JP2016216864A - Manufacturing method of liquid softener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a liquid softener composition capable of stably manufacturing the liquid softener composition containing ester type quaternary ammonium salt at high concentration.SOLUTION: There is provided a manufacturing method of a liquid softener composition containing (A) a specific quaternary ammonium salt of 15 mass% to 30 mass% and water, where an emulsification process for forming an emulsion composition is conducted under a condition in presence of a specific cationic polymer with larger water amount than the (A) content.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a liquid softener composition.

  The liquid softening agent is usually filled and sold in a plastic container having a capacity of about 600 mL to 2.5 L. In recent years, due to an increase in environmental awareness, attempts have been made to reduce the amount of plastic material used as the material of the container by further reducing the capacity of the container. In addition, with the aging of society, it is desired to reduce the mass of products so that consumers purchased at stores can easily carry the products. However, simply reducing the internal volume per container reduces the number of times it can be used. In order to solve the problem, it is desired to increase the concentration of the active ingredients in the contents and reduce the amount used per wash.

  On the other hand, it is also known to incorporate a cationic polymer for the purpose of further increasing flexibility.

Patent Documents 1 and 2 describe a method for producing a liquid softening agent composition in which a cationic polymer and a quaternary ammonium salt are mixed in a specific procedure.
Patent Document 3 includes (a) a specific polymer compound, (b) one or more selected from a specific quaternary ammonium salt and an amine compound, and (c) a solvent having water and ClogP of 2 or less. A liquid softener composition containing at least one kind of compound each having a specific range and a pH of 2 to 5 at 20 ° C. is described.

JP 2012-172283 A JP2011-236518A JP 2008-144316 A

As a soft base, a quaternary ammonium salt having a hydrocarbon group separated by an ester group, that is, a group in which a hydrocarbon group is linked by an ester group (hereinafter sometimes referred to as an ester-type quaternary ammonium salt). ), When the content of the ester-type quaternary ammonium salt is high, the mixture may thicken during production, and it may be difficult to produce stably. Specifically, at the time of preparing the liquid softening agent, in the step of emulsifying the ester type quaternary ammonium salt with water, the fluidity of the ester type quaternary ammonium salt itself is ensured by an organic solvent such as ethanol or heating. Even if it is used for the preparation of a softening agent, there is a problem that when the ester-type quaternary ammonium salt and water are mixed, the viscosity increases, and efficient and sufficient stirring cannot be performed.
The present invention provides a method for producing a liquid softener composition that can be stably produced without becoming a high viscosity during production of a liquid softener composition containing an ester-type quaternary ammonium salt at a high concentration.

The present invention is a method for producing a liquid softener composition comprising the following component (A) 15 mass% or more, 30 mass% or less, and water,
(A) The emulsification step for forming an emulsified composition containing the component and water is performed in the presence of the cationic polymer of the following component (B) and under conditions where the amount of water is larger than the amount of component (A).
The present invention relates to a method for producing a liquid softener composition.
<(A) component>
Among the four groups that are quaternary ammonium salts and covalently bonded to the nitrogen atom, one or more and three or less are groups represented by -R ^1a -OC (O) -R ^2a , A quaternary ammonium salt in which the group is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group (where R ^1a is an alkylene group having 2 or 3 carbon atoms, R ^2a is 16 or more carbon atoms, 22 or less hydrocarbon group, C (O) represents a carbonyl group.)
<(B) component>
Cationic polymer containing monomer units derived from one or more compounds selected from compounds represented by the following general formula (B1), acid salts thereof and quaternary salts thereof

[In General Formula (B1), R ^1b and R ^2b each independently represent a hydrogen atom or a methyl group, and R ^3b represents —C (O) OM (M represents a hydrogen atom or an alkali metal atom) or a hydrogen atom. Indicates. X represents —C (O) O—R ^6b —, —C (O) NR ^7b —R ^8b — or —CH ₂ —. R ^4b has the general formula (B1 ′) when X is —CH ₂ —.

In the other cases, X represents an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. R ^5b represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ^6b and R ^8b each independently represent an alkylene group having 1 to 4 carbon atoms, and R ^7b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the liquid softening agent composition which can be stably manufactured without becoming high viscosity during manufacture of the liquid softening agent composition containing ester type | mold quaternary ammonium salt in high concentration is provided. .

First, components used in the production method of the present invention and blended in the liquid softener composition will be described.
<(A) component>
(A) A component is a quaternary ammonium salt, Comprising: 1 or more and 3 or less are represented by -R < ^1a > -OC (O) -R < ^2a > among four groups covalently bonded to a nitrogen atom. A quaternary ammonium salt wherein the remaining group is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group (where R ^1a is an alkylene group having 2 or 3 carbon atoms, R ^2a is And a hydrocarbon group having 16 to 22 carbon atoms.). An object of the present invention is to emulsify the component (A) without increasing the viscosity.

  (A) As a component, the compound represented by general formula (A1) is mentioned.

[Wherein, R ^11a , R ^12a , R ^13a , R ^14a are groups in which one or more and three or less of these groups are represented by —R ^1a —OC (O) —R ^2a , and the rest Is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group (where R ^1a is an alkylene group having 2 or 3 carbon atoms, R ^2a is a hydrocarbon group having 16 to 22 carbon atoms. Show.) X ⁻ is an anionic group. ]

In general formula (A1), R ^11a , R ^12a , R ^13a , and R ^14a are flexible such that two of these groups are groups represented by —R ^1a —OC (O) —R ^2a . And preferred in terms of stability. The hydrocarbon group for R ^2a is preferably an alkyl group. R ^2a preferably has 15 or more and 21 or less carbon atoms. R ^2a is preferably an alkyl group having 16 to 22 carbon atoms.
In general formula (A1), the remaining group of R ^11a , R ^12a , R ^13a and R ^14a is preferably a hydroxyl alkyl group or alkyl group having 1 to 3 carbon atoms.
In the general formula (A1), the anion group of X ^{− is} an anion group selected from halogen ions, sulfate ions, fatty acid ions having 1 to 12 carbon atoms, and alkyl sulfate ions having 1 to 3 carbon atoms. Preferably, it is an anion group selected from halogen ions and alkyl sulfate ions having 1 to 3 carbon atoms.

(A) In general formula (A1), one, two or three of R ^11a , R ^12a , R ^13a and R ^14a are represented by —R ^1a —OC (O) —R ^2a in general formula (A1). It is preferable that at least one of the remaining groups is a mixture of compounds having an alkyl group having 1 to 3 carbon atoms.

The component (A) is a mixture of compounds represented by the general formula (A1),
The proportion of the compound having one —R ^1a —OC (O) —R ^2a is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably in the mixture. Is 35% by weight or less,
The proportion of the compound having two —R ^1a —OC (O) —R ^2a is preferably 30% by mass or more, more preferably 35% by mass or more, and preferably 70% by mass or less, more preferably in the mixture. Is 65% by mass or less,
-R ^1a -OC (O) -R ^2a has a ratio of three compounds of preferably 8% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less in the mixture. The mixture is more preferably 25% by mass or less. Also in the case of this mixture, a compound in which at least one of the remaining groups of the group represented by —R ^1a —OC (O) —R ^2a is an alkyl group having 1 to 3 carbon atoms is preferable.

<(B) component>
The component (B) is a monomer unit derived from one or more compounds selected from the compound represented by the following general formula (B1), its acid salt and its quaternary salt [hereinafter referred to as monomer unit (B1)]. It is a cationic polymer to contain. The liquid softening agent composition manufactured by this invention contains (B) component.

[In General Formula (B1), R ^1b and R ^2b each independently represent a hydrogen atom or a methyl group, and R ^3b represents —C (O) OM (M represents a hydrogen atom or an alkali metal atom) or a hydrogen atom. Indicates. X represents —C (O) O—R ^6b —, —C (O) NR ^7b —R ^8b — or —CH ₂ —. R ^4b has the general formula (B1 ′) when X is —CH ₂ —.

In the other cases, X represents an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. R ^5b represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ^6b and R ^8b each independently represent an alkylene group having 1 to 4 carbon atoms, and R ^7b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

Among the compounds represented by the general formula (B1) that are derived from the monomer unit (B1), the compound in which X in the general formula (B1) is —C (O) O—R ^6b — is acrylic acid. (Or methacrylic acid) N, N-dimethylaminomethyl, acrylic acid (or methacrylic acid) N, N-dimethylaminoethyl, acrylic acid (or methacrylic acid) N, N-dimethylaminopropyl, acrylic acid (or methacrylic acid) N, N-dimethylaminobutyl, acrylic acid (or methacrylic acid) N, N-diethylaminomethyl, acrylic acid (or methacrylic acid) N, N-diethylaminoethyl, acrylic acid (or methacrylic acid) N, N-diethylaminopropyl, Examples include acrylic acid (or methacrylic acid) N, N-diethylaminobutyl.

In addition, among the compounds represented by the general formula (B1), the compound in which X in the general formula (B1) is —C (O) NR ^7b —R ^8b — is N, N-dimethylaminopropylacrylic acid. (Or methacrylic acid) amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminobutylacrylic acid (or And methacrylic acid) amide.

When X in the general formula (B1) is —CH ₂ —, R ^4b is a group represented by the general formula (B1 ′). Examples of such a compound include diallylamine.

  As the compound represented by the general formula (B1), an acid salt or a quaternary salt thereof can be used. Examples of the acid salt include neutralized salts of the compound represented by the general formula (B1) with an inorganic acid such as hydrochloric acid or sulfuric acid, and neutralized salts with various organic acids. As the quaternary salt, a quaternary salt obtained by quaternizing the compound represented by the general formula (B1) with an alkyl halide having 1 to 3 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms or the like is used. Can be mentioned. Quaternary salts include N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N-dimethyl-N-ethyl-N- (2-methacryloyloxyethyl) ammonium ethyl sulfate, diallyldimethyl Ammonium chloride is mentioned. These compounds are sold, for example, under the trade names QDM and MOEDES by MRC Unitech Co., Ltd.

  Among the compounds represented by the general formula (B1), more preferable compounds are N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl acrylate, and acrylic acid. It is one or more selected from N, N-dimethylaminomethyl.

  The component (B) according to the present invention includes a monomer unit (B1) and a monomer unit derived from a polymerizable vinyl compound copolymerizable with the compound represented by the general formula (B1) [hereinafter referred to as a monomer unit (B2). ] May be used.

  As a monomer unit (B2), the monomer unit derived from the compound represented by the following general formula (B2) is mentioned.

[Wherein, R ^11b and R ^12b each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y represents an aryl group, —O—C (O) —R ^13b , —C ( _{^{O) O- (R 14b -O)}} n -R 15b, or an ^{-C (O) NR 16b -R 17b} . R ^13b , R ^15b and R ^17b are each independently a linear, branched, or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, or an arylalkyl having 6 to 14 carbon atoms in total. R ^14b represents an alkylene group having 2 or 3 carbon atoms, n represents a number of 0 or more and 50 or less, R ^16b represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms. ]

Y in the general formula (B2) is preferably —C (O) O— (R ^14b —O) _n —R ^15b .
In —C (O) O— (R ^14b —O) _n —R ^{15b of} Y, R ^15b is preferably an alkyl group having 8 or more carbon atoms, more preferably 10 or more, and 18 or less, and further 14 or less. R ^14b is preferably ethylene. n is a number of 0 or more, preferably 20 or less, more preferably 10 or less. n is more preferably 0.

  As a specific polymerizable vinyl compound represented by the general formula (B2) and copolymerizable with the starting material of the monomer unit (B1), the alkyl group has 1 or more carbon atoms, preferably 8 or more, and 22 or less, Acrylic acid alkyl ester or methacrylic acid alkyl ester which is preferably 14 or less is preferred in that the effects of the present invention can be more enjoyed.

  As the polymerizable vinyl compound copolymerizable with the starting material of the monomer unit (B1) other than the compound of the general formula (B2) [hereinafter referred to as other polymerizable compound], (1) vinyl alcohol, (2) hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylamide and other polyvalent compounds such as (meth) acrylic acid ester or (meth) acrylamide, (3) glycerin (meth) acrylate having a hydroxyalkyl group having 1 to 22 carbon atoms (Meth) acrylic acid ester of alcohol, (4) diacetone (meth) acrylamide, (5) N-vinyl cyclic amide such as N-vinylpyrrolidone, (6) N- (meth) acryloylmorpholine, (7) vinyl chloride (8) Acrylonitrile, (9) (Meth) acrylic acid, maleic acid, itaconic acid, Vinyl compounds having a carboxyl group such Renkarubon acid, (10) 2-acrylamido-2-methylpropane sulfonic acid, vinyl compounds having a sulfonic acid group such as styrenesulfonic acid, etc. are exemplified.

  The component (B) is (i) a compound selected from the compounds represented by the general formula (B1), an acid salt thereof and a quaternary salt thereof, specifically N, N-dimethylaminoethyl methacrylate, methacrylic acid A cationic homopolymer of a monomer selected from N, N-dimethylaminomethyl, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminomethyl acrylate, and (ii) represented by the general formula (B1) And one or more compounds selected from the acid salts and quaternary salts thereof, specifically, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminomethyl methacrylate, N, N-acrylate A monomer selected from dimethylaminoethyl and N, N-dimethylaminomethyl acrylate, a compound represented by the general formula (B2), specifically an alkyl group Prime cationic copolymer obtained by copolymerization of one or more compounds selected from 8 to 14 alkyl acrylate esters and alkyl methacrylate, cationic polymers selected from the preferred.

  The component (B) is preferably a copolymer having a monomer unit (B1) and a monomer unit (B2), particularly a monomer unit derived from the compound represented by the general formula (B2), from the viewpoint of the flexibility effect. Such a copolymer preferably has a monomer unit (B1) / monomer unit (B2) ratio of 20/80 or more and 99/1 or less, more preferably 50/50 or more and 95/5 or less. Furthermore, 70/30 or more and 95/5 or less are more preferable. In addition, the total of the monomer units (B1) and the monomer units (B2) is preferably 60 mol% or more, more preferably 80 mol% or more in the total monomer units of the component (B), from the viewpoint of improving flexibility. 100 mol% or less is preferable. The monomer unit ratio may be a molar ratio of the polymerizable compounds of the general formula (B1) and the general formula (B2) used at the time of polymerization.

  The weight average molecular weight (Mw) of the component (B) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 6,000 or more, and still more preferably 12,000 or more, from the viewpoint of the flexibility effect. And preferably 2,000,000 or less, more preferably 1,500,000 or less, still more preferably 100,000 or less, and still more preferably 60,000 or less. The ratio Mw / Mn of Mw and Mn (number average molecular weight) is preferably 1.0 or more, more preferably 1.5 or more, and preferably 40 or less, more preferably 35.

  In addition, the value by gel permeation chromatography (GPC) measurement is used for Mw, Mn, and Mw / Mn of the (B) component of this invention. As an eluent, water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile, or any combination of these solvents is used. If the polymer of component (B) is relatively hydrophilic, polyethylene glycol is used. Since it is used as a standard, it has a molecular weight in terms of polyethylene glycol (hereinafter sometimes referred to as PEG), and in the case of relatively hydrophobic, since polystyrene is used as a standard, it may be referred to as polystyrene (hereinafter also referred to as PSt). ) Molecular weight.

That is, when the polymer to be measured is considered to be relatively hydrophilic with a large proportion of monomer units (B1), it is a mixed solvent of (1% acetic acid / ethanol): water = 3: 7 (mass ratio). Using the prepared LiBr 50 mmol / L solution as a solvent, two GPC columns “α-M (manufactured by Tosoh Corp.)” for polar solvents are used in series, and the molecular weight is calculated in terms of polyethylene glycol (measurement method A). . When the polymer is considered to be relatively hydrophobic, a GPC column for organic solvents “K-804 (manufactured by Showa Denko KK) with a 1 mmol / L-CHCl ₃ solution of Farmin DM20 (manufactured by Kao Corporation) ) "Are used in series, and the molecular weight in terms of polystyrene is calculated (measurement method B).
The cationic polymer of component (B) may be used in the form of being dissolved or dispersed in the water-soluble organic solvent of component (D) in the production process of the present invention. The amount of water-soluble organic solvent used at that time should be the minimum necessary in consideration of not only the storage stability and viscosity properties of the softener composition as the final product, but also the production method and production equipment. preferable. The component (B) is preferably a hydrophilic cationic polymer.

<Other ingredients>
The liquid softening agent composition manufactured by the manufacturing method of this invention can contain components other than (A) component and (B) component. Specifically, the following components can be contained.

[Component (C)]
Nonionic surfactant The liquid softening agent composition manufactured by the manufacturing method of this invention can contain a nonionic surfactant as (C) component.
The component (C) is preferably a nonionic surfactant represented by the following general formula from the viewpoint of uniform dispersion of the component (B) during emulsification and storage stability.
R—O— (C ₂ H ₄ O) _n —H
[Wherein, R represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms. n is an average added mole number, and n is a number of 15 or more and 50 or less.
In the formula, R is preferably an alkyl group or an alkenyl group having 10 or more carbon atoms, more preferably 12 or more, and preferably 16 or less, more preferably 14 or less, and still more preferably a straight chain having 10 to 14 carbon atoms. It is an alkyl group derived from a chain primary alcohol or a linear secondary alcohol.

In the present invention, the component (B) is a compound in which R ^5b in the general formula (B1) is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, an acid salt thereof, and an acid salt thereof In the case of a cationic polymer containing a monomer unit derived from one or more compounds selected from quaternary salts, the emulsification step may be carried out in the presence of a nonionic surfactant together with the component (B) (B ) It is preferable from the viewpoint of uniformly dispersing the components.

  2. Content of (C) component in the liquid softening agent composition which concerns on this invention is 0.1 mass% or more, Preferably it is 0.5 mass% or more, More preferably, it is 1.0 mass% or more. It is 0 mass% or less, preferably 2.5 mass% or less, more preferably 2.0 mass% or less.

[Component (D)]
Water-soluble organic solvent The liquid softening agent composition manufactured by the manufacturing method of this invention can contain a water-soluble organic solvent as (D) component. The component (D) is effective for suppressing increase in viscosity when the liquid softening agent composition is frozen.
Here, about the organic solvent of (D) component, being water-soluble means what melt | dissolves 1.0g or more in 100g of deionized water of 25 degreeC.
Specifically, the component (D) is preferably at least one selected from ethanol, isopropanol, glycerin, ethylene glycol and propylene glycol, and more preferably at least one selected from ethanol, isopropanol and ethylene glycol.
The content of the component (D) in the liquid softening agent composition according to the present invention is preferably 0% by mass or more, further 1.0% by mass or more, and 5.0% by mass or less, and more preferably 3.0% by mass or less. . In the case of containing ethanol, the content in the composition is preferably 1.0% by mass or more, 2.5% by mass or less, and more preferably 2.0% by mass or less. The component corresponding to the component (D) can be used as a dispersion medium in the production process of the component (A), a solvent or a dispersion medium of the component (B), and the component (D) in such a form. Can be used for the manufacturing method of the softening agent composition of this invention. And about the (D) component taken in in the liquid softening agent composition in such a form, it shall take in in content of the said (D) component.

[(E) component]
pH adjuster The liquid softener composition produced by the present invention has a pH of the stock solution of 2.0 or more at 30 ° C. in order to suppress decomposition due to hydrolysis of the quaternary ammonium compound of component (A). It is preferable to adjust to 0 or less. Therefore, it is preferable to mix | blend a pH adjuster with (E) component in the liquid softening agent composition manufactured by this invention. Examples of the pH adjuster include a component selected from an acid agent and an alkali agent.
Examples of the acid agent include inorganic acids and organic acids. As specific examples of the inorganic acid, hydrochloric acid and sulfuric acid can be used. Specific examples of the organic acid include monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms, or monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms. More specifically, methylsulfuric acid, ethylsulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, glycolic acid, citric acid, benzoic acid And salicylic acid.
Some acid agents function as a chelating agent, which will be described later. In the present invention, the amount of an acid agent that also functions as a chelating agent is included in the amount of the chelating agent.
Examples of the alkali agent include inorganic bases and organic bases. Specific examples of the inorganic base include sodium hydroxide and potassium hydroxide. Specific examples of the organic base include monoethanolamine, diethanolamine, and triethanolamine.
(E) component of an acid agent or an alkali agent is mix | blended in the quantity from which the pH of a composition becomes the said range, and is restrict | limited to the quantity which does not impair stability.
In the present invention, the pH is measured according to “JIS K 3362; 2008, item 8.3, at a specified temperature, and at 30 ° C. if not specified.

[(F) component]
Water-soluble inorganic salt The liquid softening agent composition produced by the production method of the present invention can contain a water-soluble inorganic salt as the component (F).
Here, about the inorganic chloride of (F) component, being water-soluble refers to what is dissolved in 10 g or more in 100 g of deionized water at 25 ° C.
Examples of the water-soluble inorganic chloride of component (F) include compounds selected from alkali metal chlorides and alkaline earth chlorides. Preferred is a compound selected from sodium chloride, lithium chloride, calcium chloride and magnesium chloride, more preferred is a compound selected from calcium chloride and magnesium chloride, and even more preferred is calcium chloride. In addition, in order to suppress the viscosity increase at the time of the preservation | save of the liquid softening agent composition manufactured by the manufacturing method of this invention, it is preferable to add (F) component to the already emulsified emulsion composition.
The content of the component (F) in the liquid softening agent composition according to the present invention is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.6% by mass or more. 5% by mass or less, preferably 1.2% by mass or less, more preferably 0.9% by mass or less.

[(G) component]
Chelating agent The liquid softener composition produced according to the present invention preferably contains a chelating agent as component (G) in order to capture metal ions such as copper and iron and alkaline earth metal ions in water. .
The chelating agent used in the present invention is intended to improve the storage stability of the liquid softener composition produced according to the present invention, in addition to the purpose of capturing metal ions such as copper and iron in water and alkaline earth metal ions. It is also used to suppress discoloration of the softener composition and dye fading.
Examples of the component (G) include ethylenediaminetetraacetic acid, hydroxyethylidene diphosphonic acid, L-aspartic acid diacetic acid, S, S-ethylenediamine disuccinic acid, and N-2-hydroxy, which are superior in biodegradability compared to these. Ethyliminodiacetic acid, 3-hydroxy-2,2′-iminodisuccinic acid, L-glutamic acid-N, N-diacetic acid, and methylglycine diacetic acid can be used. As the component (G), a compound selected from hydroxyethylidene diphosphonic acid, methylglycine diacetic acid (MGDA), and salts thereof is more preferable.
In the liquid softener composition according to the present invention, the component (G) is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and further preferably 0.005% by mass in terms of acid type compound. %, More preferably 0.0075% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less.

[(H) component]
In order to suppress foaming during the use of the silicone softener composition, and to improve the texture and feel of the textile product, the liquid softener composition produced by the present invention contains silicone as a component (H). It is preferable to contain a compound.
Examples of the silicone compound include general dimethylpolysiloxane and known modified silicone. When the silicone compound is used in combination with silica fine particles, the foam suppressing power of the softening agent composition is improved. A commercially available silicone solution can be used as the silica-containing silicone.
The content of the silicone compound as component (H) is 0% by mass or more, further 0.01% by mass or more, and 2.0% by mass or less, and further 1.5% by mass in the liquid softener composition according to the present invention. % Or less is preferable.

[Other optional ingredients]
In the liquid softener composition produced according to the present invention, components known to be blended in the softener can be blended to such an extent that this effect is not impaired.
The liquid softener composition produced by the present invention includes, for example, surfactants other than the component (A) such as lauryldimethylbenzylammonium chloride, 2,6-di-tert-butyl-4-methylphenol and 2, Antioxidants such as 6-di-tert-butyl-4-ethylphenol, dyes such as CIAcid Blue 5, CIAcid Blue9 and CIAcid Blue 74, preservatives, softener compositions and fiber treatment agents commercially available as Proxel BDN It can contain a microcapsule fragrance containing a fragrance composition known to be blended in the composition, a silicate esterified product of an alcohol-based fragrance and a fragrance composition and microencapsulated.

  The liquid softener composition produced according to the present invention contains water. The balance of the composition is water. As the water, deionized water, sterilized water in which a small amount of hypochlorite is mixed in deionized water, tap water, or the like can be used.

<Method for producing liquid softener composition>
The manufacturing method of the liquid softening agent composition of this invention performs the emulsification process which forms the emulsion composition containing (A) component and water in presence of the cationic polymer of (B) component. In that case, it carries out in the state in which the mass of (A) component is less than the mass of water. The method for producing a liquid softener composition of the present invention includes an emulsification step of forming an emulsified composition containing the component (A) and water, and the emulsification step is performed in the presence of the cationic polymer of the component (B) and It is carried out under conditions where the amount of water is larger than the amount of component (A) as mass.

When component (E) is included in the component blended in the emulsion composition, (A) quaternary ammonium salt as component, (B) cationic polymer as component, (E) pH adjuster as component, And water can be used in any of the following ways to form an emulsified composition. That is, in this invention, when mix | blending (E) component with a liquid softening agent composition, the emulsion composition containing (A) component and water is formed by the method in any one of the following (i)-(vii). An emulsification step can be performed.
However, it is necessary to perform an emulsification process in the state with much quantity of water with respect to (A) component quantity. For example, when the emulsification step is started by a method of adding water or an aqueous composition containing water to the liquid composition containing the component (A), the amount of water increases when all the water is added at once. In some cases, however, when viewed over time, at the start of emulsification, emulsification is performed in a state where the amount of component (A) is greater than that of water, and the mixture may thicken during the emulsification step.
The component (B) may be used in a state dissolved or dispersed in the water-soluble organic solvent of the component (D). In the following (i) to (vii), the use of the water-soluble organic solvent is omitted. An example of doing so is also disclosed. Therefore, the following (i) to (vii) components (B) include “component (B) dissolved or dispersed in component (D)”.
(I): A method of emulsifying by adding the component (A) to an aqueous composition obtained by mixing the component (B), the component (E) and water.
(Ii): Method (iii) of adding the component (A) to the aqueous composition obtained by mixing the component (B) and water, adding the component (A) to emulsify, and adding the component (E) during or after emulsification (iii): (E) The method of emulsifying by adding the mixture of (A) component and (B) component to the aqueous composition obtained by mixing a component and water.
(Iv): A method of adding a mixture of the component (A) and the component (B) to an aqueous composition containing water to perform emulsification, and adding the component (E) during or after emulsification.
(V): A method of emulsifying by adding a mixture of the components (A), (B) and (E) to an aqueous composition containing water.
(Vi) An aqueous composition obtained by mixing the component (B) and water is added to the mixture of the component (A) and the component (B) to emulsify, and the component (E) is added during or after emulsification. how to.
(Vii) A method of emulsifying by adding a mixture of the component (A) and the component (B) to the aqueous composition obtained by mixing the component (B), the component (E) and water.

  In the present invention, a method selected from (i), (ii), (iii) and (iv) is preferable, and a method (i) or (ii) is more preferable.

  In addition, as long as it does not affect stability, you may mix | blend another component with the mixture of a mixing | blending component at any time, and may mix | blend after emulsification. Components that are easily affected by heat, such as a fragrance composition, are added after cooling the emulsion composition. (C) component, (D) component (however, (D) component mixed in the manufacturing process of (A) component and (D) component used for dissolution or dispersion of component (B)), (G) component And 1 or more types chosen from (H) component are preferably contained in the aqueous composition containing the water in said (i)-(vi). Furthermore, in the production method of the present invention, the component (C) and the component (H) are included in the blending component of the liquid softener composition, and an emulsion composition is formed in the process of producing the liquid softener composition. It is preferable that the component (C) and the component (H) coexist before being processed. The component (F) is preferably added to the emulsified composition after the emulsification step.

  In the present invention, the emulsification step is performed by converting a liquid composition containing the component (A) (hereinafter also referred to as “liquid composition (La)”) to an aqueous composition containing the component (B) and water (hereinafter referred to as “liquid composition (La)”). And may be referred to as “aqueous composition (Lwb)” for emulsification. The above-described methods (i) and (ii) correspond to this embodiment.

  The liquid composition (La) containing the component (A) preferably contains a melt of the component (A). When the component (A) is solid at room temperature, it is melted by heating. All of the liquid composition (La) may be a melt of the component (A).

In the liquid composition (La) containing the component (A), the content of the component (A) is preferably 75% by mass or more, more preferably 85% by mass or more, and preferably 100% by mass or less, more preferably Is 95 mass% or less.
The component (B) before the emulsification step is preferably blended in a solution different from the liquid composition (La) containing the component (A). Therefore, in the liquid composition (La) containing the component (A), the content of the component (B) is preferably 1% by mass or less, more preferably 0% by mass.
Although it is preferable that the content of water in the liquid composition (La) containing the component (A) is small, a small amount of water may be inevitably brought in from a substrate such as a water-soluble organic solvent described later. Considering this, it is preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.3% by mass or less.

The liquid composition (La) containing the component (A) can contain other components.
The liquid composition (La) containing the component (A) is a water-soluble organic solvent of the component (D), preferably one or more selected from ethanol, isopropanol, propylene glycol, ethylene glycol and glycerin, more preferably ethanol and isopropanol. It is preferable to contain at least one selected from the group consisting of ethanol and even more preferably ethanol. In the liquid composition (La) containing the component (A), the content of the water-soluble organic solvent of the component (D) is preferably 5% by mass or more, more preferably 15% by mass or more, and preferably 35% by mass. % Or less, more preferably 30% by mass or less.

  In the aqueous composition (Lwb) containing the component (B) and water, the content of the component (B) is 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 1.5%. It is not more than mass%, more preferably not more than 1.0 mass%.

  The aqueous composition (Lwb) containing the component (B) and water can contain components other than the component (A) in addition to the component (B). The component illustrated as another component can be contained. In order to improve the usability of the component (B) in the production process, the component (B) may be dissolved or dispersed in the water-soluble organic solvent of the component (D).

The aqueous composition (Lwb) containing the component (B) and water preferably contains a nonionic surfactant as the component (C).
In the aqueous composition (Lwb) containing the component (B) and water, the content of the nonionic surfactant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 5 mass% or less, More preferably, it is 2 mass% or less.

  When the emulsification step is performed by adding the liquid composition (La) containing the component (A) to the aqueous composition (Lwb) containing the component (B) and water, the temperature of the liquid composition (La) Is preferably at least the melting point of the component (A), specifically, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and preferably 75 ° C. or lower, more preferably 70 ° C. or lower. The temperature of the aqueous composition (Lwb) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and preferably 70 ° C. or lower, more preferably 65 ° C. or lower.

  In the present invention, the emulsification step is carried out by heating the liquid composition (La) containing the component (A) to the melting point of the component (A) or higher to obtain the aqueous composition (Lwb) containing the component (B) and water. It is preferable to add and emulsify. That is, in the present invention, the emulsification step is performed by adding the liquid composition (La) containing the melt of the component (A) to the aqueous composition (Lwb) containing the component (B) and water. More preferred. In the present invention, the liquid composition (La) containing the component (A) is prepared by heating the component (A) to the melting point of the component (A) or a mixture of the component (A) and other components ( A liquid composition containing a melt of the component (A) prepared by heating to the melting point of the component A) is preferred.

  The pH of the aqueous composition containing the component (B) and water is 65 ° C., preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 9 or less.

(A) In the emulsification step of forming the emulsified composition containing the component and water, it is preferable to form the emulsified composition by stirring the components blended in the emulsified composition.
In this invention, the emulsification process which forms the emulsion composition containing (A) component and water can be performed using apparatuses, such as a propeller type stirrer and a homomixer. The apparatus is preferably a propeller stirrer.
Using these apparatuses, emulsification can be performed by adding the liquid composition (La) to the aqueous composition (Lwb) and stirring. In that case, it is preferable to carry out emulsification by adding the liquid composition (La) little by little in a state where the aqueous composition (Lwb) on the receiver side (added side) is gently stirred.
The apparatus has a stirring blade (impeller). The stirring blade preferably has a shape such as a fan type, a propeller type, or a turbine type.
In the emulsification, the stirring conditions of the apparatus are preferably stirred at a peripheral speed of 0.5 to 10 m / s when the stirring blade is a propeller type from the viewpoint of the storage stability of the manufactured product.
The rate at which the liquid composition (La) or the aqueous composition (Lwb) is added depends on the scale of production.
The emulsion composition thus obtained exhibits good stability during storage after production.

In the present invention, from the viewpoint of suppressing the increase in viscosity during storage, the component (A) and the component (B) at the time when the total amount of the component (A) and the total amount of the component (B) blended in the liquid softener composition are mixed. The component mass ratio (A) / (B) is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, and preferably 200 or less, more preferably 170 or less, and even more preferably 100 or less. . This mass ratio is a mass ratio of the component (A) and the component (B) in the liquid softening agent composition. In the present invention, it is preferable to start the emulsification step by allowing the component (B) to exist within the range of the mass ratio of (A) / (B).
In the present invention, from the viewpoint of obtaining a uniform emulsified composition by suppressing thickening, in the emulsification step performed in the presence of component (B), a mixture to be emulsified at the end of emulsification, that is, an emulsified composition. The viscosity of the product is 65 mC, preferably 10 mPa · s or more, and preferably 500 mPa · s or less, more preferably 300 mPa · s or less.
Further, in the present invention, from the viewpoint of obtaining a uniform emulsified composition by suppressing thickening, in the emulsification step performed in the presence of the component (B), the mixture to be emulsified from the start of emulsification to the end of emulsification. The viscosity at 65 ° C. is preferably 10 mPa · s or more, and preferably 500 mPa · s or less, more preferably 300 mPa · s or less.
These viscosities were measured by the same method as the “viscosity in the emulsification process” in the examples.

In the present invention, among the total amount of the component (A) to be finally blended in the liquid softener composition, 90% by mass or more, further 95% by mass or more, further 100% by mass, that is, the total amount of the component (A), It is preferable to use in an emulsification process.
In the present invention, among the total amount of the component (B) finally blended in the liquid softening agent composition, 90% by mass or more, further 95% by mass or more, and further 100% by mass, that is, the total amount of the component (B). Is preferably used in the emulsification step.

  Components other than the component (A) and the component (B) can be used in any of the steps for producing the liquid softening agent composition. The water-soluble inorganic salt of component (F) is preferably added to the emulsified composition after the emulsification step from the viewpoint of suppressing the increase in viscosity during storage of the liquid softener composition. Therefore, in this invention, it has the process of adding the water-soluble inorganic salt of (F) component to the emulsion composition formed at the emulsification process from a viewpoint of the viscosity increase suppression at the time of the preservation | save of a liquid softening agent composition. preferable. (F) It is preferable to add the water-soluble inorganic salt of component so that it may become a ratio of 0.3 mass% or more and 1.0 mass% or less with respect to a liquid softening agent composition.

Content of (A) component in a liquid softening agent composition is 15 mass% or more, More preferably, it is 18 mass% or more, and is 30 mass% or less, Preferably it is 25 mass% or less.
The content of the component (B) in the liquid softener composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 1.0% by mass or less, more preferably Is 0.5 mass% or less.
Furthermore, the amount of water in the liquid softening agent composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, preferably 90% by mass or less, more preferably 85%. It is at most 80% by mass, more preferably at most 80% by mass.

The following are mentioned as a preferable manufacturing method of the liquid softening agent composition of this invention. The matters described above can be appropriately applied to this manufacturing method.
The liquid composition (La) containing the component (A) and the liquid composition (La) containing the melt of the component (A) are further converted into an aqueous composition (Lwb) containing the component (B) and water. A method for producing a liquid softener composition, comprising the steps of adding and preparing a mixture, stirring the mixture, and preparing an emulsified composition having the component (A) as emulsified particles. Furthermore, the manufacturing method of the said liquid softening agent composition which has the process of adding (F) component, Preferably water-soluble calcium salt to the emulsion composition prepared at the said process of preparing an emulsion composition.
In this case, stirring for emulsification may be performed before adding the liquid composition to the aqueous composition, or may be performed during or after the addition.

  (A) The emulsified composition which passed through all the emulsification processes which form the emulsified composition containing a component and water may be the target liquid softening agent composition as it is. Moreover, you may apply another process to the emulsion composition containing (A) component and water, and obtain the target liquid softening agent composition.

  The present invention is suitable as a method for producing a liquid softener composition for textiles such as clothing.

<Method for Preparing Liquid Softener Composition for Clothing>
[Preparation Method 1]
A 300 mL glass beaker is equipped with stirring blades with three turbine-type wings (installed so that the bottom of the stirring blade is 1 cm above the bottom of the beaker), and the finished mass of the liquid softener composition for clothing is 300 g. The amount of ion-exchanged water corresponding to 95% by mass of ion-exchanged water (that is, ion-exchanged water corresponding to the rest of the composition) necessary for the above was added, and the temperature was raised to 65 ° C. with a water bath. While stirring at 450 rpm, the melted component (C) (polyoxyethylene alkyl ether) and component (H) (silicone) were added. Subsequently, after adding (B) component, (G) component (chelating agent) was added. In some examples, the component (B) was added, the component (E) (hydrochloric acid) was added, and the mixture was stirred for 1 minute, and then the component (G) was added. Thereby, the aqueous composition (Lwb) containing (B) component and water was prepared. The pH of this aqueous composition (Lwb) was 2.5 to 3.5 at 65 ° C.

  Component (A) and component (D) (ethylene glycol) were mixed at 65 ° C. to prepare a liquid composition (La) having a water content of 1.0% by mass or less in which component (A) was melted.

  The emulsification process was started by adding the liquid composition (La) at 65 ° C. to the aqueous composition (Lwb) at 65 ° C., and the emulsification process was further performed by stirring at 65 ° C. for 5 minutes to obtain an emulsification composition. In Example 3, component (F) (calcium chloride) was added to the emulsified composition obtained in the emulsification step, and the mixture was stirred for 5 minutes.

  The emulsion composition obtained by adding the component (F) (calcium chloride) to the emulsion composition obtained in the emulsification step or the emulsion composition obtained in the emulsification step up to 30 ° C. in a 5 ° C. water bath. It cooled and obtained the liquid soft composition for clothes of the composition of Table 1.

[Preparation Method 2]
A 300 mL glass beaker is equipped with stirring blades with three turbine-type wings (installed so that the bottom of the stirring blade is 1 cm above the bottom of the beaker), and the finished mass of the liquid softener composition for clothing is 300 g. The amount of ion-exchanged water corresponding to 95% by mass of ion-exchanged water (that is, ion-exchanged water corresponding to the rest of the composition) necessary for the above was added, and the temperature was raised to 65 ° C. with a water bath. While stirring at 450 rpm, the melted component (C) (polyoxyethylene alkyl ether) and component (H) (silicone) were added. Subsequently, after adding (B) component, (E) component (hydrochloric acid) was added. Next, component (G) (chelating agent) and component (F) (calcium chloride) were added. Thereby, the aqueous composition (Lwb) containing (B) component and water was prepared. The pH of this aqueous composition (Lwb) was 3.0 at 65 ° C.

  Component (A) and component (D) (ethylene glycol) were mixed at 65 ° C. to prepare a liquid composition (La) having a water content of 1.0% by mass or less in which component (A) was melted.

The emulsification process was started by adding the liquid composition (La) at 65 ° C. to the aqueous composition (Lwb) at 65 ° C., and the emulsification process was further performed by stirring at 65 ° C. for 5 minutes to obtain an emulsification composition.
The obtained emulsified composition was cooled to 30 ° C. in a 5 ° C. water bath to obtain a liquid flexible composition for clothing having the composition shown in Table 1.

[Preparation Method 3]
A 300 mL glass beaker is equipped with stirring blades with three turbine-type wings (installed so that the bottom of the stirring blade is 1 cm above the bottom of the beaker), and the finished mass of the liquid softener composition for clothing is 300 g. The amount of ion-exchanged water corresponding to 95% by mass of ion-exchanged water (that is, ion-exchanged water corresponding to the rest of the composition) necessary for the above was added, and the temperature was raised to 65 ° C. with a water bath. While stirring at 450 rpm, the melted component (C) (polyoxyethylene alkyl ether) and component (H) (silicone) were added. Next, component (G) (chelating agent) was added. Thereby, the aqueous composition which does not contain (B) component was prepared. The pH of this aqueous composition was 3.05 at 65 ° C.

  Component (A) and component (D) (ethylene glycol) were mixed at 65 ° C. to prepare a liquid composition (La) having a water content of 1.0% by mass or less in which component (A) was melted.

  A liquid composition (La) at 65 ° C. was added to the aqueous composition at 65 ° C. to start the emulsification step, and the emulsification step was further performed by stirring at 65 ° C. for 5 minutes to obtain an emulsion composition.

  (B) component and (E) component (hydrochloric acid) were added to this emulsion composition, and it stirred for 5 minutes, and obtained the emulsion composition. The component (F) (calcium chloride) was added to the obtained emulsion composition and stirred for 5 minutes.

  The emulsified composition obtained by adding the component (F) was cooled to 30 ° C. in a 5 ° C. water bath to obtain a liquid flexible composition for clothing having the composition shown in Table 1.

<Viscosity in the emulsification process>
Within 1 minute after the emulsion composition obtained in the emulsification step or the emulsion composition obtained by adding the component (F) to the emulsion composition obtained in the emulsification step is heated to 65 ° C. and stirred for 5 minutes. The viscosity was measured. The viscosity was measured using a B-type viscometer (Toki Sangyo: VISCOMETER TVB-10) with shearing at 60 rpm for 1 minute. The rotor is selected so that the value of the viscometer is in the range of 20-80. When there are a plurality of target rotors or when there are no rotors to satisfy, a value close to the numerical range is adopted.
The results are shown in Table 1.

<Viscosity of liquid softener composition for clothing>
About the liquid softening agent composition for clothes of Example 3 and Example 11 manufactured by the preparation method in which the addition time of calcium chloride was different, the viscosity at 30 ° C. of the finally obtained composition was measured. Here, the viscosity of the composition is the viscosity of the composition after one day has elapsed after preparation and stored at 20 ° C. Viscosity is measured by placing a liquid softener composition for clothing into a sample bottle and using a B-type viscometer (Toki Sangyo: VISCOMETER TVB-10) to immerse the sample bottle in water in a 30 ° C constant temperature bath. Then, the measurement was performed by shearing at 60 rpm for 1 minute. The selection of the rotor was the same as the measurement of the viscosity in the emulsification process. The results are shown in Table 2. Table 2 also shows the viscosities of Comparative Examples 1 and 2.

The components in the table are as follows.
A-1: quaternary ammonium salt mixture obtained in the following synthesis example a-1 (melting point 38.0 ° C.) The numerical value (mass%) of a-1 in the table is a solid form of a-1. Concentration. The concentration of component (A) in a-1 is 80% by mass.
B-1: Dimethylaminoethyl methacrylate-lauryl methacrylate copolymer obtained in Synthesis Example b-1 below, Mw 14000 (converted to PEG)
B-2: Poly (2-methacryloyloxy-ethyltrimethylammonium chloride) obtained in Synthesis Example b-2 below, Mw10000 (converted to PEG)
B-3: Poly (2-methacryloyloxy-ethyltrimethylammonium chloride) obtained in Synthesis Example b-3 below, Mw 58000 (converted to PEG)
B-4: Poly (2-methacryloyloxy-ethyltrimethylammonium chloride) obtained in Synthesis Example b-4 below, Mw 100,000 (converted to PEG)
B-5: Poly (2-methacryloyloxy-ethyltrimethylammonium chloride) obtained in Synthesis Example b-5 below, Mw 230000 (converted to PEG)
B-6: Poly (dimethyldiallylammonium chloride), [Mw100,000 (converted to PEG), Unisense FPA102L, manufactured by Senka Corporation]
Polyoxyethylene alkyl ether: 12 carbon atoms of alkyl group (derived from lauryl alcohol), average addition mole number of ethylene oxide 29
Chelating agent: Methyl glycine diacetate [Trilon M Liquid, manufactured by BASF]
Silicone: Silicone KHE-55B (Shin-Etsu Chemical Co., Ltd.) (used as a texture improvement aid)

<Synthesis example a-1> Synthesis of a-1 A fatty acid having an acid value of 206.9 mgKOH / g and a triethanolamine from palm oil as a raw material and a reaction molar ratio of 1.65 / 1 (fatty acid / triethanolamine) Then, a dehydration condensation reaction was performed to obtain a condensate containing N, N-dialkanoyloxyethyl-N-hydroxyethylamine as a main component.

Next, the amine value of this condensate was measured, and quaternization was performed using 0.95 equivalent of dimethyl sulfate to the condensate, and N, N-dialkanoyloxyethyl-N-hydroxyethyl-N-methyl was obtained. A quaternary ammonium salt mixture (hereinafter referred to as a-1) containing ammonium methyl sulfate as a main component and containing 10% by mass of ethanol was obtained. However, the term “alkanoyl” used herein includes residues derived from unsaturated fatty acids, such as alkenoyl, in addition to saturated fatty acids, since alkanoyl is a fatty acid residue of palm oil raw material. Moreover, the preparation procedure and reaction conditions for obtaining the said condensate and a-1 were performed according to the synthesis example 2 of Unexamined-Japanese-Patent No. 2010-209493.
The proportion of the (monoalkanoyl) component which is a quaternary ammonium salt having one alkanoyl group in the quaternary ammonium salt contained in a-1 is 30% by mass, and is a quaternary ammonium salt having two alkanoyl groups. The proportion of the (dialkanoyl) component was 55% by mass, and the proportion of the (trialkanoyl) component which is a quaternary ammonium salt having three alkanoyl groups was 15% by mass. Here, the (monoalkanoyl) component is a compound having one fatty acid residue of a palm oil raw material, the (dialkanoyl) component is a compound having two fatty acid residues of a palm oil raw material, and a (trialkanoyl) component Is a compound having three fatty acid residues of palm oil raw material.
a-1 has a quaternization rate of 92% by mass, and in addition to the (monoalkanoyl) component, the (dialkanoyl) component, the (trialkanoyl) component, and ethanol, a tertiary ester of a diester structure and a triester structure The compound contained a trace amount of triethanolamine and its quaternized product, and a trace amount of fatty acid.

<Synthesis Example b-1> Synthesis of b-1 A 1 L four-neck separable flask equipped with a propeller-type stirrer, a nitrogen introduction tube, a Dimroth reflux device, and a thermometer was purged with nitrogen for a certain period of time. 73.3 g of propylene glycol monomethyl ether was added thereto, and the contents were heated and held with stirring until the temperature of the contents reached 80 ° C.
Separately, a monomer solution was prepared by uniformly mixing 213.6 g (1.36 mol) of dimethylaminoethyl methacrylate, 86.4 g (0.34 mol) of lauryl methacrylate, and 164.1 g of propylene glycol monomethyl ether.
Further, an initiator solution in which 4.22 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (v-65B: manufactured by Wako Pure Chemical Industries, Ltd.) and 40.11 g of propylene glycol monomethyl ether were uniformly mixed. Was also prepared separately.
The monomer solution and the initiator solution were dropped into the above separable flask over 3 hours. Next, a solution prepared by dissolving 8.44 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., v-65B) in 75.9 g of propylene glycol monomethyl ether was added to the flask. The solution was dropped at a constant rate over 4 hours. After completion of dropping, the polymer solution is kept at 80 ° C. for 2 hours, and then added with propylene glycol monomethyl ether, thereby containing a copolymer (b-1) of component (b), dimethylaminoethyl methacrylate and lauryl methacrylate. 1563 g was obtained. The weight average molecular weight (Mw) of the obtained copolymer was 14000. The composition of the copolymer analyzed by ¹ H-NMR was dimethylaminoethyl methacrylate / lauryl methacrylate = 8/2 (molar ratio). The composition of the polymer solution was 20% by mass of dimethylaminoethyl methacrylate-lauryl methacrylate copolymer (b-1) and 80% by mass of propylene glycol monomethyl ether. This polymer solution was used so that the amount of the copolymer (b-1) was as shown in Table 1.

<Synthesis Example b-2> Synthesis of b-2 In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 50.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM) and a polymerization solvent 200.0 g of isopropyl alcohol and 6.0 g of a polymerization initiator V-65B (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Then, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (b-2) (Mw10000) was obtained by making it reprecipitate with acetone 3000.0g, and making it dry.

<Synthesis Example b-3> Synthesis of b-3 In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 50.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM) and a polymerization solvent 50.0 g of water and 2.3 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were charged, and a polymerization reaction was performed at 80 ° C. for 6 hours. Then, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (b-3) (Mw 58000) was obtained by reprecipitation with 3000.0 g of acetone and drying.

<Synthesis Example b-4> Synthesis of b-4 In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 100.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM) and a polymerization solvent 150.0 g of ethanol and 0.4 g of a polymerization initiator V-65B (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and a polymerization reaction was performed at 70 ° C. for 6 hours. Then, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (b-4) (Mw100,000) was obtained by reprecipitation with 3000.0 g of acetone and drying.

<Synthesis Example b-5> Synthesis of b-5 In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 100.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM) and a polymerization solvent As a starting material, 66.7 g of ethanol and 0.1 g of a polymerization initiator V-65B (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Then, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (b-5) (Mw 230000) was obtained by reprecipitation with 3000.0 g of acetone and drying.

  In addition to the liquid softener composition for clothing having the composition shown in Table 1, other optional ingredients such as fragrance ingredients, preservatives, silicone as an antifoaming agent (corresponding to the (H) ingredient), dyes and the like are blended. Can do. In that case, to the emulsion composition obtained in the emulsification step, the emulsion composition obtained by adding the component (F) to the emulsion composition obtained in the emulsification step, or the composition after cooling them. After adding the said other arbitrary components, it can stir and can obtain the liquid flexible composition for clothing.

Claims (8)

The following (A) component 15 mass% or more, 30 mass% or less, and a method for producing a liquid softener composition containing water,
(A) The emulsification step for forming an emulsified composition containing the component and water is performed in the presence of the cationic polymer of the following component (B) and under conditions where the amount of water is larger than the amount of component (A).
A method for producing a liquid softener composition.
<(A) component>
Among the four groups that are quaternary ammonium salts that are covalently bonded to the nitrogen atom, one or more and three or less are groups represented by -R ^1a -OCO-R ^2a , and the remaining groups are carbon A quaternary ammonium salt which is an alkyl group or hydroxyalkyl group having a number of 1 or more and 3 or less (where R ^1a is an alkylene group having 2 or 3 carbon atoms, R ^2a is a carbon number of 16 or more and 22 or less) Indicates a hydrocarbon group.)
<(B) component>
Cationic polymer containing monomer units derived from one or more compounds selected from compounds represented by the following general formula (B1), acid salts thereof and quaternary salts thereof

[In General Formula (B1), R ^1b and R ^2b each independently represent a hydrogen atom or a methyl group, and R ^3b represents —COOM (M is a hydrogen atom or an alkali metal atom) or a hydrogen atom. X represents —COO—R ^6b —, —CONR ^7b —R ^8b — or —CH ₂ —. R ^4b has the general formula (B1 ′) when X is —CH ₂ —.

In the other cases, X represents an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. R ^5b represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ^6b and R ^8b each independently represent an alkylene group having 1 to 4 carbon atoms, and R ^7b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] Component (B) is a compound in which R ^5b in formula (B1) is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, an acid salt thereof, and a quaternary salt thereof. The liquid softener composition according to claim 1, wherein the composition is a cationic polymer containing a monomer unit derived from one or more selected compounds, and the emulsification step is performed in the presence of the nonionic surfactant together with the component (B). Manufacturing method.   The manufacturing method of the liquid softening agent composition of Claim 1 or 2 which performs an emulsification process by adding the liquid composition containing (A) component to the aqueous composition containing (B) component and water.   The emulsification step is performed by heating the liquid composition containing the component (A) to a temperature higher than the melting point of the component (A) and adding it to the aqueous composition containing the component (B) and water. The manufacturing method of the liquid softening agent composition of any one of these.   (A) The manufacturing method of the liquid softening agent composition of Claim 3 or 4 in which the liquid composition containing a component contains a water-soluble organic solvent.   (B) The manufacturing method of the liquid softening agent composition of any one of Claims 3-5 in which the aqueous composition containing a component and water contains a nonionic surfactant.   (B) The manufacturing method of the liquid softening agent composition of any one of Claims 3-6 whose pH of the aqueous composition containing a component and water is 1-10 at 65 degreeC.   The manufacturing method of the liquid softening agent composition of any one of Claims 1-7 which has the process of adding water-soluble inorganic salt to an emulsion composition.