JP2005248406A - Method for continuously producing high concentration liquid softener composition and high concentration liquid softener composition obtained by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply and continuously producing a high concentration liquid softener composition having a low viscosity and good stability with time without using a viscosity-reducing agent. <P>SOLUTION: This method for continuously producing the high concentration liquid softener composition is characterized by comprising a process for feeding an aqueous phase into a piping in which a line mixer equipped with a stirrer rotated in the circumferential direction is disposed and which is extended in the longitudinal direction, a process for continuously feeding an oil phase containing a cationic surfactant mixture into the aqueous phase-fed piping from the upstream side of the stirring blade, and a process for mixing and emulsion-dispersing the oil phase in the piping with the aqueous phase with the stirring blade to obtain the softener composition, feeding the oil phase in the process for feeding the oil phase to give a cationic surfactant concentration of 10 to 40 wt.% in the softener composition, and stirring and emulsion-dispersing the oil phase with the aqueous phase in conditions of 10≤A/B≤300, wherein (I) A m/s is a circumferential speed of the stirring blade, and (II) B m/s is a longitudinal direction linear speed of the aqueous phase and the oil phase passing through the stirring blade. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a continuous manufacturing method of a high-concentration liquid softening agent composition having an increased content of a cationic surfactant, which is a softening agent base material that imparts flexibility to fibers and clothing, and the manufacturing method. More particularly, the present invention relates to a continuous production method of a high-concentration liquid softener composition in which a high viscosity generated due to a high substrate concentration and a viscosity increase and separation with time are suppressed.

Recent softener products containing cationic surfactants are concentrated types with increased softener base content due to cost reduction during manufacture and transportation, consumer usability, etc. High concentration is the mainstream, and it is still in the direction of further concentration.
However, many of the cationic surfactants used in such concentrated softeners are sparingly soluble in water because they have hydrophobic long-chain alkyl groups. In addition, when the cationic surfactant comes into contact with water, the surface thereof has a liquid crystal structure, so that the viscosity of the surface increases to become a viscous liquid, which makes it difficult to atomize. For this reason, when trying to manufacture a concentrated softener product, the softener becomes too viscous for use, or changes in viscosity or separation with time will occur, and stability over time will become a problem. There was a thing.

Regarding the production of a concentrated softening agent, Patent Document 1 uses a liquid crystal structure of a cationic surfactant, and the cationic surfactant itself forms a dispersoid to form an o / w emulsion. A two-stage emulsification method has been proposed. In this method, since the concentration of the cationic surfactant can be increased, it is possible to produce a concentrated softening agent. However, since the process is divided into two steps, the operation becomes very complicated. Therefore, it cannot be said that it is a process efficient manufacturing method of an emulsion.
Moreover, in order to eliminate the high viscosity which is a big problem of the concentrated softening agent, an additive exhibiting a viscosity reducing effect has been added. Conventional additives for reducing the viscosity of softeners include sugar alcohols, aromatic acids, imidazolines, amide cations and the like. For example, Patent Document 2 achieves a high concentration of the cationic surfactant by adding a mixture of 10% or more aromatic acids to Patent Document 3 and sugar alcohols in Patent Document 3 to the softener composition. However, the amount of these additives added is high, and the cost becomes expensive. Moreover, in patent document 4, low-temperature stability is improved by mix | blending diester type | mold quaternary ammonium salt and imidazolines and amide cations by specific ratio. However, satisfactory results have not been obtained for the stability at room temperature, and it is expected that the cost will be high. Even when an appropriate viscosity reducing agent such as ethylene glycol was added, the viscosity and stability over time were not sufficient. Furthermore, it is conceivable to mix a solvent such as ethanol. However, since ethanol is flammable, there is a problem in safety during blending and use.

Patent Document 5 discloses a method for producing a stable oil-in-water emulsion. However, since the production method of the patent document does not perform continuous emulsification, the production efficiency is not sufficient.
Patent Document 6 discloses a method for continuously atomizing a cationic surfactant. In addition, to produce a softener containing an oil-in-water (o / w) emulsion with a high concentration of cationic surfactant as a dispersoid, the unique properties of cationic surfactants with high hydrophobicity (B) Avoid contact with water before dispersion as much as possible because it becomes a viscous liquid by contacting or mixing with water, and (b) Dispersion force initially applied Has a large effect on the particle size, so that it can be used under conditions that can sufficiently satisfy the following two points: quickly supplying to the stirring blade before it becomes a viscous liquid when it comes into contact with water and fine dispersion becomes difficult It is disclosed that it must be. However, since only di-long chain dimethylammonium chloride is used as a cationic surfactant in the patent document, the effect of suppressing liquid crystal formation by the cationic surfactant is not sufficient. Moreover, the problem in the case of manufacturing the composition containing a high concentration flexible base material is not pointed out, and the concentration of the cationic surfactant in the composition is as low as 5%.
Patent Document 7 discloses a method for producing a softening agent composition using a line mixer. This method is a method for producing a conventional soft material composition having a relatively low concentration, and a method for continuously supplying a water phase into a pipe supplying a cationic surfactant (oil phase). It is.
Patent Document 8 discloses a method for atomizing a cationic surfactant in water. However, the production method of the patent document does not use a line mixer and does not carry out continuous emulsification, so that it is not sufficient in terms of production efficiency.
Also, any of the documents discloses a method for easily obtaining a high-concentration softener composition by setting the ratio between the peripheral speed of the stirring blade and the linear velocity of the liquid passing through the stirring blade within a specific range. Absent.
As described above, a production method capable of obtaining a high-concentration softening agent composition containing a high-concentration cationic surfactant without adding a special thinning agent with a simple production method has not yet been realized. is the current situation.

JP-A-2-68137 Japanese National Patent Publication No. 9-503826 JP 10-298149 A JP-T-9-506684 JP 58-143830 A JP-A-57-102226 JP-A-1-249129 JP-A-57-5797

  Under such circumstances, the present invention provides a simple and continuous method for producing a high-concentration liquid softening agent composition having a low viscosity and good stability over time without using a special thinning agent, and thus obtained. It is an object of the present invention to provide a high-concentration liquid softening agent composition.

In order to solve the above problems, the present inventors have made extensive studies on stirring and mixing an aqueous phase and an oil phase with a line mixer equipped with a stirring blade, and as a result, an oil phase containing a cationic surfactant is obtained. During mixing and emulsification dispersion after continuous addition to the water phase, by controlling the peripheral speed of the stirring blade and the longitudinal speed of the liquid passing through the stirring blade, it is possible to promote the atomization of the oil phase, As a result, it was found that a softener composition having a low viscosity and good stability over time can be continuously produced.
That is, the present invention is a continuous production method of a high concentration liquid softener composition in which an oil phase is emulsified and dispersed in an aqueous phase,
A step of continuously supplying a water phase into a pipe extending in a longitudinal direction in which a line mixer provided with a stirring blade rotating in a circumferential direction is disposed;
A step of continuously supplying an oil phase containing a cationic surfactant mixture into the pipe supplying the aqueous phase from the upstream side of the stirring blade;
A step of mixing and emulsifying and dispersing the oil phase in the pipe with the stirring blade into the aqueous phase to obtain a softening agent composition,
In the step of supplying the oil phase, the oil phase is supplied so that the concentration of the cationic surfactant in the softener composition is 10 to 40% by weight,
The steps of mixing and emulsifying and dispersing the oil phase in the aqueous phase include: (I) the circumferential speed of the stirring blade is Am / s, and (II) the longitudinal linear velocity of the water phase and the oil phase passing through the stirring blade. Provided is a continuous production method for the high-concentration liquid softening agent composition, wherein B m / s is performed under the condition of 10 ≦ A / B ≦ 300.
In the present invention, preferably, the step of supplying the oil phase supplies the oil phase from a location that allows the supplied oil phase to reach the stirring blade before forming a liquid crystal structure by contact with the aqueous phase. To do.
In the present invention, preferably, the step of supplying the oil phase comprises a mono long chain cation containing one long chain alkyl group or one alkenyl group in the molecule with respect to the total weight of the cationic surfactant mixture. The mono long-chain cationic surfactant is supplied so that the amount of the surfactant is 10 to 80% by weight.
The present invention also provides a high-concentration liquid softener composition produced by the continuous production method according to the present invention described above.
In the composition of the present invention, the viscosity is preferably 1500 cP or less.

According to the continuous production method of the present invention, a high-concentration liquid softening agent composition having good stability over time, having a low viscosity and suppressing increase in viscosity and separation over time, despite the high content of the softening agent base material. It can be continuously and conveniently manufactured. In addition, when the step of supplying the oil phase includes the step of supplying the oil phase from a location where the supplied oil phase reaches the stirring blade before forming the liquid crystal structure by contact with the aqueous phase, the cationic interface Even when the activator comes into contact with water, the liquid crystal structure is not substantially formed, so that a high concentration liquid softener composition can be produced with high production efficiency without applying a strong shearing force.
The high-concentration liquid softener composition obtained by the production method of the present invention is excellent in usability because of its good fluidity. And since the production method of the present invention is a very simple method, not only is it suitable for the production of such a high-concentration softener composition, but also the fluidity of the system at the time of production becomes good, Since it becomes easy to uniformly disperse particles composed of a softener base material, it is possible to easily produce a high-concentration softener composition that not only has the above characteristics but also has excellent dispersion stability and stability over time. .

The concentration of the cationic surfactant mixture in the high-concentration liquid softener composition obtained by the production method of the present invention is 10 to 40% by weight, preferably 12 to 38% by weight, more preferably 15 to 35% by weight. . Within such a range, a viscosity suitable for use as a concentrated softener composition can be obtained, which is preferable.
The cationic surfactant that can be used in the present invention can be used without particular limitation, and is a mono long chain type represented by the following general formula (1), general formula (2), or general formula (3). It is preferable to contain a cationic surfactant. In particular, it is preferable to contain a mono long-chain cationic surfactant represented by the general formula (1).

In the general formula (1), R ^{1 to} R ³ groups may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or — (CH ₂ — CH (Y) —O) n—H (wherein Y is a hydrogen atom or CH ₃ , and n is a number of 2 to 3) or a benzyl group. Among these, a C1-C3 alkyl group and a C1-C3 hydroxyalkyl group are preferable. When at least one of the groups R ^{1 to} R ³ is a hydrogen atom, the general formula (1) represents a neutralized product of an amine. The group of R ⁴ is an alkyl group or alkenyl group having 10 to 26 carbon atoms, and even if it is unsubstituted, a functional group such as —O—, —CONH—, —NHCO—, —COO—, —OCO—, etc. It may be divided by a group or substituted with a functional group such as —OH. Among these, an alkyl group having 14 to 20 carbon atoms and an alkenyl group are preferable, and the structure of the functional group to be divided or not is not limited. X is a halogen atom or a monoalkyl sulfate group. Examples thereof include halogen atoms such as chlorine atom, bromine atom and iodine atom, methyl sulfate group, ethyl sulfate group and hydroxyl group. Among these, a halogen atom and a methyl sulfate group are preferable. In particular, a compound in which R ^{1 to} R ³ are a methyl group or a hydroxyethyl group, R ⁴ is a partially hydrogenated palm oil oxyethyl group, and X is a chlorine atom or a methyl sulfate group is preferable.

In the general formula (2), the groups R ^{1 to} R ³ have the same meaning as in the general formula (1). One of the groups R ⁵ and R ⁶ is an alkyl group or alkenyl group having 10 to 26 carbon atoms, and even if it is unsubstituted, —O—, —CONH—, —NHCO—, —COO— , -OCO- or the like, or may be divided or substituted with a functional group such as -OH. Among these, an alkyl group having 14 to 20 carbon atoms and an alkenyl group are preferable, and the structure of the functional group to be divided or not is not limited. The other is an alkyl group having 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, or — (CH ₂ —CH (Y) —O) n—H (wherein Y is a hydrogen atom or CH ₃ . , N is a number of 2 to 3). Among these, a C1-C3 alkyl group or a C1-C3 hydroxyalkyl group is preferable. X has the same meaning as in general formula (1).
In the general formula (3), one of R ⁷ and R ⁸ groups is an alkyl group or alkenyl group having 10 to 26 carbon atoms, and even if it is unsubstituted, —O—, —CONH—, It may be divided by a functional group such as —NHCO—, —COO—, —OCO— or substituted with a functional group such as —OH. Among these, an alkyl group having 14 to 20 carbon atoms and an alkenyl group are preferable, and the structure of the functional group to be divided or not is not limited. The other is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or — (CH ₂ —CH (Y) —O) n—H (wherein Y is a hydrogen atom or CH ₃ . , N is a number of 2 to 3). Among these, a C1-C3 alkyl group or a C1-C3 hydroxyalkyl group is preferable.

  Specific examples of the mono long-chain cationic surfactants of the above general formula (1) and general formula (2) include octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, beef tallow trimethylammonium chloride, Coconut oil trimethylammonium chloride, decyldimethylbenzylammonium chloride, oleoyloxyethyltrimethylammonium chloride, N-stearoyloxyethyl-N-, N-dimethyl-N- (2-hydroxyethyl) ammonium methyl sulfate, N-stearoyloxyethyl -N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate, N-oleoyloxyethyl-N-, N-dimethyl-N- (2-hydroxy Til) ammonium methyl sulfate, 1-taloyloxy-2-hydroxy-3-trimethylammonium propane chloride, N-oleoyloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate N-linoleyloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate, N-palmioyloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ) Ammonium methyl sulfate, N-palm oil oxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate, and the like. These may be used alone or in combination of two or more. They can be used in combination. In particular, N-stearoyloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate, N-oleoyloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ) Ammonium methyl sulfate, N-linoleyloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate, N-palmioyloxyethyl-N-methyl-N-, N-di ( 2-Hydroxyethyl) ammonium methyl sulfate, N-palmoiloxyethyl-N-methyl-N-, N-di (2-hydroxyethyl) ammonium methyl sulfate are preferred.

  The long chain carbon site in the above general formulas (1) to (3) is a residue of a fatty acid derived from a general oil or fat. Examples of the oils and fats include linseed oil, eno oil, jute deer oil, olive oil, cacao butter, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, cinnaat oil, cinnakiri oil, soybean oil, tea seed oil, camellia oil , Corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, cottonseed oil, coconut oil, tree wax, peanut oil, horse fat, beef tallow, beef leg fat, beef tallow, pork fat, goat fat, sheep fat Animal fats such as milk fat, fish oil, whale oil and the like. These fats and oils may be cured, modified, purified, etc., and two or more kinds of fats and oils may be mixed.

When the mono long-chain cationic surfactants of the above general formulas (1) and (2) are neutralized amines and the general formula (3) is a mono long-chain imidazoline salt, the neutralization is usually The acid can be used. Specific examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as benzoic acid, citric acid, malic acid, succinic acid, and acrylic acid.
Examples of neutralized mono long-chain amines of the above general formula (1) and general formula (2) include stearyl dimethylamine hydrochloride, oleyl dimethylamine hydrochloride, stearyl dimethylamine sulfate, and N-stearoyloxyethyl. -N-methyl-N- (2-hydroxyethyl) amine hydrochloride, N-oleoyloxyethyl-N-, N-di (2-hydroxyethyl) amine sulfate, 1-cocoyloxy-2-hydroxy-3 -Dimethylamine hydrochloride etc. are mentioned, These 1 type can be used individually or in combination of 2 or more types.
Specific examples of the mono long-chain imidazoline salt of the general formula (3) include 1-stearoyloxyethyl-2-methylimidazoline hydrochloride, 1-stearoyloxyethyl-2-ethylimidazoline hydrochloride, 1-stearoyloxyethyl. And 2-propylimidazoline hydrochloride.

  As a cationic surfactant mixture that can be used in the present invention, in addition to the mono long-chain cationic surfactant represented by the above general formula (1), general formula (2) and general formula (3), N-, N-dioctyl-N-, N-dimethylammonium chloride, N-, N-didodecyl-N-, N-dimethylammonium chloride, N-, N-dihexadecyl, which are di-long-chain cationic surfactants -N-, N-dimethylammonium chloride, N-, N-di beef tallow-N-, N-dimethylammonium chloride, N-, N-dicoconut oil-N-, N-dimethylammonium chloride, N-, N-di Octadecyl-N-, N-dimethylammonium chloride, N-, N-distearoyloxyethyl-N-, N-dimethylammonium chloride, N-, N-dioleoyloxy Ethyl-N-, N-dimethylammonium chloride, N-, N-distearoyloxyethyl-N-methyl-N- (2-hydroxyethyl) ammonium methyl sulfate, N-, N-dioleoyloxyethyl-N- Methyl-N- (2-hydroxyethyl) ammonium methyl sulfate, N-, N-palmioyloxyethyl-N-methyl-N- (2-hydroxyethyl) ammonium methyl sulfate, N-, N-palm oil oxyethyl- N-methyl-N- (2-hydroxyethyl) ammonium methyl sulfate, 1-, 2-ditaloyloxy-3-trimethylammonium propane chloride and the like can be mentioned. Of these, N-, N-distearoyloxyethyl-N-methyl-N- (2-hydroxyethyl) ammonium methyl sulfate, N-, N-dioleoyloxyethyl-N-methyl-N- (2-hydroxy Ethyl) ammonium methylsulfate, N-, N-palmioyloxyethyl-N-methyl-N- (2-hydroxyethyl) ammonium methylsulfate, N-, N-linoleyloxyethyl-N-methyl-N- (2 -Hydroxyethyl) ammonium methyl sulfate, N-, N-palm oil oxyethyl-N-methyl-N- (2-hydroxyethyl) ammonium methyl sulfate are preferred.

  The concentration of the mono long-chain type cationic surfactant represented by the general formula (1), the general formula (2), and the general formula (3) may be a cationic surfactant mixture in a softener composition. It is desirable that it is 10 to 80% by weight based on the total weight. Within such a range, even when the oil phase containing the cationic surfactant mixture and the aqueous phase are in contact with each other, the formation of the liquid crystal structure is suppressed, and satisfactory flexible performance can be exhibited. It is preferable because it is possible. Preferably it is 15-70 weight%, More preferably, it is 20-60 weight%.

In the softener composition of the present invention, in order to facilitate film formation by the cationic surfactant mixture, a nonionic surfactant can be blended in the oil phase together with the cationic surfactant mixture. .
Nonionic surfactants that can be used in the present invention are generally polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene castor oil, Examples thereof include polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, and the like.
Specific examples of such nonionic surfactants include hexaglyceryl monolaurate, decaglyceryl monolaurate, decaglyceryl monostearate, decaglyceryl monoisostearate, decaglyceryl diisostearate, POE monooleate (15) Glyceryl, monoisostearic acid POE (20) sorbitan, mono coconut oil fatty acid POE (20) sorbitan, monooleic acid POE (20) sorbitan, trioleic acid POE (20) sorbitan, tetraoleic acid POE (40) sorbit, tetraoleic acid POE (60) sorbit, POE (20) castor oil, POE (40) castor oil, POE (20) hydrogenated castor oil, POE (40) hydrogenated castor oil, polyethylene glycol monostearate (25EO), polyethylene monostearate (40EO), POE (20) cetyl ether, POE (40) cetyl ether, POE (20) oleyl ether, POE (20) isodecyl ether, POE (60) isohexadecyl ether, POE (40) isotridecyl ether POE (20) behenyl ether, POE (25) octyldodecyl ether, POE (20) POP (4) cetyl ether, POE (7.5) nonylphenyl ether, POE (15) nonylphenyl ether, POE (15) stearylamine, POE (15) stearamide etc. are mentioned, These 1 type can be used individually or in combination of 2 or more types.

The blending amount of the nonionic surfactant in the softener composition is 0.5 to 20% by weight, preferably 1 to 10% by weight, more preferably 2 to 5% by weight in the softener composition.
The cationic surfactant mixture used in the production method of the present invention and the nonionic surfactant used if necessary can be used without removing the water and organic solvent used in the production of the surfactant. In this case, water or solvent brought in from a cationic surfactant or a nonionic surfactant may be present. However, the ratio of the cationic surfactant, nonionic surfactant and water or organic solvent is preferably 10: 1 to 1: 1, more preferably 8: 1 to 3: 1 in terms of mass ratio. If the amount of water is within such a range, it is preferable because the oil phase can be easily emulsified without gelation and thickening. If the amount of the solvent is in such a range, it can be easily emulsified and formed into particles, particles having a small particle size can be easily obtained by monodispersion, and the stability of the resulting softener composition is also in a good range. This is preferable.
Specific examples of organic solvents brought in from cationic surfactants and nonionic surfactants include lower alcohols such as ethanol, isopropyl alcohol, and propyl alcohol, propylene glycol, ethylene glycol, and 1,3-butylene glycol. And polyhydric alcohols such as dipropylene glycol.
Furthermore, in the softener composition of the present invention, in addition to the cationic surfactant mixture, an oil component can be blended in the oil phase as necessary. Examples of such oil-based components include oil-soluble fragrances and oil-soluble antibacterial agents, and the blending amount of these components can be appropriately selected within a range not impeding the effects of the present invention.

  Examples of fragrances for enhancing the feeling of use of the softener composition include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols. , Ethers such as aliphatic ethers and aromatic ethers, oxides such as aliphatic oxides and terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes and aromatic aldehydes , Aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, ketones such as non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, Acids such as terpene carboxylic acids, hydrogenated aromatic carboxylic acids, and aromatic carboxylic acids , Acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones, lactones such as aromatic lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl Synthetic fragrances such as carboxylic acid ester, terpene carboxylic acid ester, aromatic carboxylic acid ester, etc., nitrogen compounds such as nitromusks, nitriles, amines, pyridines, quinolines, pyrrole, indole, animals, plants 1 type or 2 types or more of the blended fragrance | flavor containing the natural fragrance | flavor, natural fragrance | flavor, and / or synthetic fragrance | flavor from can be used. For example, in 1996, Chemical Industry Daily, published by Motoichi Into, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Fragrances described in “Perfume and Flavor Chemicals” by STEFEN Arctander can be used.

As an aqueous phase, water and, if necessary, a dispersion stabilizer, a low-temperature stabilizer, an inorganic salt, an organic acid salt, a dye, an antibacterial agent, a bactericide, an antiseptic, an antioxidant, a water-soluble polymer, and a water-soluble polymer An active ingredient, a pH adjuster, etc. can be included. The compounding quantity of these components can be suitably selected in the range which does not disturb the effect of the present invention.
In the present invention, when a cationic surfactant having a hydrolyzable group is used as a softener base, the base may hydrolyze during storage depending on the pH of the softener composition. In general, the pH of the composition is adjusted with an acidic compound to pH 2 to 5, which is a stabilization region of the hydrolyzing group, and the composition obtained by the production method of the present invention can also be adjusted to the above pH. desirable. In this case, as the acidic compound, for example, an aqueous solution of hydrochloric acid, sulfuric acid, citric acid, phosphoric acid or the like is preferably used. The acidic compound may be added to the aqueous phase, may be added after emulsification, or may be added in divided portions.

Next, with reference to FIG. 1, an example of the apparatus for implementing the continuous manufacturing method by this invention of a high concentration liquid softening agent composition is demonstrated. FIG. 1 is a schematic view of a dispersion apparatus for carrying out the continuous production method according to the present invention of a high-concentration liquid softener composition.
Dispersing apparatus 1 has a cationic surface activity that extends in the longitudinal direction and is provided with line mixer 2 and is connected to pipe 3 for supplying an aqueous phase from the upstream side and pipe 3 on the upstream side of line mixer 2. And a supply pipe 4 for supplying an oil phase containing the agent.
The pipe 3 is substantially linear from the supply pipe 4 to the line mixer 2. The inner diameter of the pipe 3 is slightly smaller in the upstream portion of the line mixer 2 than in the portion including the line mixer 2. The inner diameter of the portion including the line mixer 2 is, for example, 20 to 150 mm. It is preferable that the pipe 3 is arranged in the vertical direction. The aqueous phase can flow from top to bottom or from bottom to top.

The line mixer 2 is arranged coaxially with the pipe 3, and a stirring blade 5 that can rotate in the circumferential direction, extends downstream from the stirring blade 5, and rotates the stirring shaft 5, and drives the rotating shaft 6. Motor (not shown). The line mixer 2 is, for example, a conventionally used line mixer or line homomixer.
The stirring blade 5 should be selected with emphasis on the shearing effect, and does not need to be selected in consideration of the mixing effect of mixing the whole as in the application example of the in-vessel treatment. Therefore, the type of the stirring blade 5 is preferably a type capable of rotating at high speed and applying high shear, such as a disper type, a fan turbine type, a displo type, and an inclined type. Further, the number of stages of the stirring blade 5 may be one as shown in FIG. 1 or may be a plurality of stages. Further, the stirring blade 5 preferably has a blade outer diameter that covers the entire inner diameter of the pipe 3 so that the entire amount of the oil phase supplied into the pipe 3 can be entrained.
The supply pipe 4 projects almost to the center in the pipe 3, is bent downstream therefrom, and terminates at a supply port 7 facing the line mixer 2. The inner diameter of the supply port 7 is 2 of the inner diameter of the portion of the pipe 3 including the supply port 7 in order to promote the oil phase having a small flow rate to enter the aqueous phase or to reduce the pressure loss of the aqueous phase. / 3 or less is preferable, and ½ or less is more preferable. The supply port 7 is preferably provided at a location that allows the supplied oil phase to reach the stirring blade 5 before forming a liquid crystal structure by contact with the aqueous phase. This location is governed by the time from the contact between the cationic surfactant and water until the dispersion by the stirring blade before the liquid crystal structure is formed and the degree of mixing due to the turbulence in the flow. The distance between the supply port 7 and the upstream end of the stirring blade 5 should be 50 times or less, preferably 30 d or less, more preferably, where d is the tip diameter of the stirring blade 5. 20d or less is suitable.

Next, the operation and operating conditions of the above-described dispersion apparatus will be described.
The above-described aqueous phase is continuously supplied from the upstream side of the pipe 3. Next, the stirring blade 5 is rotated in the circumferential direction, and the above-described oil phase containing the cationic surfactant mixture is continuously supplied from the supply pipe 4. The supply amount of the oil phase is determined so that the concentration of the cationic surfactant in the high-concentration liquid softener composition produced by the oil phase and the aqueous phase is 10 to 40% by weight. The oil phase continuously supplied from the supply pipe 4 flows to the stirring blade 5 of the line mixer 2 together with the water phase continuously supplied in the pipe 3. The oil phase and the aqueous phase are mixed and dispersed, that is, emulsified by the stirring blade 5, thereby becoming a high-concentration liquid softener composition. Specifically, the oil phase is sheared and atomized by the stirring blade 5 to promote emulsification. Further, since the supply port 7 is provided at a location that allows the supplied oil phase to reach the stirring blade 5 before forming the liquid crystal structure by contact with the aqueous phase, it is added to the aqueous phase. The oil phase is immediately wound around the stirring blade 5 and sheared to be atomized. Thus, the high-concentration liquid softening agent composition that is a dispersed aqueous solution is continuously produced and discharged from the outlet (not shown) of the pipe 3.

The circumferential velocity A m / s of the stirring blade and the longitudinal linear velocity B m / s of the water phase and the oil phase passing through the stirring blade are determined so as to satisfy the condition of 10 ≦ A / B ≦ 300.
Specifically, the peripheral speed of the stirring blade, i.e., the peripheral speed of the blade tip, is sufficient to make the cationic surfactant finer in relation to the turbulence intensity generated by the rotation. m / s or more, preferably 7 m / s or more, more preferably 10 m / s or more. However, since the energy consumed to rotate the stirrer becomes large and the rotating shaft 5 is likely to be shaken, it is dangerous. Therefore, the peripheral speed is preferably 25 m / s or less. However, the peripheral speed may be 25 m / s or more depending on the capability of the line mixer 4. If the blade tip diameter is 25 mm, such a peripheral speed can be obtained by setting the rotational speed of the line mixer to preferably 6000 rpm or more, more preferably 8000 rpm or more, and even more preferably 10,000 rpm or more. By applying a shearing force under such conditions, emulsion particles having a particle size of 0.1 to 0.2 μm can be obtained, and dispersion stability is improved, which is preferable.

Further, the linear velocity B of the liquid passing through the stirring blade 5 is expressed by the formula:
(Water phase flow rate + Oil phase flow rate) / (Rotor outer diameter (wing outer diameter) / 2) ² × π
Is a value obtained by Here, the diameter of the tip of the rotating shaft 5 is set to zero for easy calculation. In the production method of the present invention, B is preferably in the range of 0.05 to 0.4 m / s, more preferably in the range of 0.1 to 0.25 m / s.
The conditions of rotation of the stirring blade with respect to the flow rate of liquid passing through the stirring blade are as follows. The peripheral speed of the stirring blade is Am / s, and the linear velocity of the liquid passing through the stirring blade is B m / s. It is a necessary condition that / B is 10 to 300. When A / B is within such a range, the emulsion particles can be made finer, so that the dispersion stability of the resulting liquid softener composition is improved, which is preferable. Moreover, since the quantity of the liquid softening agent composition obtained per unit time is large and high productivity can be achieved, it is preferable. Furthermore, it is preferable because a large load is not applied to the line mixer. Furthermore, it is preferable because it can suppress the occurrence of lumps in the oil phase. A / B is preferably 80 to 250, more preferably 90 to 220, and still more preferably 100 to 200.

  The temperature of the oil phase is preferably heated to a temperature higher than the transition temperature of the oil phase. In particular, it is preferable to heat to a temperature 5 to 15 ° C. higher than the transition temperature of the oil phase. The temperature of the aqueous phase can be raised to a temperature equal to or higher than the transition temperature of the oil phase, for example, 0-10 ° C. higher than the transition temperature of the oil phase, but as disclosed in JP-A-58-143830 The temperature may be lower than the transition temperature and near normal temperature. The temperature of the aqueous phase is preferably 5 to 10 ° C. lower than the transition temperature of the oil phase. Furthermore, you may cool after an emulsification process.

  The viscosity of the softener composition obtained by the above-described dispersing device varies depending on the type, blending amount, composition, etc. of the cationic surfactant, but the BL type rotational viscometer is used as the viscosity of the composition at 25 ° C. When used and expressed in terms of viscosity measured after rotating the rotor at 30 rpm for 20 seconds, it is usually desirable to be 1500 cP or less, particularly 500 cP or less. When the viscosity is higher than 1500 cP, the fluidity of the softener product is extremely poor, which causes problems such as clogging inside the general-purpose bottle of the softener product. In addition, it is desirable that the appearance of the softening agent composition is in a uniformly dispersed state from the beginning, and is maintained without being separated over time.

Next, with reference to FIG. 2, another example of an apparatus for carrying out the continuous production method according to the present invention of a highly concentrated liquid softening agent composition will be described. FIG. 2 is a schematic view of a dispersion apparatus for carrying out a continuous production method for a high-concentration liquid softening agent composition. Since this dispersing apparatus has the same structure as the dispersing apparatus 2 described with reference to FIG. 1 except that the pipe shape on the upstream side of the line mixer is different, the same reference numerals are given to the same components. Different components are indicated by adding “′” to the reference numerals.
The inner diameter of the pipe 3 ′ of the dispersing device 1 ′ in the upstream portion of the line mixer 2 tapers toward the line mixer 2 and rapidly increases immediately before the line mixer. In this way, the diameter of the blade tip of the stirring blade 5 of the line mixer 2 can be made smaller than the diameter of the portion of the pipe 3 ′ including the line mixer 2.
In the two dispersing devices described above, the supply port 7 is provided at a location that allows the supplied oil phase to reach the stirring blade 5 before forming a liquid crystal structure by contact with the aqueous phase. If the oil phase is mixed and dispersed by the stirring blade 5, it may be provided on the upstream side.
Further, in the two dispersing devices described above, the supply pipe 4 protrudes into the pipe 3, but it is sufficient if the oil phase is supplied into the pipe, and therefore does not need to protrude. Further, the supply pipe 4 protrudes in a direction perpendicular to the longitudinal direction of the pipe 3, but may protrude in an oblique direction. Further, the supply port 7 of the protruded supply pipe 4 may face in any direction, and the protruded supply pipe 4 may not be bent. Further, the supply pipe 4 may be tapered toward the supply port 7.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example at all.
[Examples 1-8, Comparative Examples 1-6]
As an emulsifier, Robomix (made by Tokushu Kika Kogyo) pipeline homomixer was used. The stirring blade is four inclined paddle blades. The diameter of the blade tip is 25 mm, the clearance between the stirring blade and the pipe is 0.5 mm, and the distance between the oil phase supply port and the stirring blade is 2 mm.
[Example 1]
Prepare a mixture of cationic surfactant in ethanol (15000 g, 85% solution), nonionic surfactant (15000 g) and fragrance (382 g) in a container in advance as Heated. Meanwhile, as a water phase, a mixture of water (55616 g), a water-soluble antibacterial agent (0.75 g) and a water-soluble dye (0.53 g) was prepared in a container and heated to 40 ° C. A water phase was continuously supplied to the emulsifier at 3.4 kg / min, and an oil phase was continuously supplied thereto at 1.0 kg / min (linear velocity 0.15 m / s). Further, the stirring blade was stirred at a rotational speed of 15000 rpm (circumferential speed 19.6 m / s) to carry out emulsification dispersion. An inorganic salt aqueous solution (33 g, 15% calcium chloride aqueous solution) was added to the obtained emulsion (967 g) and mixed by stirring to obtain a liquid softening agent composition of Example 1.
[Example 2]
In the same manner as in Example 1, the water phase is continuously supplied at 2.6 kg / min, but the oil phase is continuously supplied at 0.75 kg / min. An agent composition was obtained.

[Example 3]
Oil in which the amount of the cationic surfactant ethanol solution was changed to 26471 g while the water phase was changed to 44146 g in the same manner as in Example 1 and was continuously fed at 2.7 kg / min. The softener composition of Example 3 was obtained by changing the conditions to continuously supply the phase at 1.7 kg / min.
[Example 4]
In the same manner as in Example 1, an aqueous phase in which the amount of water was changed to 44146 g was continuously supplied at 2.0 kg / min, while the amount of the cationic surfactant ethanol solution was changed to 26471 g. The softener composition of Example 4 was obtained by changing the conditions to continuously supply the phase at 1.3 kg / min.
[Examples 5 to 8]
Example 5 is the method of Example 1, Example 6 is the method of Example 2, Example 7 is the method of Example 3, and Example 8 is performed by changing the cationic surfactant species. The procedure of Example 4 was followed.

[Comparative Example 1]
In the same manner as in Example 1, the rotation speed of the stirring blade is 1500 rpm (circumferential speed 2.0 m / s) and the water phase is continuously supplied at 8.7 kg / min. The softening agent composition of Comparative Example 1 was obtained by changing the conditions to supply continuously at kg / min.
[Comparative Example 2]
In the same manner as in Example 1, an aqueous phase in which the amount of water was changed to 26499 g was continuously fed at 1.1 kg / min, while the amount of the cationic surfactant ethanol solution was changed to 44118 g. The softener composition of Comparative Example 2 was obtained by changing the conditions to continuously supply the phase at 2.0 kg / min.
[Comparative Example 3]
It carried out like the comparative example 1 except having changed the cationic surfactant seed | species.
[Comparative Example 4]
It carried out similarly to the comparative example 2 except having changed the cationic surfactant seed | species.
[Evaluation methods]
The obtained softener composition is subjected to initial viscosity at 25 ° C., viscosity measurement after standing at 25 ° C. for 2 months, and appearance observation. The viscosity measurement method uses a BL type rotational viscometer, and measures the viscosity after rotating the rotor at 30 rpm for 20 seconds. Appearance was evaluated by ◎: Uniform dispersion, ○: Very slight classification (uneven density), Δ: Clearly classified, ×: Two-phase separation or gelation. The results are shown in Tables 1 and 2.

According to Table 1, in the case of the present invention (Examples 1 to 4), the weight of the mono long-chain type cationic surfactant represented by the general formula (1) is 27 with respect to the total weight of the cationic surfactant. %, 41%, the composition of the cationic surfactant in the softener composition is 17% and 30%, the peripheral speed of the stirring blade is Am / s, and the liquid passing through the stirring blade is mixed. By setting A / B to 130 and 180 when the linear velocity is set to B m / s, the initial viscosity is about 20 to 190 cP. Maintains dispersion. On the other hand, when A / B is lowered to 5 as in Comparative Example 1, although the initial viscosity is low, the speed of thickening is high and the appearance causes two-layer separation. Further, when the cationic surfactant concentration in the softening agent composition is increased to 50% by weight as in Comparative Example 2, the viscosity becomes very high in a gel state from the beginning.
According to Table 2, in the case of the present invention (Examples 5 to 8), a mono long chain type different from the mono long chain type cationic surfactant represented by the general formula (1) used in Table 1 Mix the cationic surfactant to 40% and 58% of the total weight of the cationic surfactant and 17% and 30% of the cationic surfactant in the softener composition. By setting the A / B to 130 and 180 when the peripheral speed of the blade is A m / s and the linear velocity of the liquid passing through the stirring blade is B m / s, the initial viscosity is about 20 to 190 cP. After 2 months, the viscosity is hardly increased, and the appearance is not changed and the uniform dispersion is maintained. On the other hand, when A / B is lowered to 5 as in Comparative Example 3, the initial viscosity is low, but the speed of thickening is high and the appearance causes two-layer separation. Further, when the concentration of the cationic surfactant in the softening agent composition is increased to 50% by weight as in Comparative Example 4, the viscosity becomes very high in a gel state from the beginning.

It is the schematic which shows an example of the dispersion apparatus which implements the continuous manufacturing method by this invention. It is the schematic which shows the other example of the dispersion apparatus which implements the continuous manufacturing method by this invention.

Explanation of symbols

1, 1 'Dispersing device 2 Line mixer 3, 3' Piping 4 Feeding pipe 5 Stirring blade 6 Rotating shaft 7 Feeding port

Claims (5)

A method for continuously producing a high-concentration liquid softener composition in which an oil phase is emulsified and dispersed in an aqueous phase,
A step of continuously supplying a water phase into a pipe extending in a longitudinal direction in which a line mixer provided with a stirring blade rotating in a circumferential direction is disposed;
A step of continuously supplying an oil phase containing a cationic surfactant mixture into the pipe supplying the aqueous phase from the upstream side of the stirring blade;
A step of mixing and emulsifying and dispersing the oil phase in the pipe with the stirring blade into the aqueous phase to obtain a softening agent composition,
In the step of supplying the oil phase, the oil phase is supplied so that the concentration of the cationic surfactant in the softener composition is 10 to 40% by weight,
The steps of mixing and emulsifying and dispersing the oil phase in the aqueous phase include: (I) the circumferential speed of the stirring blade is Am / s, and (II) the longitudinal linear velocity of the water phase and the oil phase passing through the stirring blade. When B m / s, the continuous production method of the high-concentration liquid softener composition is performed under the condition of 10 ≦ A / B ≦ 300.   The step of supplying the oil phase includes the step of supplying the oil phase from a location that allows the supplied oil phase to reach the stirring blade before forming a liquid crystal structure by contact with the aqueous phase. The continuous manufacturing method of the high concentration liquid softening agent composition of Claim 1 characterized by these.   The step of supplying the oil phase comprises 10 to 10 mono-long-chain type cationic surfactants containing one long-chain alkyl group or alkenyl group in the molecule with respect to the total weight of the cationic surfactant mixture. The method for continuously producing a high-concentration liquid softener composition according to claim 1 or 2, comprising a step of supplying a mono long-chain type cationic surfactant so as to have an amount of 80% by weight. .   The high concentration liquid softening agent composition manufactured by the manufacturing method of any one of Claims 1-3.   Viscosity is 1500 cP or less, The high concentration liquid softening agent composition of Claim 4 characterized by the above-mentioned.

Images