JP2019085668A - Method of producing liquid softening agent composition - Google Patents

Abstract

To provide a method of producing a liquid softening agent composition for blending a functional capsule substrate stably in a long-term storage by a small total surface active agent amount and without resort to a polymer.SOLUTION: A method of producing a liquid softening agent composition includes producing by the following Process 1-4. Process 1 is processes of respectively preparing an oil phase having a temperature of 50°C or higher obtained by mixing a cationic surface active agent, a nonionic surface active agent, and an oil-soluble constituent, and an aqueous phase having a temperature of 50°C or higher obtained by mixing water and a water-soluble constituent. Process 2 is a process of mixing the oil phase and a part of the aqueous phase prepared in the process 1 to form a liquid crystal where the mixing ratio of the oil phase and the aqueous phase (a mass ratio of the aqueous phase/the oil phase) is 0.8-1.2. Process 3 is a process of adding a residual aqueous phase to the liquid crystal prepared in the process 2 and mixing to form an emulsion where the aqueous phase is 50-85 mass% to a liquid softening agent composition total amount. Process 4 is a process of adding a functional capsule substrate to the emulsion prepared in the process 3 and mixing.SELECTED DRAWING: None

Description

  The present invention relates to a method of making a liquid softener composition.

In order to enhance the texture of textile after laundering, a textile treatment agent called textile finish or fabric softener is used.
As the fiber treatment agent, generally used is an oil-in-water emulsion which is prepared by mixing an oil phase containing a cationic surfactant which is a flexibility imparting component and an aqueous phase. In addition, it is known that the softener preparation has a great influence on the stability such as separation and thickening depending on the composition and the emulsification method, and a method related to the stabilization technology is disclosed.

  In recent years, it has become common for functional softeners to be compounded with a functional capsule base material in order to impart functions in addition to the softness effect. A composition formulated with a functional capsule base material is required to have a quality that does not cause floating or sedimentation of the functional capsule base material. In order to achieve dispersion stabilization of this functional capsule base material, a method of blending a dispersing agent with the functional capsule base material is disclosed (see, for example, Patent Document 1).

JP 2012-167389 A

  However, in the technology described in Patent Document 1, since the total amount of surfactant is large and the viscosity is set to be high, it is possible to suppress floating and sedimentation of the functional capsule base material, but surface activity There are problems such as the concern that the thickening agent or the water absorbability with time may deteriorate due to the large amount of the agent, and the usability.

On the other hand, a method of stabilizing the dispersion of the functional capsule base material by keeping the viscosity of the emulsion to be the base of the fiber treatment agent containing the functional capsule base material stable after preparation can be considered. On the other hand, there is a method of using a polymer in combination, but there is also a problem that the polymer is easily decomposed during high temperature storage, and there is a problem that thickening is caused by the storage temperature, even if the total surfactant amount is small As a method for stably blending the capsule base material for long-term storage, it is possible to float by using the viscosity adjusting agent such as a polymer and a dispersing agent newly and aligning the specific gravity of the softener and the specific gravity of the functional capsule base material. There is also a method of suppressing sedimentation. However, in this method, in order to control the specific gravity, it is necessary to adjust the inner base material of the functional capsule base material, which significantly extends the examination period and limits the functional component itself to be inner-clad. It is not practical because it

  The present invention has been made in view of the above circumstances, and has a production method for stably blending a functional capsule base material with a small amount of total surfactant and without relying on polymers for long-term storage. The task is to provide.

  In order to stably blend the functional capsule base material in long-term storage even if the total amount of surfactant is small, the oil phase and the water and the water solubility which mixed the cationic surfactant, the nonionic surfactant, the perfume and the like in the manufacturing method Stabilization was made possible by limiting the ratio of oil phase / water phase in the liquid crystal formation step of mixing the part of the aqueous layer consisting of the base material to generate liquid crystal, and adjusting the temperature at the time of blending.

The method for producing the liquid softener composition of the present invention is
The following (A) to (C) components:
(A) Cationic surfactant (B) Functional capsule base material (C) A method for producing a liquid softener composition containing a nonionic surfactant, wherein the total amount of surfactant is less than 15%,
The mixing ratio of oil phase to water phase (mass ratio of water phase / oil phase) in step 2 is 0.8 to 1.2 times, and the water phase in step 3 includes the following steps 1 to 4 It is characterized by being 50 to 85% by mass with respect to the total amount of the liquid softener composition.
Step 1: A step of respectively preparing an oil phase of 50 ° C. or more in which a cationic surfactant, a nonionic surfactant and an oil-soluble component are mixed, and an aqueous phase of 50 ° C. or more in which water and a water-soluble component are mixed.
Step 2: A step of mixing a part of the oil phase and the aqueous phase prepared in Step 1 to form a liquid crystal.
Step 3: A step of adding the remaining aqueous phase to the liquid crystal prepared in step 2 and mixing to form an emulsion.
Step 4: A step of adding a functional capsule base to the emulsion prepared in step 3 and mixing it.

  According to the method for producing a liquid softener composition containing the functional capsule base of the present invention, the functional capsule base can be stably blended in long-term storage even if the total amount of surfactant is small.

The method for producing the liquid softener composition of the present invention is
The following (A) to (C) components:
(A) Cationic surfactant (B) Functional capsule base material (C) A method for producing a liquid softener composition containing a nonionic surfactant, wherein the total amount of surfactant is less than 15%,
The mixing ratio of oil phase to water phase (mass ratio of water phase / oil phase) in step 2 is 0.8 to 1.2 times, and the water phase in step 3 includes the following steps 1 to 4 It is characterized by being 50 to 85% by mass with respect to the total amount of the liquid softener composition.
Step 1: A step of respectively preparing an oil phase of 50 ° C. or more in which a cationic surfactant, a nonionic surfactant and an oil-soluble component are mixed, and an aqueous phase of 50 ° C. or more in which water and a water-soluble component are mixed.
Step 2: A step of mixing a part of the oil phase and the aqueous phase prepared in Step 1 to form a liquid crystal.
Step 3: A step of adding the remaining aqueous phase to the liquid crystal prepared in step 2 and mixing to form an emulsion.
Step 4: A step of adding a functional capsule base to the emulsion prepared in step 3 and mixing it.

INDUSTRIAL APPLICABILITY The present invention can be suitably used as a method for producing a fiber finishing agent such as a fabric finish containing a functional capsule base, a fabric softener, a fabric washing agent and the like.

  The liquid softener composition produced by the production method of the present invention contains a cationic surfactant, a nonionic surfactant, water, and a functional capsule base.

[(A) component]
The component (A) contained in the liquid softener composition produced by the production method of the present invention is a hydrocarbon group having 10 to 26 carbon atoms which may be separated by an ester group and / or an amide group (hereinafter referred to as “the present In the specification, the compound is at least one compound selected from the group consisting of an amine compound having 1 to 3 of “long-chain hydrocarbon groups” in the molecule, a salt thereof and a quaternary compound thereof. The component (A) is blended to impart flexibility to fiber products and the like and to improve the dispersibility of the functional capsule base material (component (B)).
The carbon number of the long chain hydrocarbon group is 10 to 26, preferably 17 to 26, and more preferably 19 to 24. When the carbon number is 10 or more, the flexibility is good, and when it is 26 or less, the handling property is good. The long chain hydrocarbon group may be saturated or unsaturated. When the long chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is long chain carbonized. It is preferable that it is at the center of the hydrogen group or around the center.
The long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in its structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

The long chain hydrocarbon group may be separated by an ester group (-COO-) and / or an amido group (-NHCO-). That is, the long chain hydrocarbon group has at least one kind of dividing group selected from the group consisting of an ester group and an amide group in the carbon chain thereof, and the carbon chain is divided by the dividing group. May be Having the dividing group is preferable from the viewpoint of improving the biodegradability.
In the case of having such a split group, the number of split groups possessed by one long chain hydrocarbon group may be one or two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be separated at two or more places. When it has two or more dividing groups, each dividing group may be the same or different.
In addition, when it has a parting group in a carbon chain, the carbon atom which a parting group has shall count to carbon number of a long chain hydrocarbon group. The long-chain hydrocarbon group is usually an industrially used non-hydrogenated fatty acid derived from beef tallow, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated portion, a vegetable-derived non-hydrogenated vegetable, such as palm It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated portion.
The amine compound as the component (A) contained in the liquid softener composition produced by the production method of the present invention is preferably a secondary amine compound or a tertiary amine compound, and more preferably a tertiary amine compound.

  More specifically, examples of the amine compound as the component (A) contained in the liquid softener composition produced by the production method of the present invention include compounds represented by the following general formula (A1).

[Wherein, R ^{1 to} R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is 7 carbon atoms Or — (CH 2) n NHCOR ⁵ (where n is 2 or 3 and R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, or 1 to 4 carbon atoms. 4 alkyl group, -CH ₂ CH (Y) OH, or-(CH ₂ ) n NH ₂ , and at least one of R ^{1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms, -CH ₂ CH (Y) OCOR ⁴ or-(CH ₂ ) n NHCOR ⁵ ; ]
Wherein (A1), the number of carbon atoms of the hydrocarbon group having 10 to 26 carbon atoms in R ¹ to R ³ is preferably 17 to 26, 19 to 24 is more preferable. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably an alkyl group or an alkenyl group.
In —CH ₂ CH (Y) OCOR ⁴ , Y is a hydrogen atom or CH ₃ , with a hydrogen atom being particularly preferred. R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When a plurality of R4 is present in the compound represented by the formula (A1), the plurality of R ⁴ may be identical to each other or may be different from each other.
Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is It may be saturated fatty acid or unsaturated fatty acid, and may be linear fatty acid or branched fatty acid. Among them, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorbency to soft-treated clothing, the saturated / unsaturated ratio (mass ratio) of the fatty acid that is the basis of R ⁴ is preferably 90/10 to 0/100, and 80/20 to 0 / 100 is more preferable. When R ⁴ is an unsaturated fatty acid residue, a cis form and a trans form exist, but the mass ratio of the cis form / trans form is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.
Specifically, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value: 10 to 60), and the like as the fatty acid which is the basis of R ⁴ Hydrogenated beef tallow fatty acid (iodine value 10 to 60) and the like can be mentioned. Among them, fatty acids prepared to satisfy the following conditions (a) to (c) by combining predetermined amounts of two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid. It is preferred to use the composition.

(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100. (B) The cis / trans ratio (mass ratio) is 40/60 to 100/0, more preferably 70/30 to 90/10. (C) fatty acid having 18 carbon atoms is 60% by mass or more, preferably 80% by mass or more, fatty acid having 20 carbon atoms is less than 2% by mass, and fatty acid having 21 to 22 carbon atoms is less than 1% by mass .
In-(CH ₂ ) n NHCOR ⁵ , n is 2 or 3, and 3 is particularly preferred. R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably 15 to 19 carbon atoms. When R5 in the compound represented by formula (A1) there are a plurality, it may be R ⁵ of said plurality of mutually identical, may be different. As R ⁵ , those similar to R ⁴ can be mentioned.
At least one of R ^{1 to} R ³ is a long chain hydrocarbon group (hydrocarbon group having 10 to 26 carbon atoms, -CH ₂ CH (Y) OCOR ⁴ , or-(CH ₂ ) n NHCOR ⁵ ), It is preferred that two be long chain hydrocarbon groups. When one or two of R ^{1 to} R ³ are a long chain hydrocarbon group, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -CH ₂ CH (Y) OH, or - (CH ₂₎ a NNH _2, the alkyl group having 1 to 4 carbon _{atoms, -CH 2 CH (Y) OH} , or - (CH ₂₎ is preferably NNH _2. Among these, as a C1-C4 alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is especially preferable. Y in -CH ₂ CH (Y) OH is the same as Y in -CH ₂ CH (Y) OCOR ₄ . - n is the (CH ₂₎ nNH _2, - is the same as n in (CH ₂₎ nNHCOR _5.
Preferred examples of the compound represented by Formula (A1) include compounds represented by the following Formulas (A1-1) to (A1-8).

[Wherein, R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms. ]
As the hydrocarbon group for R ⁷ and R ^8, are the same as those of the hydrocarbon group having 10 to 26 carbon atoms in the R ¹ to R ^3.
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ^9, R ^10, those similar to the hydrocarbon group of 7 to 21 carbon atoms in the R ^4. When R ⁹ is more present in the formula, R ⁹ of the plurality of may be the same as each other, it may be different.
Component (A) in the softener composition produced by the production method of the present invention may be a salt of an amine compound.

The salt of the amine compound is obtained by neutralizing the amine compound with an acid. The acid used to neutralize the amine compound may be either an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid and methyl sulfuric acid. The neutralization of the amine compound can be carried out by known methods.
The quaternary compound of the amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent used for quaternization of the amine compound include alkyl halides such as methyl chloride and dialkyl sulfuric acids such as dimethyl sulfuric acid. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced to the nitrogen atom of the amine compound to form a salt of quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion. . The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The quaternization of the amine compound can be carried out by known methods.

As the component (A) contained in the softener composition produced by the production method of the present invention, at least one selected from the group consisting of a compound represented by the above general formula (A1), a salt thereof and a quaternary compound thereof One kind is preferable, and at least one kind selected from the group consisting of the general formulas (A1-1) to (A1-8), a salt thereof and a quaternary compound thereof is more preferable, and (A1-4) to (A1-6) And at least one selected from the group consisting of salts thereof and quaternary compounds thereof.
A commercially available thing may be used for the compound represented by Formula (A1), its salt, and its quaternary compound, and you may use what was manufactured by the well-known method.
For example, compounds represented by general formula (A1-2) (hereinafter “compound (A1-2)”) and compounds represented by general formula (A1-3) (hereinafter “compound (A1-3)”) are The fatty acid composition can be synthesized by condensation reaction of methyldiethanolamine with a fatty acid methyl ester composition in which the fatty acid in the fatty acid composition or the fatty acid composition is replaced with a methyl ester of the fatty acid. At that time, from the viewpoint of improving the flexibility, synthesis is performed such that the abundance ratio represented by “compound (A1-2) / compound (A1-3)” is 99/1 to 50/50 in mass ratio It is preferable to do.
Furthermore, in the case of using the quaternary compound, it is more preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by “quaternized compound of compound (A1-2) / quaternized compound (A1-3)” is 99/1 to 50/50 in mass ratio It is preferable to synthesize so that

Compound Represented by General Formula (A1-4) (hereinafter “Compound (A1-4)”) Compound Represented by General Formula (A1-5) (hereinafter “Compound (A1-5)”) General Formula The compound represented by (A1-6) (hereinafter, “compound (A1-6)”) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition with triethanolamine. At that time, the content ratio of the individual components to the total mass of the compounds (A1-4), (A1-5) and (A1-6) is 1 to 60 mass% of the compound (A1-4) from the viewpoint of flexibility. %, The compound (A1-5) is preferably 5 to 98% by mass, the compound (A1-6) is preferably 0.1 to 40% by mass, the compound (A1-4) is 30 to 60% by mass, the compound It is more preferable that A1-5) is 10-55 mass%, and a compound (A1-6) is 5-35 mass%.
Moreover, when using the quaternization thing, it is more preferable to use dimethyl sulfate as a quaternizing agent in that the quaternization reaction is sufficiently advanced. The abundance ratio of each of the quaternary compounds (A1-4), (A1-5), and (A1-6) is 1 to 4 of the quaternary compound (A1-4) in terms of mass ratio from the viewpoint of flexibility. The compound (A1-4) is preferably 60% by mass, 5 to 98% by mass of the quaternary compound of the compound (A1-5), and 0.1 to 40% by mass of the quaternary compound of the compound (A1-6). 30 to 60% by mass of the quaternized compound of 10), 10 to 55% by mass of the quaternary compound of the compound (A1-5), and 5 to 35% by mass of the quaternary compound of the compound (A1-6) preferable. When the compounds (A1-4), (A1-5) and (A1-6) are quaternized, an esteramine which is not quaternized generally remains after the quaternization reaction. In that case, it is preferable that the ratio of "quaternary / non-quaternized ester amine" is in the range of the mass ratio of 70/30 to 99/1.

  The compound represented by the general formula (A1-7) (hereinafter “compound (A1-7)”) and the compound represented by the general formula (A1-8) (hereinafter “compound (A1-8)”) From fatty acid compositions and adducts of N-methyl ethanolamine and acrylonitrile, J.F. Org. Chem. , 26, 3409 (1960), and can be synthesized by the condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by the known method described in U.S. Pat. In that case, it is preferable to synthesize | combine so that the abundance ratio represented by "compound (A1-7) / compound (A1-8)" may be 99/1-50/50 by mass ratio. When using the quaternized compound, it is preferable to use methyl chloride as a quaternizing agent, and it is represented by "quaternized compound of compound (A1-7) / quaternized compound (A1-8)" It is preferable to synthesize | combine so that an abundance ratio will be 99/1-50/50 by mass ratio.

  In the softener composition produced by the production method of the present invention, the blending amount of the component (A) is preferably 3% to 15% with respect to the total mass of the softener composition from the viewpoint of flexibility and water absorption. %, More preferably 7% to less than 15% by mass, and further preferably 9 to 12% by mass. If the compounding amount of the component (A) is 3% by mass or more, better flexibility imparting effect and dispersion stability of the functional capsule base material can be obtained. Water absorption is more favorable in the compounding quantity of (A) component being less than 15 mass%.

[(B) component]
The functional capsule base of the component (B) contained in the softener composition produced by the production method of the present invention imparts a function to the textile treated with the liquid softener composition. It is blended in order to make the flavoring of the fiber product better by making the inner cover base material into a perfume, to improve the persistence of the flavor, or to provide a flavoring effect by friction when using the fiber product.

The functional capsule base is composed of a core substance and a wall substance covering the core substance.
The core material comprises a perfume composition.
As the flavor and fragrance composition, those used in the liquid softener composition field can be used without particular limitation, and can be appropriately selected according to the purpose. For example, essential oils and absolutes generally used for softeners for clothes, detergents for clothes, etc., hydrocarbons, alcohols, aldehydes, ketones, ethers, acetals, ketals, nitriles, etc. And synthetic perfume ingredients of

Examples of preferable perfume ingredients to be incorporated into the perfume composition are described in JP-A-2010-520928, and for example, Agrumex, Aldron, Ambrettolide, Ambroxan, benzyl cinnamate, benzyl salicylate, Boisambrene, cedrol, acetic acid Cedryl, Celestolide / Crysolide, Cetalox, Citronellol etoxalate, Fixal, Fixolide, Galaxolide, Guaiacwood Acetate, cis-3-hexenyl salicylate, hexyl cinnamic aldehyde, hexyl salicylate, IsoE Super, linalyl benzoate, linalyl cinnamate, phenyl Linalyl acetate, Javanol, methyl cedryl ketone, Moskene, Musk Ketone, Musk Tibetine, Musk Xylol, Myraldyl Acetate, nerolidyl acetate, Novalide, Okoumal, paracresyl caprylate, paracresyl phenylacetate, Phantoliid, phenylethyl cinnamate, phenyl salicylate Ethyl, Rose Crystals Rosone, Sandela, tetradeconitrile, Thibetolide, Traseolide, Trimofix O, 2-methylpyrazine, acetaldehyde phenylethylpropyl acetal, acetophenone, alcohol C6 (in the following, notation Cn represents n carbon atoms and one hydroxyl function Alcohol C8, aldehyde C6 (in the following, notation Cn includes all isomers having n carbon atoms and one aldehyde function), aldehyde C7, aldehyde C8, aldehyde C9, nonenyl aldehyde (nonylic aldehyde), allyl amyl glycolate, allyl caproate, amyl butyrate, aldehyde anisic, benzaldehyde, benzyl acetate, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl butyrate, benzyl formate, iso Benzyl malate, benzyl methyl ether, benzyl propionate, Bergamyl acetate, butyl acetate, camphor, 3-methyl-5-propyl-2-cyclohexenone, cinnamaldehyde, cis-3-hexenol, cis-3-hexenyl acetate, formic acid Cis-3-hexenyl, cis-3-hexenyl isobutyrate, cis-3-hexenyl propionate, cis-3-hexenyl tiglate, citronellal, citronellol, citronellyl nitrile, 2-hydroxy-3-methyl-2-cyclopentene 1-one, cumin aldehyde, cyclal C, acetic acid (cyclohexyloxy) -2-propenyl ester, damacenone, alpha-damascusone, beta-damascone, decahydrobeta-naphthyl formate, diethyl malonate, dihydrojasmon, dihydrorinaro Le, dihydromyrcenol, dihydroterpineol, dimethyl anthranilate, dimethyl benzyl carbinol, dimethyl benzyl carbinyl acetate, dimethyl octenone, dimethol (Dimetol), dimylacetol, estragol, ethyl acetate, ethyl acetoacetate, ethyl benzoate, Ethyl heptanoate, ethyl linalool, ethyl salicylate, ethyl 2-ethyl butyrate, eucalyptol, eugenol, phenethyl acetate, fenquil alcohol, 4-phenyl-2,4,6-trimethyl 1,3-dioxane, methyl 2-octynoate, 4-isopropylcyclohexanol, 2-sec
-Butylcyclohexanone, stilallyl acetate, geranyl nitrile, hexyl acetate, alpha-ionone, isoamyl acetate, isobutyl acetate, iso-cyclo citral, dihydroisojasmone, iso-menton, iso-pentylate, iso-pregol, cisjasmon, levotactic Carboxyl, phenylacetaldehyde glyceryl acetal, carbinic acid 3-hexenyl methyl ether, 1-methyl-cyclohexa-1,3-diene, linalool, linalool oxide, pentanoic acid 2-ethyl ethyl ester, 2,6-dimethyl-5 -Heptenal, menthol, menthone, methylacetophenone, methyl amyl ketone, methyl benzoate, alpha-methyl cinnamic aldehyde, methyl heptenone, methyl hexyl ketone, methyl parach Resole, methylphenyl acetate, methyl salicylate, neral, nerol, 4-tert-pentyl-cyclohexanone, para-cresol, para-cresyl acetate, para-t-butylcyclohexanone, para-toluylaldehyde, phenylacetaldehyde, phenylethyl acetate, phenyl Ethyl alcohol, phenylethyl butyrate, phenylethyl formate, phenylethyl isobutyrate, phenylethyl propionate, phenylpropyl acetate, phenylpropylaldehyde, tetrahydro-2,4-dimethyl-4-pentyl-furan, 4-methyl-2- ( 2-Methyl-1-propenyl) tetrahydropyran, 5-methyl-3-heptanone oxime, stilallyl propionate, styrene, 4-methylphenylacetaldehyde, terpineol, Rupinoren, tetrahydro - linalool, tetrahydro - myrcenol, trans-2-hexenal, acetic Berujiru and Viridine the like.
In the flavor composition, one flavor component may be blended, or two or more flavor components may be blended.

As the wall material, those generally used as a perfume encapsulating material in the liquid softener composition field can be used without particular limitation. For example, the wall substance is composed of a polymer substance, and specifically, natural type polymers such as gelatin and agar, oil-based film forming substances such as oil and fat, wax, polyacrylic acid type, polyvinyl type, polymethacrylic acid type, Examples thereof include synthetic high molecular substances such as melamine type and urethane type, and one of them may be used alone or two or more may be used in combination.
The wall material is preferably an aminoplast polymer consisting of a melamine-formaldehyde resin or a urea-formaldehyde resin, a polyacrylic acid-based polymer, or a polymethacrylic acid-based polymer from the viewpoint of odorant properties when the encapsulated perfume is broken . Particularly preferred are aminoplast polymers as described in JP 2010-520928. Specifically, it is preferable to be a terpolymer consisting of an alkylene and alkyleneoxy moiety having a polyamine-derived moiety / aromatic polyphenol-derived moiety / methylene unit, dimethoxymethylene and dimethoxymethylene.
Component (B) is readily available in the market or can be synthesized by known methods.
As the component (B), one type of encapsulated fragrance may be used alone, or two or more types may be used as a mixture.
The compounding amount of the component (B) (the compounding amount as the amount of the perfume in the component (B)) is not particularly limited as long as the compounding purpose can be achieved, but the fragrance relative to the total mass of the liquid softener composition Preferably it is 0.01-3 mass%, More preferably, it is 0.05-2 mass%, More preferably, it is 0.1-1 mass%. If the blending amount of the component (B) is 0.01% by mass or more, the aroma is strong, and a more satisfactory aroma persistence can be obtained. The deterioration of coating peeling is suppressed more as the compounding quantity of (B) component is 3 mass% or less.

[(C) ingredient]
The nonionic surfactant of the component (C) contained in the liquid softener composition produced by the production method of the present invention is a liquid softener composition produced by the production method of the present invention is an emulsion. It can be blended mainly for the purpose of improving the emulsion dispersion stability of the oil-soluble component in the emulsion. When a nonionic surfactant is blended, it is easy to ensure freeze recovery stability sufficient for commercial value.
As the nonionic surfactant, for example, those derived from polyhydric alcohol, higher alcohol, higher amine or higher fatty acid can be used. More specifically, a glycerin fatty acid ester or pentaerythritol in which a fatty acid having 10 to 22 carbon atoms is ester bonded to glycerin or pentaerythritol; an alkyl group or alkenyl group having a carbon number of 10 to 22; Polyoxyethylene alkyl ether having 10 to 100 moles; polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester; polyoxyethylene alkylamine having an average added mole number of ethylene oxide of 10 to 100 moles; carbon number And alkyl polyglucosides having 8 to 18 alkyl groups or alkenyl groups; hydrogenated castor oil having an average addition mole number of ethylene oxide of 10 to 100 moles. Among them, polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and having an average added mole number of ethylene oxide of 20 to 80 moles is preferable.
One type of nonionic surfactant may be used alone, or two or more types may be used as a mixture.
The blending amount of the nonionic surfactant is not particularly limited as long as the blending purpose can be achieved, but it is preferably 0.01 to 10% by mass, more preferably 0.1 based on the total mass of the liquid softener composition. The amount is 8 to 8% by mass, more preferably 0.5 to 5% by mass.
The nonionic surfactant may be blended in the oil phase or in the water phase. Moreover, it is also possible to divide | segment and mix | blend nonionic surfactant. By blending 10 to 50% by mass of the total amount of nonionic surfactants in step 4, the component (B) can be dispersed more stably.

[Optional ingredient]
In the liquid softener composition produced by the production method of the present invention, optional components other than the essential components of the above (A) to (C) are blended as needed within the range that does not impair the effects of the present invention. May be

[(D) component]
The component (D) contained in the liquid softener composition produced by the production method of the present invention is a water-soluble structurant. Here, "water-soluble" means that 1 g of the target structuring agent is added to 1000 g of water at 25 ° C., stirred, and then allowed to stand at 25 ° C. for 24 hours. Can be a solution that can not
Specifically, high molecular weight dextrin (Sanwa Starch Co., Ltd. trade name: Sandeck # 30), cyclic structure-containing branched glucan (described in JP 2012-120471), highly branched cyclic dextrin (Glyco Nutrition Foods Co., Ltd.) Trade name: cluster dextrin), Lupasol SK (manufactured by BASF), Lupasol PS (manufactured by BASF), Rheovis FRC (manufactured by BASF), Rheovis CDE (manufactured by BASF), etc. may be used.
In the liquid softener composition produced by the production method of the present invention, the dispersibility of the functional capsule base material in the softener composition is improved by blending the component (D) by 0.05% or more. Can.
Other optional components may include those generally formulated in liquid softener compositions. Specific examples thereof include water, perfumes, water-soluble salts, dyes, water-soluble solvents, preservatives, ultraviolet light absorbers, antibacterial agents, deodorants, skin care ingredients and the like.
Hereinafter, some optional components will be described in detail.

[water]
The liquid softener composition produced by the production method of the present invention is preferably an aqueous composition comprising water.
As water, any of tap water, purified water, pure water, distilled water, ion-exchanged water and the like can be used. Among them, ion exchange water is preferred.
The compounding amount of water is not particularly limited, and can be appropriately compounded to achieve a desired component composition.

[Perfuming]
In the liquid softener composition produced by the production method of the present invention, a perfume other than the component (B) can be blended as an optional component.
As a fragrance, a general-purpose fragrance can be used in the art and is not particularly limited, but a list of usable fragrance raw materials can be found in various documents, for example, “Perfume and Flavor Chemicals”, Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic Perfume Chemistry and Commodity Knowledge", Motoichi Intoh, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994) and "Encyclopedia of Aroma", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flowers oils and Floral Compounds In Perfumery" , Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc.
As the flavor, one flavor may be used alone, or two or more flavors may be used as a mixture.
The blending amount of the perfume is not particularly limited as long as the blending purpose can be achieved, but it is preferably 0.1 to 3% by mass, more preferably 0. 3% by mass with respect to the total mass of the liquid softener composition. It is 5 to 2% by mass, more preferably 0.5 to 1.5% by mass.

[Water soluble salts]
In order to control the viscosity of the liquid softener composition produced by the production method of the present invention, inorganic or organic water-soluble salts can be used. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, sodium citrate and the like can be used, among which calcium chloride, magnesium chloride and sodium citrate are preferable. These water-soluble salts can be compounded in an amount that does not impair the dispersibility of the functional capsule base material, and the compounding amount thereof is, for example, 0 to 0.5% by mass based on the total mass of the liquid softener composition Preferably, it is 0-0.3 mass%, More preferably, it is 0-0.1 mass%. The water-soluble salts may be blended at any process of liquid softener composition production.
The viscosity of the liquid softener composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

[Method for producing functional capsule base-containing fiber treatment agent]
The manufacturing method of the liquid softening agent manufactured by the manufacturing method of this invention is demonstrated.
The manufacturing method of this embodiment is manufactured through the following four steps.
Step 1: A step of respectively preparing an oil phase of 50 ° C. or more in which a cationic surfactant, a nonionic surfactant and an oil-soluble component are mixed, and an aqueous phase of 50 ° C. or more in which water and a water-soluble component are mixed.
Step 2: A step of mixing part of the oil phase and the aqueous phase prepared in step 1 to form a liquid crystal, wherein the mixing ratio of oil phase to water phase (mass ratio of water phase / oil phase) is 0.8 A step which is ~ 1.2 times.
Step 3: A step of adding the remaining aqueous phase to the liquid crystal prepared in step 2 and mixing to form an emulsion, wherein the aqueous phase is 50 to 85% by mass based on the total amount of the liquid softener composition .
Step 4: A step of adding and mixing a functional capsule base to the emulsion prepared in Step 3.

<Step 1>
Step 1 is a step of preparing an oil phase of 50 ° C. or more in which a cationic surfactant, a nonionic surfactant and an oil-soluble component are mixed, and an aqueous phase of 50 ° C. or more in which water and a water-soluble component are mixed. is there.

[Oil phase creation]
The oil phase is a step of melting the cationic surfactant by heating in advance to 50 ° C. or higher and mixing it with the similarly melted nonionic surfactant to form an oil phase.
In the oil phase, an oil-soluble component may be blended in addition to the cationic surfactant and the nonionic surfactant. Examples of the oil-soluble component include perfumes, silicone compounds and the like.
In addition, water and water-soluble components to be brought in from raw materials can also be converted as an oil phase.

[Water phase creation]
In the aqueous phase preparation step, an aqueous phase mainly composed of water is prepared.
The aqueous phase is a process in which the main component is water, and if necessary, a water-soluble component (preservative, pH adjuster, dispersant, etc.) is added and the mixture is heated to 50 ° C. or higher. The aqueous phase may be 100% by mass (entirely water), and a nonionic surfactant may be blended. The content of the nonionic surfactant in the aqueous phase is not particularly limited, and is preferably 5% by mass or less, more preferably 0.1 to 4% by mass, and still more preferably 0.1 to 3% by mass. If the blending amount of the nonionic surfactant is equal to or less than the preferable upper limit value, the dispersion stability of the emulsion obtained in Step 2 becomes better. If it is more than a lower limit value, it is effective as an emulsification assistant of the oil-soluble ingredient mixed with an oil phase.
Moreover, the oil-soluble component brought in from a raw material can also be converted as an aqueous phase.

<Step 2>
Step 2 is a step of mixing part of the oil phase and the aqueous phase prepared in step 1 to form a liquid crystal, and the mixing ratio of oil phase to water phase (mass ratio of water phase / oil phase) is 0. It is a step which is 8 to 1.2 times.
In step 2, the oil phase obtained in step 1 and a part of the water phase (liquid crystal forming water) are mixed to form liquid crystal.
In the present invention, the liquid crystal-forming water means the amount of the aqueous phase used when preparing the liquid crystal, and indicates the mass ratio of a part of the amount of the aqueous phase to the amount of the oil phase. From this mass ratio, the blending amount of a part of the aqueous phase and the blending amount of the remaining part of the aqueous phase are determined.
In the present specification, the aqueous phase to be mixed in step 2 (liquid crystal-forming water) is also referred to as "first aqueous phase".
In Step 2, the mass ratio represented by the first aqueous phase (liquid crystal-forming water) / oil phase is within the range of 0.8 to 1.2 because it is easy to form fine emulsion particles. Preferably, it is more preferably in the range of 0.9 to 1.15, and still more preferably in the range of 0.9 to 1.05. When the liquid crystal formation water ratio is less than the lower limit value, the particle size of the final emulsified product becomes uneven, and the stability is deteriorated. Moreover, when it is more than an upper limit, particle size will become small and there exists a possibility that a functional capsule base material may float by reducing viscosity.
The temperature condition in the emulsification step of step 2 is 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 58 ° C. or higher. If the temperature is 50 ° C. or less, the viscosity of the final emulsion may be low, and the functional capsule base may be suspended.

<Step 3>
Step 3 is a step of adding the remaining aqueous phase to the liquid crystal prepared in step 2 and mixing to form an emulsion, and the aqueous phase is 50 to 85% by mass based on the total amount of the liquid softener composition. It is a process.
In the present specification, the aqueous phase added and mixed in step 3 is also referred to as a "second aqueous phase".
The temperature of the aqueous phase in this step is 50 ° C. or more, preferably 55 ° C. or more, more preferably 58 ° C. or more. If the temperature is 50 ° C. or less, the viscosity of the final emulsion may be low, and the functional capsule base may be suspended.

<Step 4>
Step 4 is a step of adding a functional capsule base to the emulsion prepared in step 3 and mixing (capsule mixing step).
In the capsule particle mixing step, the functional capsule base is finally obtained by mixing the emulsion prepared in step 3 and the functional capsule base containing the core substance in the water-insoluble polymer compound. A liquid softener composition is produced.
In step 4, various substrates can be blended in addition to the functional capsule substrate. For example, nonionic surfactants, perfumes, water-soluble salts, dyes, water-soluble solvents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, skin care ingredients and the like can be mentioned.
The manufacturing steps of these steps 2 to 4 may be batch type or continuous type.

[Viscosity of liquid softener composition]
The viscosity of the liquid softener composition produced by the production method of the present invention is not particularly limited as long as the usability thereof is not impaired, but the viscosity at 25 ° C. is preferably less than 800 mPa · s. The viscosity at 25 ° C. of the liquid softener composition immediately after production is more preferably less than 500 mPa · s, still more preferably less than 300 mPa · s, in consideration of viscosity increase due to storage age. When it is in such a range, usability such as handling property at the time of charging to a washing machine is good. The viscosity can be measured using a BL type rotary viscometer manufactured by Tokyo Keiki Co., Ltd.

[TI value]
In order to suppress the floating of the functional capsule base material, it is necessary that the viscosity at the time of standing still satisfies a high level. Therefore, the functional capsule base material floating is predicted by measuring the thixotropic index value (TI value).
The TI value can be determined according to the following equation.

TI value = 6 rpm viscosity of liquid softener composition / 60 rpm viscosity of liquid softener composition The above-mentioned TI value becomes TI value = 1 in the case of a Newtonian fluid such as water having no change in viscosity even if the shear rate changes. . When the TI value is larger than 1, it indicates that the smaller the shear force, the higher the viscosity than the case where the shear force is large, and a liquid having thixotropic properties.
In the liquid softener composition produced by the production method of the present invention, the range of the TI value showing thixotropy is preferably 2.0 or more, more preferably 2.0 to less than 5.0, still more preferably 2. 5 to 4.0. When the TI value is 2.0 or more, excellent thixotropy is obtained, and the dispersion stability of the component (B) is further improved. On the other hand, if it exceeds 5.0, thixotropy will be enhanced and the dispersion stability of the component (B) will be good, but problems such as difficulty in taking out the composition to the cap when measuring the liquid softener composition may occur. .

[PH of liquid softener composition]
The pH of the liquid softener composition produced by the production method of the present invention is not particularly limited, but from the viewpoint of suppressing hydrolysis of the ester group contained in the molecule of the component (A) accompanied with storage days, It is preferable to adjust the pH in the range of 1 to 6 and more preferably 2 to 4.
For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytic acid, ethylene diamine tetraacetic acid, Short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates, etc. Modifiers can be used.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the examples, the component blending amounts all indicate% by mass (in terms of pure parts except when designated).

[(A) component]
A-1: Cationic surfactant (compound described in Example 4 of JP-A No. 2003-12471) A-1 is a compound represented by General Formulas (A1-4), (A1-5) and (A1-6) (Wherein R ⁹ is an alkyl group having 15 to 17 carbon atoms and an alkenyl group in each formula) are quaternized with dimethyl sulfate.
A-2: manufactured by Tonan Gosei Co., Ltd., trade name: HITEX RO16E
A-3: made by Stepan, trade name: Stepantex SE-88
[(B) component]
B-1: GREEN BREEZE CAPS (manufactured by GIVAUDAN)
B-2: RAINBOW CAPS (manufactured by GIVAUDAN)
Both of B-1 and B-2 are encapsulated perfumes having a perfume composition as a core substance and a melamine-formaldehyde resin as a capsule wall.

[(C) ingredient]
C-1: 60 moles of polyoxyethylene isotridecyl ether EO (a product obtained by adding ethylene oxide to Lutensol TO3 manufactured by BASF Corp. (60 moles of EO indicates that the average addition mole number of ethylene oxide is 60), lion Product name: TA600-75)
[(D) component]
D-1: Highly branched cyclic dextrin (manufactured by Glyco Nutrition Foods Co., Ltd. trade name: cluster dextrin, weight average molecular weight: 400,000)
D-2: Cationic (meth) acrylic polymer (manufactured by BASF, trade name: Rheovis FRC)
[Common component]
The common components shown in Table 1 were used as common components of the liquid softener produced by the production method of the present invention.
Table 1: Common components · E-1:

The flavor components are shown in Table 2.

Table 2: Perfume Composition

[Liquid Softener Composition: Examples 1 to 11 and 13 to 14 Preparation Methods of Comparative Examples 1 to 4]
Using a glass container with an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), the blending amounts of each component are as described in Tables 3 to 5, and a liquid softener composition is prepared by the following procedure. did.

Step 1: The component (A), the component (C) and the flavor are mixed and stirred at the temperature specified in the example to obtain an oil phase mixture.
BIT was added to ion exchange water for balance and heated to the temperature designated in each example (water phase).

Step 2: While the temperature-controlled oil phase mixture was placed in a glass container and stirred, the divided aqueous phase was added and stirred for 3 minutes at a rotational speed of 1,500 rpm to obtain a liquid crystal. In addition, the amount of the first aqueous phase is the ratio specified in each example with respect to the oil phase (described as “the amount of the first aqueous phase (step 2)” in Tables 3 to 5).

Step 3: The liquid crystal prepared in Step 2 was added at a rotational speed of 1,500 rpm for 2 minutes after the second addition of the aqueous phase mixture. The second aqueous phase mixture is the remaining total amount of the aqueous phase prepared in step 1 (described as “second aqueous phase amount (step 3)” in Tables 3 to 5).

Step 4: Calcium chloride, component (B) and component (D) were added to the emulsified dispersion prepared in step 3. In addition, if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 2.5, and the desired liquid softener composition 1000 g of the product (Examples 1 to 11, 13, 14 and Comparative Examples 1 to 3) were obtained.

[Liquid Softener Composition: Preparation Method of Example 12]
Based on the description of Table 4, the liquid softener composition was prepared according to the following procedure using a glass container with an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation).

Step 1: 70% of the components (A) and (C), and the perfume were mixed and stirred at the temperature specified in each example to obtain an oil phase mixture.
BIT was added to ion exchange water for balance and heated to the temperature specified in the example (aqueous phase).

Step 2: While the temperature-controlled oil phase mixture was placed in a glass container and stirred, the divided aqueous phase was added and stirred for 3 minutes at a rotational speed of 1,500 rpm to obtain a liquid crystal. In addition, the amount of the first aqueous phase is the ratio specified in each example with respect to the oil phase (described as "the first aqueous phase amount (step 2)" in Table 4).

Step 3: The liquid crystal prepared in Step 2 was added at a rotational speed of 1,500 rpm for 2 minutes after the second addition of the aqueous phase mixture. The second aqueous phase mixture is the total amount of the remaining aqueous phase (described as “second aqueous phase amount (step 3)” in Table 4).

Step 4: Calcium chloride, (B) component, and the remaining (C) component were added to the emulsified dispersion prepared in step 3. In addition, if necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 2.5, and the desired liquid softener composition 1000 g of the product (Example 12) was obtained.

[Dispersibility evaluation of (B) component]
80 mL of the liquid softener composition prepared as described above is placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed up, and the dispersibility of the component (B) is evaluated according to the three-stage evaluation method shown below I made an evaluation. The evaluation sample was stored for 3 months under the condition of 25 ° C. for the sealed sample as well, and was visually evaluated by five expert panelists based on the following criteria. In terms of commercial value, ○ or more is preferable. The results are shown in Tables 3 to 5 below.
<Evaluation criteria>
○: It is considered equivalent to the sample before storage.
Δ: Slight suspension is observed.
X: Clearly floating is observed.

[Separation evaluation of liquid softener composition]
80 mL of the liquid softener composition prepared as described above was placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed up, and separation evaluation was performed according to the following three-stage evaluation method. The evaluation sample similarly stored the tightly sealed sample under two conditions of 25 ° C. and 5 ° C. for 3 months, respectively, and was visually evaluated by five expert panelists based on the following criteria. In terms of commercial value, Δ or more is preferable. The results are shown in Tables 3 to 5 below.
<Evaluation criteria>
○: It is considered equivalent to the sample before storage.
Δ: Slight separation is observed.
X: Clearly recognized separation.

Table 3

Table 4

Table 5

Claims (1)

The following (A) to (C) components:
(A) Cationic surfactant (B) Functional capsule base material (C) A method for producing a liquid softener composition containing a nonionic surfactant, wherein the total amount of surfactant is less than 15%,
Including the following steps 1 to 4,
The mixing ratio of oil phase to water phase (mass ratio of water phase / oil phase) in step 2 is 0.8 to 1.2 times,
50 to 85% by mass of the aqueous phase in step 3 with respect to the total amount of the softener composition,
A method of producing a liquid softener composition, characterized in that
Step 1: A step of respectively preparing an oil phase of 50 ° C. or more in which a cationic surfactant, a nonionic surfactant and an oil-soluble component are mixed, and an aqueous phase of 50 ° C. or more in which water and a water-soluble component are mixed.
Step 2: A step of mixing a part of the oil phase and the aqueous phase prepared in Step 1 to form a liquid crystal.
Step 3: A step of adding the remaining aqueous phase to the liquid crystal prepared in step 2 and mixing to form an emulsion.
Step 4: A step of adding a functional capsule base to the emulsion prepared in step 3 and mixing it.