present inventors have made extensive studies to achieve the above object, and as a result, have an average value of polyalkylene ether chain length within a predetermined range, or an alkyl ether sulfate having a polyalkylene ether chain length of 2. It has been found that those containing a certain ratio or more can exhibit an excellent function in the balance between the characteristics of rinsing properties and detergency.

Furthermore, in terms of performance and quality other than the price, it is considered that the consumer mainly demands the following items for the surfactant.
1. Detergency against oil stains There are various components, such as mud stains and protein stains, to be cleaned, but the main target is oil stains. Of course, it is considered that the higher the affinity for the lipophilic compound, the better the detergency against oil stains and the dispersibility of the removed stains.
2. Rinseability after washing It is desirable to easily and quickly remove dirt and excess surfactant itself that has been removed after washing from the substrate. Even if the affinity for the lipophilic compound is high and the dispersibility of the removed dirt is high, it becomes a major drawback if the surfactant itself cannot be sufficiently removed from the substrate.
3. Handling operability The surfactant is mainly used in the form of an aqueous solution as one of the components of the composition, but it is desired that there are few restrictions on the composition. In view of the chemical structure, there is a demand for a surfactant having a narrow concentration range in which the viscosity of the blended liquid is high and the fluidity is low, or the fluidity of the liquid is lost and becomes a gel.
4). Handling safety There are two perspectives on the actual consumer or the environment that is discharged after use. In the former, it is desired that there is no irritation when directly touching a consumer's skin and no odor that is felt during use. In response to these multiple representative requirements, the launch of surfactants with excellent overall balance is awaited.

  Thus, in order to meet consumer demands for surfactants, it is necessary to further optimize molecular design. That is, it is an object of the present invention to provide a surfactant that satisfies the demands of oil stain cleaning power, rinsing properties after cleaning, handling operability, and handling safety in a well-balanced manner.

  Accordingly, an object of the present invention is to provide an anionic surfactant having a secondary alkyl ether sulfate salt type structure which has an excellent balance of oil stain detergency, rinsability, handling operability, and handling safety. is there.

  In addition, an object of the present invention is to provide a composition containing a secondary alkyl ether sulfate ester salt that is a sulfated alkoxide having an excellent balance between rinsing properties and detergency, and a surfactant using the same. An object of the present invention is to provide a cleaning agent using the surfactant.

  Furthermore, the objective of this invention is providing the liquid cleaning composition useful for clothes, dishwashing, etc.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific surfactant has an excellent balance of oil stain cleaning power, rinsing performance, handling operability, and handling safety, The present invention has been completed.

  That is, the present invention provides an anionic surfactant of a secondary alkyl ether sulfate ester salt represented by the chemical formula 1 having an average polyalkylene ether chain length of 1.5 to 2.5:

However, in the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, and A has 2 or more carbon atoms, preferably 2 Is an alkylene group of ˜8, n is the number of repeating units of the oxyalkylene group, the average value thereof is in the range of 1.5 to 2.5, M is an alkali metal, alkaline earth metal, ammonium group, or It is a hydrogen atom-substituted ammonium group, and m represents the valence of M.

  The present invention also provides a chemical formula 2

However, in the formula, R ₁ and R ₂ are each independently a straight-chain or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, preferably 7 to 19, and A has a carbon number. Two or more alkylene groups, M is an alkali metal, alkaline earth metal, ammonium group, or hydrogen atom-substituted ammonium group, m represents the valence of M,
And a secondary alkyl ether sulfate ester salt (also referred to as “secondary alcohol alkoxylate sulfate salt”) represented by the formula: It is related with the secondary alkyl ether sulfate ester composition which is the mass% or more.

  Furthermore, the present invention provides a compound of formula 3

In the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, preferably 7 to 19, and A has 2 or more carbon atoms. An alkylene group of
A method for producing a secondary alkyl ether sulfate ester salt-containing composition represented by Chemical Formula 2 obtained by subjecting a raw material secondary alcohol alkoxylate represented by formula (II) to a sulfation reaction and then neutralizing with a basic substance , Regarding.

  The present invention also provides the chemical formula 2

In the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, preferably 7 to 19, and A has 2 or more carbon atoms. M is an alkali metal, alkaline earth metal, ammonium group, or a hydrogen atom-substituted ammonium group, m represents the valence of M,
A secondary alkyl ether sulfate ester salt represented by the formula:

  According to the secondary alkyl ether sulfate (chemical formula 1) anionic surfactant of the present invention, there is an effect of excellent oil stain detergency, rinsing property, handling operability, and handling safety.

  The secondary alkyl ether sulfate salt (chemical formula 2) -containing composition of the present invention contains 40% by mass of an alkyl ether sulfate having a polyalkylene ether chain length of 2 with respect to the anionic surfactant in the composition. Since it contains the above, the characteristic which was excellent in the balance of the characteristic of rinse property and detergency is shown.

(I. Secondary alkyl ether sulfate ester type anionic surfactant)
The secondary alkyl ether sulfate ester type anionic surfactant according to the present invention has a chemical structure represented by Formula 1.

In Chemical Formula 1, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having 7 to 29 synthetic carbon atoms, preferably 7 to 19 carbon atoms. When the total value is less than 7, the detergency against oil stains becomes low. On the other hand, if it exceeds 29, the rinsing properties after washing are poor, and a sticky feeling on the washing substrate tends to remain.
Specific examples of R ₁ or R ₂ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group. 2-ethylbutyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, 3,5,5-trimethylhexyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.

  The secondary alkyl ether sulfate ester (Chemical Formula 1) not only exhibits high detergency to oil stains derived from high penetrability compared to that of the primary alkyl ether sulfate ester salt, but also contains a mixed aqueous solution. Has the advantage of excellent handling operability such as low viscosity and low gelation range.

Further, R ₁ is a methyl group, component R ₂ is an alkyl group having 2 or more carbon atoms, with respect to total anionic surfactant is preferably in the range of 30 to 70 wt%. That is, the proportion of the component having a structure in which the polyalkylene ether chain length extends from the second carbon from the end in the lipophilic group occupies 30 to 70%. About the remaining components, both R ₁ and R ₂ are optional, and include an alkyl group having 1 to 18 carbon atoms and a component having 7 to 29 synthetic carbon atoms.

  AO in Chemical Formula 1 represents an oxyalkylene group having 2 or more carbon atoms, preferably 2 to 8 carbon atoms. Specific examples include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group, an oxyhexylene group, an oxypeptylene group, an oxyoctylene group, and an oxyphenylene group. These can be arbitrarily selected according to the properties expected for the finished product, but oxyethylene groups and oxypropylene groups are preferred from the viewpoint of the availability of raw materials and the expectation of working as a hydrophilic group. Moreover, AO may be comprised only by 1 type, but may be comprised by 2 or more types. When AO is comprised by 2 or more types, you may arrange | position at random or in the block. For example, a structure in which a part of the polyoxyethylene long chain is replaced with an oxypropylene group may be used.

  N in Chemical Formula 1 represents the average value of the polyalkylene ether chain length or the number of repeating units of AO, and the average added mole number nAve is 1.5 to 2.5 mol, preferably 1.7 to 2.3. . If it is less than 1.5, the detergency against oil stains is high, but the rinsability after washing becomes poor. On the other hand, if it exceeds 2.5, the rinsing properties are good, but the cleaning power is low.

  This repeating unit is an indicator that exerts a good balance between oil stain detergency and rinsing properties. By specifying the repeating unit itself or its average value, an anionic surfactant that functions effectively can be prepared. it can. Specifically, it is preferable that the proportion of the component having a polyalkylene ether chain length of 1 or 2 which is the number of repeating units of AO is 60% or more of the whole.

The average value of the polyalkylene ether chain length is determined by H ¹ NMR analysis of an alkyl ether sulfate ester salt. However, as a simpler method, it can be estimated by analyzing the alkyl ether before sulfation by the GC method (gas chromatography). In this case, the average value of the polyalkylene ether chain length is an average value of polyalkylene ethers having different chain lengths, and is the sum of products obtained by multiplying each chain length by the respective proportion. If an alcohol component having no polyalkylene ether chain is included, this content is also assumed to correspond to polyalkylene ether chain length = 0 and added to the calculation. For example, when the components of polyalkylene ether chain length = 0, 1, 2, 3, and 4 are 30%, 20%, 15%, 10%, and 5%, respectively, the average chain length is 1. 0 (0 × 0.3 + 1 × 0.2 + 2 × 0.15 + 3 × 0.1 + 4 × 0.05). The GC method is described in the example column. At the time of analysis, if the ether chain end is silylated as a pretreatment, the boiling point of the target compound can be lowered, so that GC analysis at a low temperature becomes possible.

  M in Chemical Formula 1 is any one of an alkali metal, an alkaline earth metal, an ammonium group, and a hydrogen atom-substituted ammonium group. These are determined by the basic compound used for neutralization after sulfation, but are preferably an alkali metal such as sodium or potassium, or an ammonium group from the viewpoint of availability of the compound.

That is, the secondary alkyl ether sulfate represented by the chemical formula 1 of the present invention is a mixture containing compounds having different polyalkylene ether chain lengths when R ₁ , R ₂ , A, and M are constant. , Meaning that the average value of the polyalkylene ether chain length is n.

(Method for producing secondary alkyl ether sulfate type anionic surfactant)
The secondary alkyl ether sulfate ester (chemical formula 1) type anionic surfactant of the present invention can be produced by the following method. That is, it can be obtained by using a secondary alcohol as a starting material and adding, sulfating and neutralizing alkylene oxide.

  Moreover, it can also manufacture based on the method as described in JP-A-10-251216. That is, using a crystalline aluminosilicate as a catalyst, an alkylene glycol is added to a double bond of a long-chain olefin to prepare a secondary alcohol alkoxylate, or an alkylene oxide is added thereto to add a large number of moles. This is a production method in which a secondary alcohol alkoxylate is prepared and then sulfated and neutralized.

The latter method has the following advantages:
(1) Alkenyl glycol is added to olefin, and since almost no unreacted olefin remains, alkenyl sulfate is hardly formed even after the subsequent addition of alkylene oxide.
(2) In the latter production method, since almost no unreacted olefin remains, alkyl sulfate ester is hardly generated. On the other hand, when an alkylene oxide is added to a normal alcohol, an unreacted alcohol remains, so that an alkyl sulfate ester that causes skin irritation after sulfuric acid is generated.
(3) The addition of alkylene oxide was not a secondary alcohol, but was obtained because it targeted an alkylene glycol mono secondary alkyl ether having the same structure as that of a 1 mol addition product of alkylene oxide to alcohol. The distribution of the number of moles added of the alkylene oxide adduct is within a relatively narrow range.
(4) In the latter production method, an alkyl ether having a narrow distribution of the number of added moles can be prepared even when a general-purpose alkali catalyst is used. On the other hand, in order to obtain an alkyl ether having a narrow distribution of the number of added moles of an alkylene oxide adduct, a special catalyst called a so-called narrow range catalyst is usually required. Of course, as the number of added moles of alkylene oxide increases, the distribution of the number of added moles becomes wider, but in the range where the number of added moles of alkylene oxide is relatively small, the distribution is extremely narrow.

(Liquid detergent composition containing a secondary alkyl ether sulfate ester type anionic surfactant)
The secondary alkyl ether sulfate ester (chemical formula 1) type anionic surfactant according to the present invention can be used alone as a cleaning agent, but a known surfactant for cleaning agents may be used in combination.

  Examples of such surfactants that can be used in combination include nonionic surfactants such as alkylphenol alkoxylates, higher primary alcohol alkoxylates, higher secondary alcohol alkoxylates, and fatty acid alkoxylates, alkylamine salts, Examples include cationic surfactants such as quaternary ammonium salts and amphoteric surfactants such as alkylbetaines. Furthermore, the performance of the surfactant of the present invention is impaired also for conventional anionic surfactants such as alkyl allyl sulfonates, higher primary alcohol sulfates and higher primary alkyl ether sulfates. It is also possible to use a combination of a proper amount within a range that does not exist and can exhibit the action and effect of each surfactant.

  Furthermore, various additives used in ordinary cleaning agents can be added to the cleaning agent containing the secondary alkyl ether sulfate (chemical formula 1) type anionic surfactant of the present invention. .

  For example, as an additive in the case of detergent use, for example, alkaline agent, fragrance, fluorescent whitening agent, colorant, foaming agent, foam stabilizer, glossing agent, bactericidal agent, bleaching agent, enzyme, preservative, Examples include dyes and solvents. However, these additives may be mixed in an appropriate amount in the surfactant of the present invention, or may be added as a cleaning agent component to be described later separately from the surfactant of the present invention.

(II. Secondary alkyl ether sulfate type anionic surfactant having a polyalkylene ether chain length (average value) = 2)
(Secondary alkyl ether sulfate represented by chemical formula 2)
In Chemical Formula 2, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, and each has a synthetic carbon number of 7 to 29, preferably 7 to 19, and more preferably 7 to 15. . When the total number of carbon atoms is less than 7, the lipophilicity is not obtained, the surface activity is lowered, and it becomes difficult to express the effects of the present invention. When the total number of carbon atoms exceeds 29, the secondary alkyl ether sulfate ester salt becomes a solid substance and becomes insoluble, hydrophilicity does not appear, surface activity decreases, and the effects of the present invention are exhibited. It becomes difficult.

  In Chemical Formula 2, the number of carbon atoms in AO is 2 or more, preferably 2 to 10, more preferably 2 to 4.

  M in Chemical Formula 2 represents an alkali metal, an alkaline earth metal, an ammonium group, or a hydrogen atom-substituted ammonium group. Preferably, it is an alkali metal ion from the viewpoint of easy neutralization after the sulfation process. These may be cation species of a neutralizing substance used when neutralizing a sulfated secondary alcohol alkoxylate as will be described later. Note that n represents the valence of M.

(Secondary alkyl ether sulfate salt-containing composition)
In the composition of the present invention, the component represented by Chemical Formula 2 is contained in an amount of 40% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more, based on the anionic surfactant in the composition. Has been. When the component represented by Chemical Formula 2 is contained in an amount of 40% by mass or more based on the anionic surfactant in the composition, the balance between the characteristics of rinsing properties and detergency is particularly excellent. When the component represented by Chemical Formula 2 is less than 40% by mass, the balance between the properties of rinsing properties and detergency is poor and one of the properties is improved, while the other property is low and satisfactory. Ineffective.

  In the anionic surfactant in the composition, as the component other than the secondary alkyl ether sulfate ester salt component represented by the chemical formula 2, the secondary alkyl ether sulfate mainly having a polyalkylene ether chain length other than 2 is used. Ester salts are included. The polyalkylene ether chain length is preferably 1 or 3 to 20. For example, higher secondary alcohol alkoxysulfate salts obtained by the production method described in JP-A-59-175463 and higher secondary alkyl ether sulfates obtained by the production method of JP-A-10-251216 , Primary alcohol sulfates, primary alcohol alkoxylates, alkyl sulfate esters, α-olefin sulfonates, alkylbenzene sulfonates, and other anionic surfactants; alcohol alkoxylates, fatty acid alkanolamides, sorbitan fatty acid esters , Nonionic surfactants such as polyoxyethylene acyl ester, alkyl polyglycoside, fatty acid glycoside ester, fatty acid methyl glycoside ester, alkyl methyl glucamide; alkyl betaine, alkyl hydroxysulfo betaine, Kill betaines, imides sledding betaine, N- alkyl amino acids, the compounds or compositions having known surface activity, such as amphoteric surfactants such as amine oxides.

  Moreover, the composition of this invention may contain water other than an above-described component. Since such water is produced during the production process of the secondary alkyl ether sulfate ester salt (Chemical Formula 2), it is possible to use or sell a composition containing water depending on the intended use.

  Therefore, the content of water in the composition of the present invention is not particularly limited and varies depending on the production method, but is usually 20 to 80% by mass, preferably 30 to 50% by mass with respect to the composition. It is in the range.

  Moreover, in the composition of this invention, it is also possible to mix | blend the solvent which does not affect the effect of this invention instead of water or with water. In addition, in the composition of this invention, it prescribes | regulates on the basis of the anionic surfactant in this composition so that the ratio of the component represented by Chemical formula 2 may not fluctuate | variate by such adjustment of the amount of solvents. That is, in the composition of the present invention, the component represented by Chemical Formula 2 contained in the anionic surfactant in the composition is 40% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more. Contained. Examples of the solvent include ethanol and propylene glycol.

  The secondary alkyl ether sulfate salt (chemical formula 2) -containing composition of the present invention comprises an alkyl ether sulfate having a polyalkylene ether chain length of 2 as a proportion of 40% by mass or more based on the anionic surfactant in the composition. Therefore, it is possible to provide a composition containing an alkyl ether sulfate excellent in the balance between the properties of rinsing properties and detergency, which has not been achieved conventionally.

  Therefore, by using the composition of the present invention as a surfactant, particularly a liquid cleaning composition useful for detergents, particularly dishwashing, etc., in addition to vegetables and fruits, especially tableware, cooking utensils, etc. Excellent detergency against heavy oil stains and stubborn sticking.

  In addition, since the rinsing property is high, it is possible to quickly wash off dirt and cleaning agent by simple water washing after washing, for example, washing with running water or pool water.

  The secondary alkyl ether sulfate ester-containing composition of the present invention, a surfactant using the same, and a cleaning agent using the surfactant, particularly a liquid cleaning composition useful for dishwashing, etc. are also used in the existing high grade. Similar to secondary alkyl ether sulfates, it is easy to handle and surface tension because of its low viscosity and resistance to gelation compared to existing higher primary alcohol sulfates and higher primary alkyl ether sulfates. The penetrating power is good, the foam is good, the detergency and the emulsifying power are superior, and this is also useful.

  The rinsability refers to the ease with which the active agent can be removed from dishes to be cleaned such as dishes and cooking utensils. Foaming property refers to the ease with which the active agent remains but no bubbles are present. However, since the active agent remains, the detergency remains. Therefore, rinsing properties and foaming properties are technical terms meaning different characteristics and are clearly distinguished.

(Method for producing secondary alkyl ether sulfate ester-containing composition)
Next, the manufacturing method of the secondary alkyl ether sulfate ester (chemical formula 2) containing composition of this invention is demonstrated.

  The secondary alkyl ether sulfate salt (chemical formula 2) -containing composition of the present invention can be produced by the following method:

In the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, preferably 7 to 19, and A has 2 or more carbon atoms. An alkylene group of
By subjecting the raw material secondary alcohol alkoxylate represented by the formula below to sulfation reaction, and then neutralizing with a basic substance,

In the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, preferably 7 to 19, and A has 2 or more carbon atoms. M is an alkali metal, alkaline earth metal, ammonium group, or a hydrogen atom-substituted ammonium group, m represents the valence of M,
A composition comprising a secondary alkyl ether sulfate ester salt represented by the formula: wherein the component represented by the chemical formula 2 is contained in an amount of 40% by mass or more based on the anionic surfactant in the composition. A composition containing a secondary alkyl ether sulfate salt is obtained.

  The raw material secondary alcohol alkoxylate used in the above production method is desirably produced by adding dialkylene glycol to a linear olefin having 8 to 30 carbon atoms. When the raw material obtained in this way is sulfated, alcohol partially generated by the decomposition reaction is mixed, but the abundance is extremely small. Therefore, since the purification process by the extra distillation described in JP-A-59-175463 is unnecessary, the production cost can be suppressed, and a low-cost product can be provided, which is highly practical and economical. Is also advantageous. Furthermore, since the raw material alcohol hardly remains in the composition, it is advantageous in that there is no problem of skin irritation and salt resistance (crystallization).

  Further, as the secondary alcohol alkoxylate represented by the chemical formula 3, the alkoxylate obtained by the above method is used as a raw material, so that the polyalkylene ether chain length of the alkyl ether sulfate represented by the chemical formula 2 is 2 It is advantageous in that the components can be obtained selectively or preferentially with high purity (high content).

  For example, in Example 2 and Example 1 described later, the average value of the polyalkylene ether chain length before sulfation is almost the same between 2.0 and 2.1. However, in Example 2, the secondary alcohol alkoxylate represented by Chemical Formula 3 is produced by the above method and used as a raw material, whereby the component represented by Chemical Formula 2 is obtained at a high content rate of 93% by mass. . On the other hand, when the raw material obtained by the method described in Example 1 is used, a composition containing alkyl ether sulfate in a form in which the range of polyalkylene ether chain length is widely distributed is obtained. Therefore, the component represented by Chemical Formula 2 is about 31% by mass. As a result, in the case of Example 2, the component content represented by Chemical Formula 2 is high, and an excellent balance between rinsing properties and detergency can be obtained (see the table).

  Hereinafter, these manufacturing methods will be described as examples.

(Synthesis of secondary alcohol alkoxylate)
First, the secondary alcohol alkoxylate represented by Chemical Formula 3 is produced by adding dialkylene glycol to a linear olefin having 8 to 30 carbon atoms.

  Specifically, dialkylene glycol is appropriately adjusted to an appropriate molar ratio as necessary to a linear olefin having 8 to 30 carbon atoms, and further added in the presence of an acid catalyst as necessary. Can be obtained by distillation, extraction or other methods.

  Examples of the linear olefin having 8 to 30 carbon atoms include hydrocarbons having 8 to 30 carbon atoms, preferably 10 to 18 carbon atoms, and more preferably 12 to 16 carbon atoms having an ethylenically unsaturated bond. Specific examples include octene, decene, dodecene, tetradecene, hexadecene, octadecene, and eicosene. These may be used alone or in a mixture of two or more.

  In addition, these linear olefins can be used without particular limitation, whether the unsaturated bond is in the α-position, in the inner position, or in both the α-position and the inner position. . Of course, two or more of these linear olefins having different unsaturated bond positions can be used in combination.

  Examples of the dialkylene glycol used for obtaining the secondary alcohol alkoxylate include diethylene glycol and dipropylene glycol. These may be used alone or in a mixture of two or more.

  Although the molar ratio of the said linear olefin and the said dialkylene glycol for obtaining a secondary alcohol alkoxylate is not specifically limited, Usually, it is 0.05-20, Preferably it is 0.1-10. By adjusting the molar ratio of the straight chain olefin and the dialkylene glycol within the above range, the amount of the unreacted raw material recycled can be reduced, so that the reactor can be downsized and the energy cost required for the recycling. This is advantageous in that it can be reduced.

  Moreover, as reaction conditions for adding the dialkylene glycol to the unsaturated bond of the linear olefin, the reaction temperature is usually 50 to 250 ° C., preferably 100 to 200 ° C. The reaction pressure may be any of reduced pressure, normal pressure, or increased pressure, but is preferably in the range of normal pressure to 0.2 MPa because of an equilibrium advantage due to the addition reaction in which the number of moles decreases. When the reaction temperature is less than 50 ° C., the reaction rate is too slow. On the other hand, when the reaction temperature exceeds 250 ° C., polymerization of linear olefins, decomposition of dialkylene glycol, condensation polymerization, and the like occur, and the selectivity is increased. It is not preferable because it decreases.

  Examples of the acid catalyst used for the reaction of the linear olefin and the dialkylene glycol include strongly acidic ion exchange resins, crystalline aluminosilicates, dodecylbenzenesulfonic acid, sulfuric acid, and heteropolyacids. From the viewpoint of reactivity and separability after reaction, crystalline aluminosilicates (eg, BEA type zeolite, MFI type zeolite, MEL type zeolite, MWW type zeolite, etc.) are preferable, and BEA type zeolite is particularly desirable.

  The amount of the acid catalyst is usually in the range of 0.1 to 100% by mass, preferably 0.5 to 50% by mass with respect to the linear olefin. When the amount of the catalyst is less than 0.1% by mass, the addition reaction cannot be sufficiently promoted. On the other hand, when the amount exceeds 100% by mass, many side reactions such as olefin polymerization and alkylene glycol condensation occur. In addition, an effect corresponding to the additional amount cannot be obtained, and this is uneconomical.

As described above, the secondary alcohol alkoxylate represented by Chemical Formula 3 can be obtained. Note that the description and preferred range of R ₁ , R ₂ and A in Chemical Formula 3 are the same as the description and preferred range of R ₁ , R ₂ and A in Chemical Formula 2.

  In the production method of the present invention, a secondary alcohol alkoxylate represented by Chemical Formula 3 (simply abbreviated as a raw material secondary alcohol alkoxylate) is reacted, and then sulfated and neutralized with a basic substance. Is a composition containing a secondary alkyl ether sulfate ester salt represented by the chemical formula 2, wherein the component represented by the chemical formula 2 is contained in an amount of 40% by mass or more with respect to the anionic surfactant in the composition. A composition containing a secondary alkyl ether sulfate ester salt is obtained.

(Sulfation)
For such sulfation, for example, sulfuric acid, chlorosulfonic acid, anhydrous sulfuric acid, sulfamic acid and the like can be used. In industrial use, sulfation is preferably performed using chlorosulfonic acid or sulfuric anhydride mainly from the viewpoint of economy.

  Therefore, (i) the case of sulfation using chlorosulfonic acid and (ii) the case of sulfation using sulfuric anhydride will be described.

  (I) When chlorosulfonic acid is used, chlorsulfonic acid is dropped into the secondary alcohol alkoxylate by a known method, for example, directly or with air, inert gas, or JP-B- By the method described in 1-36823, sulfation is performed in a batch manner by mixing using a sulfation apparatus equipped with an external circulation with a line mixer.

  When chlorosulfonic acid is used, the dropping time is suitably 1 to 2 hours. As the reaction proceeds, the viscosity of the circulating liquid increases and the raw material concentration decreases, so that the yield and quality due to decomposition of the sulfate are likely to occur in the latter half of the reaction. Therefore, it is preferable to gradually reduce the supply rate of chlorosulfonic acid as the reaction proceeds. Although reaction temperature is not specifically limited, Usually, 20 degrees C or less, Preferably 15 degrees C or less is suitable. When the reaction temperature exceeds 20 ° C., the product is likely to be decomposed, resulting in a decrease in the yield and quality of the sulfate.

  (Ii) When sulfuric anhydride is used, the secondary alcohol alkoxylate is flowed down into a thin film using a co-current thin film reactor as described in a known method, for example, JP-B-51-17538, Sulfation is carried out continuously by bringing the anhydrous sulfuric acid gas diluted with an inert gas into parallel flow and bringing them into gas-liquid contact.

  When anhydrous sulfuric acid is used, the speed of the inert gas is preferably 15 to 90 m / sec. If the speed is less than 15 m / sec, the thin film is poorly stirred, so that a local reaction proceeds and the product is likely to be decomposed. On the other hand, when it exceeds 90 m / sec, the thin film becomes mist and the residence time cannot be controlled, and the decomposition reaction occurs due to the residence for a long time. The sulfuric anhydride concentration in the gas is preferably 0.3 to 1.6% by volume. If it is less than 0.3% by volume, the reactivity decreases and the amount of unreacted raw materials increases. If it exceeds 1.6% by volume, the yield is improved, but the color tone is significantly lowered. The molar ratio of sulfuric anhydride to secondary alcohol alkoxylate is preferably 0.9 to 1.2. If it is less than 0.9, the reactivity decreases and the amount of unreacted raw materials increases. When it exceeds 1.2, the decomposition reaction of the product becomes remarkable. The reaction temperature is usually -20 to 80 ° C, more preferably 20 to 60 ° C. Since this reaction is an exothermic reaction, in order to control the reaction temperature, it is preferable to have a structure that can remove heat from a reactor wall such as a jacketed reactor.

  In the present invention, by using a solvent in the sulfation step, a secondary alkyl ether sulfate ester salt containing “secondary alkyl ether sulfate ester salt represented by Chemical Formula 2 with high yield and high quality” is further contained. It is also possible to produce a composition.

  Examples of the solvent used include chloroform, carbon tetrachloride, ethyl chloride, ethylene chloride, chlorinated solvents such as 1,1,1-trichloroethane, 1,1,1,2-tetrachloroethane, n-pentane, n- Examples thereof include hydrocarbon solvents such as hexane, n-heptane and cyclohexane, and ether solvents such as diethyl ether and isopropyl ether. The solvent concentration is usually preferably 10 to 90% by mass in the reaction solution. When the solvent concentration is less than 10% by mass, the effect of using a solvent such as a decrease in viscosity cannot be obtained because the material concentration is high. Conversely, when the solvent concentration exceeds 90% by mass, the material concentration becomes too dilute and the reaction efficiency is poor. It is not preferable because it causes a decrease in rate.

(Neutralization)
After the sulfation, the obtained reaction solution is neutralized with a basic substance, and when a solvent is used, the solvent is removed to obtain the desired secondary alkyl ether sulfate ester-containing composition.

  Suitable basic substances for the neutralization step are alkali metal hydroxides, preferably sodium hydroxide, potassium hydroxide and lithium hydroxide; alkaline earth metal oxides and hydroxides, preferably magnesium oxide, hydroxide Magnesium, calcium oxide and calcium hydroxide; ammonia, alkanolamines, preferably mono-, di- and triethanolamine, and primary, secondary and tertiary alkylamines containing 1 to 4 carbon atoms per alkyl group is there. These cationic species constitute a secondary alkyl ether sulfate ester salt as M in Chemical Formula 2.

  The secondary alkyl ether sulfate ester salt (Chemical Formula 2) -containing composition according to the present invention obtained by the above-described production method of the present invention can be used and sold as it is as a product such as a surfactant. Moreover, you may increase / decrease the water content byproduced by the neutralization process as needed after the said neutralization process. Furthermore, if necessary, other compounds and compositions having surface activity, and various additives may be appropriately blended.

By using the apparatus shown below, water used in the sulfation step can be removed, and a high-purity sulfate can be obtained from an aqueous solution of about 25%.
1. Evaporator: A general evaporator can be used, but operation under reduced pressure is preferable in order to suppress decomposition of sulfate by heat. For example, it is preferable to remove moisture using a rotary thin film evaporator. .
2. Distiller: A general distillation column can be used, but it is preferable to distill water in a multistage distillation column in order to increase the removal rate of moisture. Batch processing is more preferred because the desired product remains at the bottom of the column after the removal of moisture.

  As a general multistage distillation column, for example, a plate column type or a packed column type is used. As an example of the shelf tower type shelf, a bubble bell tray, a perforated plate tray, a valve tray and the like are used. Examples of the packed column include Raschig rings, Lessing rings, Dixon packing, Sulzer packing, McMahon packing, pole rings, Berle saddles, interlock saddles, helipacks, and melapacks.

Further, by using the apparatus shown below, almost 100% of the product can be obtained by removing the secondary alcohol alkoxylate contained as an impurity by solvent extraction or distillation.
1. Solvent extraction: A general extraction apparatus can be used, and a raw material alcohol alkoxylate can be phase-separated and removed using a hydrophobic solvent such as petroleum ether.

Examples of the extraction apparatus include a mixer-settler extractor, counter-current spray tower, packed tower, plate extraction tower, non-stirring perforated plate extraction tower, baffle tower, stirring stirbell tower, rotating disk extraction tower, etc. Is used.
2. Distillation column: A general distillation column can be used, but it is preferable to distill in a multistage distillation column in order to increase the removal rate of alcohol alkoxylate. Batch treatment is more preferred because the desired product remains at the bottom of the column after removal of the alcohol alkoxylate.

  As a general multistage distillation column, for example, a multistage column type or a packed column type is used. For examples of the plate tower and packed column packings, see what is described when removing the water.

  Also, the production method of the secondary alcohol alkoxylate is not limited to the above production method, and for example, also by the method described in JP-A-2-295941, JP-B-61-51570, etc. Can be manufactured.

(Surfactant)
The surfactant of the present invention is characterized in that it contains the secondary alkyl ether sulfate ester salt (chemical formula 2) -containing composition according to the present invention as an anionic surfactant.

  As the surfactant of the present invention, for example, the secondary alkyl ether sulfate (chemical formula 2) -containing composition obtained by the above-described production method of the present invention is used as it is, or the water content is adjusted as necessary. Therefore, it can be used as an anionic surfactant. That is, the secondary alkyl ether sulfate ester salt (Chemical Formula 2) -containing composition of the present invention can be used alone as an anionic surfactant.

  Also, known surfactants depending on the use, for example, detergents for detergents, preferably surfactants for liquid detergents, more preferably surfactants for kitchen liquid detergents May be used in combination. However, the surfactant of the present invention is not limited to use in these applications, and can be used in other applications. In such a case, various types of conventionally used for the application are used. The surfactant can be used in combination in an appropriate amount so long as it does not impair the performance of the surfactant of the present invention and can exhibit the action and effect of each surfactant.

  For specific examples of such surfactants that can be used in combination, see the surfactants that can be used together in the above (liquid detergent composition containing a secondary alkyl ether sulfate ester type anionic surfactant).

  Furthermore, the surfactant of the present invention includes various additives that are usually used for each application, in addition to various surfactants (compounds or compositions having surface active ability) that are normally used for each application. Can be added in an appropriate amount within a range that does not affect the operational effects of the present invention and can exhibit the operational effects of the additive.

  For specific examples of such additives, see the additives described above (liquid detergent composition containing a secondary alkyl ether sulfate ester type anionic surfactant).

(Washing soap)
The cleaning agent of the present invention uses the anionic surfactant (Chemical Formula 2) according to the present invention.

  Further, the cleaning agent of the present invention has various additives used in ordinary cleaning agents within the range that does not affect the operation and effect of the present invention, and yet exhibits the operation and effect of the additive. An appropriate amount can be added within a possible range.

  For specific examples of such additives, see the additives described above (liquid detergent composition containing a secondary alkyl ether sulfate ester type anionic surfactant).

  This is strongly demanded for a liquid cleaning composition useful for dishwashing and the like because the composition containing the secondary alkyl ether sulfate (chemical formula 2) of the present invention is contained as an anionic surfactant. This is because the characteristics of rinsing properties and detergency can be expressed in a balanced manner. That is, when used as a liquid cleaning composition useful for dishwashing, etc., in addition to vegetables and fruits, especially tableware such as tableware and cooking utensils, persistent oil stains and stubborn sticking to cooking utensils, etc. Demonstrates high detergency. Further, since the rinsing property is high, the dirt and the detergent can be quickly washed away by simple water washing after washing, for example, washing with running water or pool water.

  Furthermore, since the secondary alkyl ether sulfate (chemical formula 2) -containing composition of the present invention is contained as an anionic surfactant, the raw alcohol of the anionic surfactant remains in the product. Therefore, there is no problem of skin irritation and salt tolerance (crystallization). Therefore, it is not necessary to go through a complicated process for removing the alcohol in the production stage, and the product can be provided at a low cost.

  Moreover, since it is hypoallergenic, it can suppress roughening of the hand skin, and since the detergent attached to the hand can be quickly washed away with water, the roughening of the hand skin can be further prevented.

  Furthermore, in Japan, 80% of domestic water is soft water of 80 ppm or less, but there are places where hard water is used as domestic water in some areas, and even when such hard water is used, it does not crystallize due to salt resistance. Moreover, the characteristics of detergency and rinsing properties are expressed in a well-balanced manner, and further, low irritation can be effectively expressed.

(emulsifier)
The secondary alkyl ether sulfate ester (chemical formula 2) -containing composition of the present invention may be used alone as an emulsifier, but may contain other conventionally known emulsifiers as necessary. For example, a nonionic surfactant, a cationic surfactant or a zwitterionic surfactant generally used as an emulsifier can be used in combination.

  There is no restriction | limiting in particular about the oily substance used for the emulsifier of this invention, Mineral oil, animal and vegetable oil, a synthetic oil, etc. can be used. These may be used alone or in combination of two or more. Examples of mineral oil include spindle oil, machine oil, liquid paraffin oil, and the like. Examples of animal and vegetable oils include beef tallow, lard, fish oil, whale oil, rapeseed oil, sesame oil, coconut oil, soybean oil, palm oil, camellia oil, castor oil, and the like.

  The emulsifier of the present invention can be used for agricultural chemicals, metal processing oils, paints, emulsifiers for emulsion polymerization, and the like.

(Secondary alkyl ether sulfate ester salt)
The secondary alkyl ether sulfate ester salt of the present invention is represented by Chemical Formula 2. Since it is as having demonstrated with the secondary alkyl ether sulfate ester salt (Chemical formula 2) containing composition of this invention regarding this, description here is abbreviate | omitted. That is, the water in the composition containing the secondary alkyl ether sulfate ester salt is removed so that the component represented by the chemical formula 2 is 100% by mass as a ratio to the anionic surfactant in the composition. It can be said that it is an example of the secondary alkyl ether sulfate ester salt (Chemical Formula 2) -containing composition of the present invention. This is achieved by appropriately adjusting the production conditions of the secondary alcohol alkoxylate represented by the chemical formula 3, the sulfation reaction conditions of the raw materials, the neutralization conditions by the basic substance, and the like. A secondary alkyl ether sulfate ester salt can be obtained. If this is used for a surfactant or a cleaning agent as described above, the same effect as that obtained using the secondary alkyl ether sulfate-containing composition of the present invention can be obtained.

  The secondary alkyl ether sulfate ester composition according to the present invention, the surfactant and the liquid detergent composition using the same, and other optional components conventionally used in the liquid detergent composition of the present invention. You may mix | blend in the range which does not impair the detergency and the performance of a rinse feeling. Optional components include amphoteric surfactants such as amine oxides, alkyl butines, alkylhydroxysulfobetaines, alkylamidobetaines, imidazoliniums, N-alkylamino acids, in addition to the anionic surfactants and nonionic surfactants. Agents, metal chelating agents such as glycolic acid, citric acid and EDTA, inorganic salts such as magnesium salts and calcium salts, liquid solvents such as ethanol and propylene glycol, antioxidants such as BHT and ascorbic acid, benzoic acid (salts), etc. Preservatives, thickeners such as natural polysaccharides and water-soluble polymer substances, fragrances, pigments and the like can be added.

(Possibility of industrial use)
Liquid detergent composition comprising secondary alkyl ether sulfate type anionic surfactant and secondary alkyl ether sulfate type anionic surfactant according to the present invention, secondary alkyl ether sulfate salt Compositions, surfactants using the same, detergents and liquid detergent compositions include clothing, textile products, tableware, containers, sundries, food, building maintenance products, houses, furniture, automobiles, aircraft, metal products, etc. It can be effectively used as a cleaning agent, shampoo, body shampoo, hand soap, etc. It is particularly suitable for use as a detergent for clothing or kitchen detergent that is intended to be cleaned with oil stains and is expected to contact the user's skin.

(Evaluation methods)
About the detergency as a detergent for clothes, it evaluates by the method recommended by JISK3362. Specifically, an artificial soiled cloth prepared by soaking a cotton cloth with an artificial stain obtained by mixing an oily pigment with animal oil or vegetable oil was washed with a stirring type detergency tester, The reflectance of light before and after cleaning is measured to determine the cleaning rate.

  The cleaning power for kitchen detergents can be evaluated by the peanut test recommended in JIS K3362, but it is performed by an evaluation test that assumes more consumer usage. Specifically, several artificial contamination dishes prepared by applying artificial stains obtained by mixing oily pigments to animal oils or vegetable oils on a dish and drying to remove the solvent are prepared. Measure the cleaning power by counting the number of dishes visually judged to have been cleaned thoroughly with a sponge containing an activator.

  With regard to rinsing properties for kitchen detergents, a tableware having a predetermined amount of a surfactant dropped on the surface is immersed in still water for a predetermined time, and then the stickiness of the surface is judged by the texture.

  Skin irritation is evaluated by monitoring the affected area in administration tests using animals such as rabbits, or in a patch-type open test in the human body.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

(Gas chromatography (GC) method)
The polyalkylene ether chain length is determined under the following conditions using GC.

Column: SUS0.5m, 3mm diameter Filler: Liquid phase DEXSIL 300GC, 2wt%
Carrier CHROMOSORB W AWDMCS, 80/100
MESH
Carrier gas: Nitrogen gas (for example, 80 ml / min)
Detector: FID
As pretreatment of a sample before GC analysis, for example, silylation can be performed under the following conditions.

Silylating agent: BSTFA: TMSC = 99: 1
Where BSTFA: bistrimethylfluoroacetamide
TMSC: Trimethylchlorosilane.

Addition amount of silylating agent: 10 times the amount of sample Reaction temperature: 70 ° C
Reaction time: 1 hour.

Although the area ratio of each chromatographic peak determined by the GC method is calculated as the ratio of each component having a different polyalkylene ether chain length, it is consistent with the H ¹ NMR analysis results for the alkyl ether sulfate after sulfation. Sex has been confirmed. For example, in the analysis result of the secondary dodecyl ether sulfate ester salt described in Example 1, both the H ¹ NMR analysis result and the GC analysis result coincided with the polyalkylene ether chain length = 2.1.

  Detergency is evaluated by the following method.

1. Washing power for clothing
(Evaluation method) Based on JISK-3362, the test was implemented on the following conditions using the stirring type detergency tester (Terg-O-meter: tergotometer).

(Contaminated cloth) 5 x 5 cm
(Oil stain liquid composition (%)) Oleic acid 28.3, triolein 15.6, cholesterol oleate 12.2, liquid paraffin 2.5, squalene 1.6, cholesterol 7.0, gelatin 29.8, carbon black 0.5
(Used water)
(Temperature) 25 ℃
(Time) Wash 5 minutes / Rinse 5 minutes (Bath ratio) 3 sheets / 1 pot (1 L)
(Activator concentration) 0.03%
(Evaluation of detergency) Using a reflectometer, measure the reflectivity of the raw fabric before contamination, artificial contamination fabric, and washed fabric after cleaning at three locations for each piece of fabric for each test piece. Detergency (%) was calculated.

Detergency (%) = 100 (Rw−Rs) / (Ro−Rs)
However, in the formula, Ro: reflectance of raw cloth, Rs: reflectance of artificially contaminated cloth, Rw: reflectance of washed cloth.

2. Detergency for kitchen (Procedure) Pour oil stain liquid into a dish and dry it, and adjust many oil stain dishes. After the synthesized surfactant is included in the sponge as an aqueous solution of a predetermined concentration and the oil stain dish is continuously washed and rinsed, it is visually judged that the oil stain remains without being visually removed. Count the number of dishes washed.

(Tableware) Ceramic, diameter 20cm
(Oil stain liquid composition (%)) Beef tallow 10.0, soybean oil 10.0, monoolein 0.25, oil red 0.1, n-hexane 80.0.
(Drying) Temperature 25 ° C. × Time 30 minutes (Synthetic product aqueous solution) Concentration 0.02%, dripping amount onto sponge 20 g
(Sponge) Commercial product for general kitchen cleaning W7.5cm × L11.0cm
(Rinsing water) Tap water Rinse (Evaluation method) Dip a tableware coated with an activator in still water for a predetermined time, evaluate the surface with a touch after pulling up, and measure the immersion time until it is determined that there is no stickiness. .

(Tableware) Ceramic, diameter 20cm
(Temperature) Room temperature (Activator aqueous solution concentration) 0.5%
(Addition amount) 3.0g
(Used water) Pure water
(Temperature) Room temperature Skin irritation
(Test method) Open 24 hours a day (Number of subjects) 20 (Sample concentration) 1.0%
(Judgment) Percentage of subjects who were aware of skin irritation such as rash (secondary alkyl ether sulfate anionic surfactant)
An anionic surfactant was synthesized by the method shown below.

Example 1
<Synthesis> Synthesis of secondary dodecyl ether sulfate ester salt (polyalkylene ether chain length (average value) = 2.1) (Synthesis of alkyl ether)
A dodecene isomer mixture obtained by treating 1-dodecene with 5 mass% of BEA type zeolite (trade name: VALFOR CP811 BL-25) manufactured by PQ at 10O 0 C for 10 hours (1-dodecene 25 mol%, inner dodecene) 810 g (4.82 mol) consisting of 75 mol%), 900 g (14.52 mol) of monoethylene glycol, and 100 g of B20EA zeolite (supra) manufactured by PQ as a catalyst, made of 3000 ml of glass equipped with a stirring blade and a reflux condenser. The reactor was charged. After replacing the gas phase part of the reactor with nitrogen, the reactor was kept in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150 ° C. while stirring at 600 rpm, and the reaction was carried out at the same temperature for 3 hours. Then, the reaction solution was cooled to room temperature, and the upper dodecene phase was separated and distilled. After distilling off unreacted dodecene, 155 g (0.67 mol) of secondary dodecanol monoethoxylate was obtained in a boiling point range of 129 to 131 ° C. under a reduced pressure of 2 mmHg.

This intermediate product and 0.2 g of sodium hydroxide as a catalyst were charged into a stainless steel autoclave. After the inside was replaced with nitrogen, the pressure in the reactor was set to 1.0 kg / cm ² G with nitrogen, the temperature was raised to 150 ° C., and 29.5 g (0.68 mol) of ethylene oxide was introduced into the autoclave in 3 hours. After introduction, the mixture was kept at 150 ° C. for an additional hour, then cooled to room temperature and purged with the internal pressure, whereby a secondary dodecanol ethoxylate having an average polyalkylene ether chain length of 2.1 (GC method) was obtained. Got.

(Sulfation)
The obtained secondary dodecanol monoethoxylate is used as a reaction tube that forms a cylindrical reaction zone having an inner diameter of 5 mm and a length of 100 cm. Along the inner wall, the film was allowed to flow in a thin film at a rate of 16.2 g / min. At the same time, anhydrous sulfuric acid diluted with nitrogen gas was allowed to flow from a nozzle provided at the top of the reaction tube. The flow rate of all the introduced nitrogen gas in the reaction tube was 30 m per second, and the concentration of sulfuric anhydride in all the introduced mixed gas was 4% by volume. The molar ratio of sulfurized anhydrous sulfuric acid to sulfurized secondary dodecanol ethoxylate was 1.1. The reaction heat generated by the reaction of ethoxylate and sulfuric anhydride was removed by a refrigerant flowing outside the reaction tube and kept at 15 ° C. The fluid exiting the reaction tube was separated into nitrogen gas and reaction products by a cyclone. The reaction product was immediately neutralized with aqueous sodium hydroxide to give an approximately 25% aqueous solution of the desired secondary dodecyl ether sulfate salt.

  The synthesized surfactants were evaluated for apparel detergency and the results are shown in Table 1.

(Example 2)
<Synthesis> Synthesis of secondary dodecyl ether sulfate ester salt (polyalkylene ether chain length (average value) = 2.0) (alkyl ether (chemical formula 3 (wherein R ₁ + R ₂ = 11, carbon number in A) = Synthesis of secondary dodecanol diethoxylate represented by 2))
168.3 g (1.0 mol) of 1-dodecene, 318.4 g (3.0 mol) of diethylene glycol, and 35.4 g of BEA type zeolite (trade name: VALFOR CP811 BL-25) manufactured by PQ as a catalyst were stirred and reflux cooled. A 1000 ml glass reactor equipped with a vessel was charged and the gas phase was replaced with nitrogen, and then kept in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150 ° C. while stirring at a rotation speed of 300 rpm, and the mixture was reacted at the same temperature for 20 hours. Then, the reaction solution was cooled to room temperature, and the upper dodecene phase was separated and distilled. After distilling unreacted dodecene and diethylene glycol, secondary diethylene glycol monododecyl ether (secondary dodecyl ether (polyalkylene ether chain length = 2.0), poly The proportion of alkylene ether chain length 2 was 93.5%, and the remaining 6.5% was composed of secondary dodecyl ether other than polyalkylene ether chain length 2 (gas chromatograph (GC) area ratio)) 67.4 g (0.25 mol) was obtained.

(Sulfation)
An approximately 25% aqueous solution of a secondary dodecyl ether sulfate ester salt was obtained in the same manner as in Example 1 except that the obtained secondary dodecanol diethoxylate was used instead of the secondary dodecanol ethoxylate.

(Comparative Example 1)
<Synthesis> Synthesis of primary dodecyl ether sulfate ester salt (polyalkylene ether chain length (average value) = 3.1) (Synthesis of alkyl ether)
Secondary dodecyl ether sulfate ester salt 1-dodecene is treated with PQ BEA zeolite (trade name: VALFOR CP811 BL-25) 5% by mass and treated at 150 ° C. for 10 hours, dodecene isomer 810 g (4,82 mol) of a mixture (1-dodecene 25 mol%, inner dodecene 75 mol%), 900 g (14.52 mol) of monoethylene glycol, and a BEA type zeolite manufactured by PQ as a catalyst (trade name: VALFOR CP811 BL-25) 100 g was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase portion was replaced with nitrogen, and then kept at normal pressure in a nitrogen atmosphere. Subsequently, while stirring at a rotation speed of 600 rpm, the temperature was raised to 150 ° C. and reacted at the same temperature for 3 hours, and then the reaction solution was cooled to room temperature, and the upper dodecene phase was separated and distilled. After distilling unreacted dodecene, 155 g of secondary dodecanol monoethoxylate was obtained in a boiling point range of 129 ° C. to 131 ° C. at a reduced pressure of 2 mmHg.

  155 g (0.67 mol) of secondary dodecanol monoethoxylate and sodium hydroxide 0.2 as a catalyst were charged into a stainless steel autoclave. After nitrogen substitution, the pressure in the reactor was adjusted to 1.0 kg / cm 2 G with nitrogen, After raising the temperature to 150 ° C., 62 g (1.41 mol) of ethylene oxide was introduced into the autoclave in 3 hours. After the introduction, the mixture was further maintained for 1 hour at 150 ° C., cooled to room temperature, and purged with the internal pressure to obtain a secondary dodecanol ethoxylate having an average polyalkylene ether chain length of 3.1.

(Sulfation)
An approximately 25% aqueous solution of a primary dodecyl ether sulfate ester salt was obtained in the same manner as in Example 1 except that the obtained secondary dodecanol ethoxylate was used in place of the secondary dodecanol ethoxylate.

(Comparative Example 2)
<Synthesis> Synthesis of secondary dodecyl ether sulfate ester salt (polyalkylene ether chain length (average value) = 1.0) (Synthesis of alkyl ether)
Secondary dodecyl ether sulfate ester salt 1-dodecene is treated with PQ BEA zeolite (trade name: VALFOR CP811 BL-25) 5% by mass and treated at 150 ° C. for 10 hours, dodecene isomer 810 g (4,82 mol) of a mixture (1-dodecene 25 mol%, inner dodecene 75 mol%), 900 g (14.52 mol) of monoethylene glycol, and a BEA type zeolite manufactured by PQ as a catalyst (trade name: VALFOR CP811 BL-25) 100 g was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase portion was replaced with nitrogen, and then kept at normal pressure in a nitrogen atmosphere. Subsequently, while stirring at a rotation speed of 600 rpm, the temperature was raised to 150 ° C. and reacted at the same temperature for 3 hours, and then the reaction solution was cooled to room temperature, and the upper dodecene phase was separated and distilled. After distilling unreacted dodecene, 155 g of secondary dodecanol monoethoxylate was obtained in a boiling point range of 129 ° C. to 131 ° C. at a reduced pressure of 2 mmHg.

(Sulfation)
An approximately 25% aqueous solution of a secondary dodecyl ether sulfate ester salt was obtained in the same manner as in Example 1 except that the obtained secondary dodecanol monoethoxylate was used instead of the secondary dodecanol ethoxylate.

  The surfactants obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated, and the results are shown in Table 1.

Claims (8)

An anionic surfactant of the secondary alkyl ether sulfate type, which is represented by Chemical Formula 1 having an average polyalkylene ether chain length of 1.5 to 2.5:

(However, in the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, and A is an alkylene group having 2 or more carbon atoms. N represents the number of repeating units of the oxyalkylene group, the average value thereof is in the range of 1.5 to 2.5, and M is an alkali metal, alkaline earth metal, ammonium group, or hydrogen atom-substituted ammonium group And m represents the valence of M).   The surfactant according to claim 1, wherein the proportion of the component having a polyalkylene ether chain length of 1 or 2 is 60% or more. The surfactant according to claim 1 or 2, wherein the component in which R ₁ is a methyl group and R ₂ is an alkyl group having 2 or more carbon atoms is 30 to 70%.

(However, in the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, and A is an alkylene group having 2 or more carbon atoms. And M is an alkali metal, alkaline earth metal, ammonium group, or hydrogen atom-substituted ammonium group, and m is a valence of M. A secondary alkyl ether sulfate ester composition, wherein the component represented by Chemical Formula 2 is 40% or more of the anionic surfactant. The component represented by Chemical Formula 2 is represented by Chemical Formula 3

(However, in the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, and A is an alkylene group having 2 or more carbon atoms. 5. The secondary alcohol according to claim 4, wherein the secondary alcohol alkoxylate represented by formula (2) is obtained by sulfating and neutralizing with a basic substance. An alkyl ether sulfate ester-containing composition.   The secondary alkyl ether sulfate composition according to claim 5, wherein the raw material secondary alcohol alkoxylate is produced by adding dialkylene glycol to a linear olefin having 8 to 30 carbon atoms.   A surfactant comprising the secondary alkyl ether sulfate ester-containing composition according to any one of claims 4 to 6 as an anionic surfactant.

(However, in the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, each having a synthetic carbon number of 7 to 29, and A is an alkylene group having 2 or more carbon atoms. And M is an alkali metal, alkaline earth metal, ammonium group, or hydrogen atom-substituted ammonium group, and m is a valence of M.