WO2004061197A1 - Liquid softener composition - Google Patents

Abstract

A liquid softener composition which comprises: (a) 1 to 30 wt.% cationic compound containing an ester group in the molecule; (b) 0.5 to 20 wt.% silicone which at 25°C has a specific gravity of 0.96 to 1.10 and a viscosity of 5,000 to 500,000 mm2/s, excluding 5,000 mm2/s; and (c) 0.1 to 10 wt.% alcohol ethoxylate in which the monovalent hydrocarbon group has a linear chain/branched chain ratio of from 5/95 to 95/5 (by weight). The composition can retain viscosity stability, is highly effective in imparting softness, and improves the slipping properties of chemical fibers to impart a dry wear feeling.

Description

 Specification

Liquid softener composition Technical field

 The present invention relates to a liquid softener composition, particularly to a body softener composition for textiles. Background art

 In recent years, as a flexible base material used for a household softener, it has become mainstream to use a base material having an ester group in its molecule and having good biodegradability. However, a cationic flexible base material containing an ester group in the molecule has a tendency that the ester group is hydrolyzed by long-term storage or storage at a high temperature, and as a result, the viscosity increases as a softener composition, and It becomes an unfavorable state.

 As a solution, Japanese Patent Application Laid-Open No. 2003-106669 proposes a technique for limiting the ratio of cis-form to 90% or more in a flexible base material containing an unsaturated group. However, the fragrance of the softener composition may deteriorate under specific storage conditions, and further improvement is required.

 Examples of a combination of an ester group-containing cationic compound with a silicone compound and a specific nonionic surfactant (Japanese Patent Application Laid-Open No. 2000-64979), and an ester group-containing thione and a specific structure silicone compound (Japanese Patent Application Laid-Open No. 2000-640180) has been proposed, but the present invention is trying to solve the problem of securing the viscosity stability of a flexible substrate after hydrolysis. It was still insufficient. Furthermore, a combination of an ester group-containing cation and a silicone having a specific viscosity has been proposed (Japanese Patent Application Laid-Open No. 9-510263), but there are cases where the viscosity of the silicone is low and the flexibility is reduced. Yes, and it was still insufficient to ensure viscosity stability after hydrolysis

Disclosure of the invention

The present invention can secure the viscosity stability of a flexible base material containing an ester group after being hydrolyzed by aging or storage at high temperatures, is excellent in imparting flexibility, and improves the slipperiness of synthetic fibers. The purpose of the present invention is to provide a liquid softener composition that gives a smooth and comfortable feeling.

 The present inventors have found that the ratio of a cationic compound having an ester group in the molecule, a silica cone having a specific gravity and a specific viscosity, and a linear / branched alkyl group has a specific ratio.

 H-I

It has been found that the above object can be achieved by using a liquid softener composition containing a specific ratio of alcohol-13 ethoxylate.

 Accordingly, the following invention is provided.

 [1] · (a) 1 to 30% by mass of a cationic compound containing an ester group in the molecule,

(b) Silicon having a specific gravity of 0.960 at 25 ° C, a viscosity of more than 5,000 mm ² / s and not more than 500,000 mm ² Zs 0.5 to 20% by mass, (c) monovalent carbonization Alcohol ethoxylate whose hydrogen group is linear / branched (mass ratio) is 5/95 to 95/5 0.1 to 10% by mass

A liquid softener composition comprising:

 [2]. The liquid softener composition according to [1], further comprising (d) 0.4 to 10% by mass of a quaternary alkanolamine having 4 to 10 carbon atoms in total.

[3]. The liquid softener according to [1] or [2], wherein the silicone as the component (b) is a polyoxyalkylene-modified silicone represented by the following general formula (1) or (2). Composition.

CH ₃

Si-CH ₃ (1)

CH₃

CH ₃

(CH ₂ ) _L -0- (C ₂ H ₄₀ ) _p- (C ₃ H ₆₀ ) _q -X

(In the formula, n is 50 to 10,000, m is a number represented by 1 to 100, L is ;! to 5, p is 1 to 50, q is a number represented by 0 to 50, X is a hydrogen atom or It is an alkyl group having 1 to 3 carbon atoms.)

CH ₃ CH ₃

Xi-SiO- Si— R—— (OC ₂ H ₄ ) _p- (OC ₃ H ₆ ) _q -OR- X (2) C CH CH (Wherein, s is 1 to: L 0,000, t is a number of 1 to 1,000, p, q and X have the same meanings as described above. R is an alkylene group having 1 to 5 carbon atoms. )

[4]. The silicone as the component (b) is a polyoxyalkylene-modified silicone represented by the general formula (1), wherein X is a methyl group or an ethyl group. 6. The liquid softener composition according to item 1.

 [5]. The silicone of component (b) is a polyoxyalkylene-modified silicone represented by the above general formula (1), wherein n is 160 to 10,000. [3] or [3]. 4] The liquid softener composition according to the above.

 [6]. The component (a) is a cationic compound obtained by quaternizing an esteramine obtained by a condensation reaction of triethanolamine with a fatty acid or a fatty acid methyl ester with dimethyl sulfate. The liquid softener composition according to any one of [1] to [5]. BEST MODE FOR CARRYING OUT THE INVENTION

The component (a) of the present invention is a cationic compound containing an ester group in the molecule, and is not particularly limited as long as it is a cationic compound containing an ester group in the molecule. They can be used in combination. Examples of the component (a) include a tertiary amine represented by the following general formulas (3) to (9), a neutralized product thereof with an organic or inorganic acid, and a quaternized product thereof. The component (a) is preferably a quaternized product obtained by quaternizing an esteramine obtained by a condensation reaction between tolamine and a fatty acid or a fatty acid methyl ester with dimethyl sulfate. R ¹ COOCH ₂ CH _{2 N} ^

_Λ N-C¾ (3)

I ^ COOCi ^ CHz ノ³

R ¹ COOCH ₂ CH ₂

 -C¾ (4)

HOCH ₂ CH ₂

R ^ OOC ^ CHa

 \

CH ₂ CH ₂ OH (5)

R ¹ COOCH ₂ CH ₂ / ^N "

R ^ OOCH ^ Hz

 \

, N-CH ₂ CH ₂ OH (6)

HOCH ₂ CH ₂ '

(7)

R ¹ COOCH ₂ CH ₂

 \

-N-CH ₃ (8)

R ¹ CONHCH ₂ CH ₂ CH ₂

HOCH ₂ CH ₂ ,

 C¾ (9)

R ¹ CONHCH ₂ CH ₂ CH ₂ ^/ wherein, wherein R ¹ is a linear or branched alkyl or alkenyl group having 9 to 23 carbon atoms, particularly 11 to 21 carbon atoms, and May be different. Examples of the acid used for neutralizing the tertiary amine include hydrochloric acid, sulfuric acid, and methyl sulfate. The tertiary amine used in the present invention is preferably used in the form of an amine salt neutralized with hydrochloric acid, sulfuric acid, or methyl sulfate. In the neutralization step, the tertiary amine which has been neutralized in advance may be dispersed in water, or the tertiary amine may be added in a liquid or solid state to an aqueous acid solution. Of course, the tertiary amine and the acid component may be simultaneously added. Further, as the quaternizing agent used for the quaternization of the tertiary amine, methyl chloride-dimethyl sulfate can be mentioned. The tertiary amines represented by the above general formulas (5) to (7) are quaternized with dimethyl sulfate, and those represented by the following general formulas (10) to (12) are exemplified.

θΟ. Η ₂ ΟΪ ₂ , ^ CHaCHOH

R ^ OOCH ^^ X ^ ^CH 3 ^S ° 4- ⁽¹⁰ )

I ^ COOCi ^ CH ^, CH ₂ CH ₂ OH

 N CH3SO4 "(11)

HOCH ₂ CH ₂ Z, _C H ₃

(a) R ¹ constituting the component is a residue obtained by removing the force Rupokishiru groups from fatty acids having 10 to 24 carbon atoms, saturated fatty acids, unsaturated fatty acids, derived from Re Izu linear fatty acids, branched fatty acids Group. In the case of unsaturated fatty acids, cis form and trans form exist. The mass ratio is preferably cis-form / trans-form = 25/75 to 80/20, and more preferably 40 to 60,720. Is a fatty acid as a of R ¹ material, stearic acid, palmitic acid, myristic acid, lauric acid, Orein acid, elaidic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partially hydrogenated tallow fatty acid (Iodine value 10 to 60). Among them, a plant-derived stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid are combined in a predetermined amount, and the saturated / unsaturated ratio is 95Z5 to 5050 (mass ratio). The ratio is 40 60-80Z20, the iodine value is 10-50, the ratio of 18 carbons is 80% by mass or more, the fatty acids with 20 carbons are 2% by mass or less, and the fatty acids with 22 carbons are 1% by mass or less. It is preferable to use a fatty acid composition adjusted so that

The compounds of the general formulas (3) and (4) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition with methylgenolamine. At this time, it is preferable that the compounds (3) and (4) are synthesized so that the abundance ratio of the compounds is 991 to 50/50 by mass. When using the quaternary compound, Although quaternized with methyl, the abundance ratio of quaternized and non-quaternized esteramine is as follows: quaternized compound, non-quaternized esteramine (mass ratio) = 99/1 to 50/50 It is preferable to synthesize so that

 The compounds of the general formulas (5), (6) and (7) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition with triethanolamine. At that time, based on the total amount of (5), (6) and (7), (5) is 1 to 60% by mass, (6) is 0.5 to 98% by mass, and (7) is 0.1 Preferably, it is present at a ratio of 5 to 20% by mass, (5) is present at a ratio of 5 to 20% by mass, (6) is present at a ratio of 0.5 to 30% by mass, and (7) is present at a ratio of 70 to 95% by mass. Is particularly preferred. Further, when the quaternary compound is used, it is quaternized with dimethyl sulfate to obtain the compounds of (10), (11) and (12). (10), (11), and (12) are present in a proportion of 1 to 60% by mass, and (11) is based on the total amount of (10), (11), and (12). It is preferable that 25 to 98% by mass, (12) be present in a ratio of 0.1 to 40% by mass, (10) be 30 to 60% by mass, (11) be 10 to 55% by mass, (12) Is more preferably present in a proportion of from 5 to 35% by weight. Further, the quaternary compound and the non-quaternized esteramine may be present in a ratio of quaternary non-quaternized esteramine (mass ratio) = 70Z30 to 99Z1. However, in order to suppress the hydrolysis of the ester group contained in (10) to (12), it is preferable to reduce the proportion of non-quaternized (5) to (7). The compounds of the general formulas (8) and (9) were prepared from the above fatty acid composition and an adduct of N-methylethanolamine and acrylonitrile by a known method [J. Org. Chem., 26, 3409, (1960)]. [2] can be synthesized by a condensation reaction with 1- (2-hydroxyethyl) 1-methyl-1,3-propylenediamine. At this time, it is preferable to synthesize the compounds (8) and (9) such that the mass ratio of the compounds (9) and (9) is 99Ζ1 to 50Ζ50. Furthermore, when the quaternized product is used, the quaternized product is quaternized with methyl chloride. However, the ratio of the quaternized product to the non-quaternized esteramine is changed to the quaternized / unquaternized esteramine (mass It is preferable that the composition is made so that the ratio is 99 to 1Ζ50Ζ50.

The amount of the component (a) is 1 to 30% by mass based on the total amount of the composition, and is preferably 4-20% by mass. If the amount is too large, it is difficult to keep the viscosity after hydrolysis at a low level. On the other hand, if the amount is less than 1% by mass, it is necessary to use a large amount of the softener composition in order to secure the flexibility performance in actual use.

Used in the present invention component (b) is a silicone is 0.5 specific gravity at 25 ° C 96~1. 10, viscosity is 5, 000 mm 500 exceed ² / s, 000mm ² Z s or less, one They can be used alone or in combination of two or more. The specific gravity of the silicone used in the present invention is an important factor for keeping the viscosity of the flexible base material after hydrolysis low, and it is necessary that the specific gravity of the silicone is in the range of 0.96 to 1.10 at 25. , Preferably 0.97 to 1.07, more preferably 0.98 to 1.05.

The viscosity of the silicone at 25 ° C must be more than 5,000 mm ² Zs and less than 500,000 mm ² / s, and more than 5, OO Omm ² / ^ and less than 200,00 Omm ² Zs It is preferable that If the viscosity is 5,000 mm ² / s or less, the flexibility performance may decrease, and if it exceeds 500,000 mm ² / s, the viscosity of the liquid softener composition may increase. Viscosity of the silicone itself is 5, 00 Omm ² exceeds the Zs 500, 000 mm ² Z s but less, in order to improve the actual handling property, low-viscosity silicone, ethanol, isopropoxy propanol, butyl carbitol, It may be diluted with a solvent such as 1,3-butanediol, ethylene glycol, dipropylene glycol, phenoxyethanol, and hexanediol. As for the viscosity of silicone, the numerical value as it is described in the manufacturer's catalog was used. Unless otherwise stated, the value obtained by multiplying the value measured using a B-type viscometer (BL viscometer manufactured by TOK I MEC) at 25 ° C with the specific gravity is multiplied, and values less than 1,000 are rounded down. Displayed. The refractive index of the silicone used in the present invention is preferably in the range of 1.35 to 1.44. Examples of the silicone include dimethylpolysiloxane, amino-modified silicone, amide-modified silicone, polyether-modified silicone, epoxy-modified silicone, silicone-modified silicone, aminopolyether-modified silicone, and amide polyether silicone. In order to suppress yellowing of the treated cloth, an amino-modified silicone having an amino equivalent of not more than 10,000, preferably not more than 5,000 is preferred. Epoxy-modified silicone having an epoxy equivalent of 4,000 or less, preferably 1,000 or less is preferred to keep the texture of the treated cloth good, and the carboxy equivalent is kept low to keep the texture of the treated fabric good. Preference is given to carboxy-modified silicones of 3,000 or less, preferably 2,000 or less. In addition, amide-modified silicone and polyether-modified silicone are preferable, and polyether-modified silicone is particularly preferable.

 As the polyether-modified silicone, those represented by the following general formulas (1) and (2) are preferable.

CH ₃

Si-CH ₃ (1)

CH₃

CH ₃

(CH ₂ ) _L -0- (C ₂ H ₄₀ ) _p- (C ₃ H ₆₀ ) _q -X

(Wherein, n is 50 to: L 0,000, preferably 100 to 10,000, more preferably 160 to 10,000, m is 1 to: a number represented by L 00, and L is 1 To 5, p is 1 to 50, q is a number represented by 0 to 50, and X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

CH 3 CH, CH ₃

x- SiOH- Si Si— R—— (OC ₂ H ₄ ) _p- (OC ₃ H ₆ ) _q -OR- X (2)

CH, C CH 3

(Wherein, s is 1 to; L is 0,000, t is a number of 1 to 1,000, p, Q and X have the same meanings as above. R is an alkylene group having 1 to 5 carbon atoms. )

 As the silicone, a polyether-modified silicone and an amino-modified silicone represented by the above general formulas (1) and (2) are preferable from the viewpoint of flexibility. Since the amino-modified silicone may cause the treated cloth to yellow, the polyester-modified silicone represented by the general formulas (1) and (2) is more preferable.

The most preferred silicone is a silicone represented by the general formula (1), wherein, in the formula (1), n is 160 to: L 000, m is 1 to 20, p force is 1 to 20, q is a number represented by 0 to 10, and X is a silicone represented by a methyl or ethyl group. Is preferred.

 In the silicone represented by the general formula (1), it is necessary to increase the degree of polymerization of the dimethyl silicone moiety (n) to increase the molecular weight in order to improve the flexibility and slipperiness of the polyether-modified silicone with respect to the cloth. However, accompanying this, when X is hydrogen, the viscosity of the polyether-modified silicone increases significantly, and the handling properties decrease. As a remedy, when X is a methyl or ethyl group, an increase in the viscosity of the polyether-modified silicone can be suppressed. Therefore, the handling properties are improved, and the lower viscosity reduces the ease of blending into the softener.

 Specific examples of the silicone used in the present invention include the following.

Examples of the dimethylpolysiloxane include the following.

TSF451—6000 (GE Toshiba Silicone Co., Ltd., viscosity: 6,000 mm ² / s, specific gravity: 0.98)

TSF451-1M (GE Toshiba Silicone Co., Ltd., viscosity: 10,000 mm ² s, specific gravity: 0.98)

TSF451-3M (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 30,000 mm ² / s, specific gravity: 0.98)

TSF451-5M (GE Toshiba Silicone Co., Ltd., viscosity: 50,000 mm ² s, specific gravity: 0.98)

TSF451 -6M (GE Toshiba Silicone Co., Ltd., viscosity: 60,000 mm ² Roh s, specific gravity: 0.98)

TSF451—10M (GE Toshiba Silicone Co., Ltd., viscosity: 1

, Specific gravity: 0.98)

TSF451-20M (GE Toshiba Silicone Co., Ltd., viscosity: 200,000 mn ^ Zs, specific gravity: 0.98)

TSF451-30M (GE Toshiba Silicone Co., Ltd., viscosity: 300,000 mm ² Zs, specific gravity: 0.98)

TSF451-50M (GE Toshiba Silicone Co., Ltd., viscosity: 500,000 mm ² Zs , Specific gravity: 0.98)

TSF456—1M (GE Toshiba Silicone Co., Ltd., viscosity: 10,000 mm ² s, specific gravity: 0.97)

YF33-1M (GE Toshiba Silicone Co., Ltd., viscosity: 10,000 strokes ² / s, specific gravity: 0.98)

SH200— 10, OOO cs (manufactured by Dow Corning Toray Co., Ltd., viscosity: 10,000 mm ² Z s, specific gravity: 0.97)

SH200- 12,500 cs (manufactured by Dow Corning Toray Co., Ltd., viscosity: 1.250,000 mm ² / s, specific gravity: 0.98)

SH200-30, OOO cs (manufactured by Dow Corning Toray Co., Ltd., viscosity: 30,000 mm ² / s, specific gravity: 0.98)

SH200—60, OOO cs (manufactured by Dow Corning Toray Co., Ltd., viscosity: 60,000 mm ² s, specific gravity: 0.98)

SH200-100, OOO cs (manufactured by Toray Dow Corning Co., Ltd., viscosity: 100,000 mm ² Zs, specific gravity: 0.98)

SH200-200, OOO cs (manufactured by Toray Dow Corning Co., Ltd., viscosity: 200,000 mm ² / s, specific gravity: 0.98)

BY 1 1-014 (manufactured by Toray Dow Corning Co., Ltd., viscosity: 130000 mm ² Zs, specific gravity: 0.96)

BY 11-026 (manufactured by Toray Dow Corning Co., Ltd., viscosity: 100,000 mm ² / s, specific gravity: 0.98)

 Examples of the amino-modified silicone include the following.

TSF4704 (GE Toshiba Silicone Co., Ltd., viscosity: 40,000 mm ² s, specific gravity: 0.98)

TS F 4705 (GE Toshiba Silicone Co., Ltd., viscosity: 70,000 mm ² Zs, specific gravity: 0.98)

 Examples of the polyether-modified silicone include the following.

XF42-B 5370 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 20,000 mm ² / s, specific gravity: 1.02) XF42-B 5371 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 50,000 mm ² Zs, specific gravity: 1.01)

F Z-2222 (manufactured by Nihon Rikiichi Co., Ltd., viscosity: 250,000 mm ² / ^ specific gravity: 1.01)

FZ-2101 (manufactured by Nippon Tunicer Co., Ltd., viscosity 7,600 mm ² Z s, specific gravity: 1.05)

FZ-2108 (manufactured by Nippon Tunicer Co., Ltd., viscosity: 20,000 mm ² / s, specific gravity: 1 · 00)

FZ-2109 (manufactured by Nippon Tunicer Co., Ltd., viscosity: 5,500mm ² Zs, specific gravity: 1.00)

 Epoxy-modified silicone

TS F 4730 (GE Toshiba Silicone Co., Ltd., viscosity: 8,000 mm ² / s, specific gravity: 0.98)

L-1 9300 (manufactured by Nippon Rikiichi Co., Ltd., viscosity: 6,000 mm ² / s, specific gravity: 0.98)

 The amount of the component (b) is 0.5 to 20% by mass, and preferably 0.5 to 8% by mass, based on the total amount of the composition. If the amount is too small or too large, the viscosity after storage becomes high.

 The component (c) used in the present invention is an alcohol ethoxylate in which the ratio (mass ratio) in which the monovalent hydrocarbon group is a linear Z-branched chain is 5/95 to 95Z5. Two or more kinds can be used in an appropriate combination so as to obtain such a ratio. In order to stabilize the viscosity of the liquid softener after the decomposition of the soft base material, alcohol ethoxylates in which monovalent hydrocarbon groups (alkyl and alkenyl groups) are linear and alcohol ethoxylates in which branched chains are used It is necessary that the ratio (mass ratio) of the linear / branched chain is 5/95 to 95/5, preferably in the range of 5/95 to 50Z50, more preferably 1090 to 50/50. It is in the range of 50.

Examples of the monovalent hydrocarbon group include an alkyl group and an alkenyl group.The number of carbon atoms in these groups is 8 to 20 in both straight and branched chains. May be used in combination. When using an alkenyl group In this case, either the cis form or the trans form may be used, or a mixture thereof may be used, but the cis form is preferred.

 The alcohol ethoxylate used in the present invention may be a mixture of a separately synthesized straight-chain alcohol ethoxylate and a branched-chain alcohol ethoxylate, or a mixture of a straight-chain higher alcohol and a branched-chain higher alcohol. After mixing, a predetermined mole number of the alkylene oxide may be added. Furthermore, using butene and propylene as raw materials

The trimer or tetramer may be prepared, and alkylene oxide may be added to the alcohol obtained by the oxo method.

 Alkylene oxide added to a higher alcohol having a linear or branched monovalent hydrocarbon group is preferably ethylene oxide, propylene oxide, or butylene oxide, and the mass ratio of ethylene oxide in alkylene oxide Is preferably 50 to 100% by mass. When ethylene oxide and propylene oxide or butylene oxide are added together, they may be added at random or in blocks. The number of moles of ethylene oxide to be added is preferably from 100 to 100 mol, more preferably from 20 to 80 mol, and particularly preferably from 30 to 60 mol.

 Specific examples of higher alcohols used as raw materials include Exal manufactured by Exxon Chemical Co., Ltd., 1 ^ tens 01 series manufactured by 883 ?, Oxocol C13 manufactured by Kyowa Hakko Kogyo Co., Ltd., and Ge napo manufactured by Hoechst AG. One series (C series, T series), Shell Dobanol series, CONDEA (S ASOL) I SOFOL series, etc. can be used. As the raw material alcohol, either a primary alcohol or a secondary alcohol can be used, but the dispersibility of the composition is better when the primary alcohol is used.

Specific examples of alcohol ethoxylates include Emarex series manufactured by Nippon Emulsion, Inc., Emulmin series manufactured by Sanyo Chemical Co., Ltd., TDA series, TA series manufactured by Lion Chemical Co., Ltd., and Nippon Shokubai Co., Ltd. Examples thereof include a softanol series such as Sofu Nol 300, a Lu tenso 1 series manufactured by BAS F, and an Emu 1 an series. These alcohol ethoxylates may be used such that the mass ratio of the above-mentioned straight-chain Z-branched chains is 5/95 to 95Z5. it can. In addition, the above-mentioned compounds contain, as a reaction by-product, alcohols and polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol as raw materials within 10% by mass of alcohol ethoxylate. May be.

 The amount of component (c) is 0.1 to 10% by mass, and preferably 0.5 to 5% by mass, based on the total amount of the composition. If the amount is too small, the viscosity after storage increases, and if it is too large, the initial viscosity immediately after production increases.

 The liquid softener composition of the present invention contains (d) a quaternized alkanolamine having a total carbon number of 4 to 10 in order to reduce the viscosity of the liquid softener composition after hydrolysis to a lower viscosity. It is preferable that they are contained, and one kind can be used alone, or two or more kinds can be used in appropriate combination. (d) Examples of the component alkanolamine as a component include methylgenoylamine, triethanolamine, diethanolamine and the like. Examples of the quaternizing agent for alkanolamine include methyl chloride and dimethyl sulfate, and specific examples thereof include compounds represented by the following general formulas (13) and (14).

HOCH ₂ CH ₂ , NO CH ₂ CH ₂ OH

N CH ₃ SO _A "(13)

HOCH ₂ CH ₂ , CH ₃

The amount of the quaternized alkanolamine (d) is preferably from 0.4 to 10% by mass based on the total amount of the composition in order to keep the viscosity of the flexible base material after hydrolytic decomposition at a low level. It is particularly preferably 0.5 to 5% by mass. If the amount is less than 0.4% by mass, the effect of lowering the viscosity may be reduced. If the amount exceeds 10% by mass, the flexibility may be reduced.

In addition, the liquid softener composition of the present invention includes the following compounds for the purpose of improving viscosity stability, improving performance, adding functions, improving manufacturability, improving appearance, and improving aroma, as long as the object of the present invention is not impaired. The following various components usually blended in the softener composition can be blended as (f) component. These various components may be used alone or in combination of two or more. They can be used in appropriate combination.

 The cationic surfactant is mainly used for the purpose of improving flexibility, and examples thereof include mono-, di- and trialkyl cations having 1 to 3 long-chain hydrocarbon groups. Specifically, two long-chain alkyl groups containing 10 to 22 carbon atoms, one long-chain alkyltrimethylammonium chloride containing one alkenyl group, two long-chain alkyl groups having 10 to 22 carbon atoms, two alkenyl groups Dialkyl long chain alkyldimethylammonium chloride containing, long chain alkyl group having 8 to 22 carbon atoms, and tri long chain alkylmethylammonium chloride containing three alkenyl groups.

 When a cationic surfactant is blended into the liquid softener composition of the present invention, the blending amount is preferably 10% by mass or less, more preferably 0.1 to 10% by mass, based on the total amount of the composition.

 As the amphoteric surfactant, sulfobetaine and carboxybetaine having one or two long-chain groups can be used. The long chain group is a hydrocarbon group, and the hydrocarbon group may contain an ester group, an amide group, or a ether group. Further, the ratio of the saturated / unsaturated hydrocarbon group, the carbon chain length distribution, the mass ratio of the cis-form to the trans-form of the unsaturated group and the like are not particularly limited. It may be a hydrocarbon group derived from a fatty acid or a fatty acid methyl ester which is a raw material of the component (a). Specific examples of the amphoteric surfactant include betaines such as N, N-diacyloxyxethyl-N-methylammonioethyl I-le-fluoroethylcarboxylate, and N-acylo. N-N-Hydroxyethyl-N-methylammoniobetaine, N-Acylamidopropyl N, N-Dimethylammoniobetaine, N-Acylamidopropyl-N, N, —Dimethyl-N, I 3-Hydroxypropylammoniobein can be used. The long-chain groups include single-chain and double-chain groups, and they can be used alone or as a mixture. In addition, the above compounds contain a small amount of aminobetaine such as a compound whose nitrogen atom is not quaternized, a raw material alkanolamine, a neutralized product thereof, and a quaternized product thereof. May be included. These may be used alone or in combination of two or more.

When an amphoteric surfactant is added to the liquid softener composition of the present invention, the amount is preferably 10% by mass or less, more preferably 0.1 to 5% by mass, based on the total amount of the composition. It is preferably 0.1 to 3% by mass.

 As the hydrocarbon, liquid paraffin such as liquid paraffin at room temperature or paraffin having a melting point of 70 to 30 ° C can be used in the composition at 10% by mass or less, preferably 0.1 to 3% by mass. .

 Solid oils and fats such as wax and polyurethane can be used as a control agent for improving texture and smoothness and for absorbing and releasing water. Waxes include hydrocarbons selected from alkanes, alkenes, and petroleum waxes, as well as animal and plant waxes.

One type may be used alone, or a mixture of two or more types may be used.

'' When the solid fat is an alkane, the one with 22 or more carbon atoms is most preferred.Specifically, decosan, trichosan, tetrachosan, penyukosan, hexakosan, heppukosan, oktacosan, nonacosan, Triacontan, Hentriacontan, Dotriacontan, Tritriacontan, Tetratriacontan, Pentatriacontan, Hexatriacontan, Hepbeatriacontan, Octatriacontan, Nonatriacontan and the like. Further, the alkane may have a hydrocarbon bonded in a three-dimensional manner such as linear, branched or polyalkylene.

 When the solid fat is an argen, it is preferably one having 24 or more carbon atoms. Specifically, 1-tetracosene, 1-hexacocene, 11-year-old cocene, 1-triacocene, 1-dotriacene , 1-tetratriacontene, 1-hexatriacontene, 1-year-old kutatriacontene, 1-tetracontene and the like. When the solid fat is petroleum wax, paraffinic powder having a melting point of 40 ° C. or more, microcrystalline wax, and petrolatum are most preferable. Specific examples of commercially available petroleum waxes include HNP-3 and HNP— 12, HNP—14G, SP—0160, SP-1035, Hi-Mic—1045, Hi—Mic—2045, JP—1500, JP—105, JP—131T (all Nippon Seiki Co., Ltd.).

When the solid fat is an animal or plant wax, specific examples thereof include candelillax, carnauba wax, hydrogenated jojoba wax, wood wax, beeswax, and whale wax. The above compounds can also be used in the form of emulsions. Ingredient On the other hand, on the other hand, high melting point polyethylene emulsion (Eponol 900) and Polyurethane Emulsion (UPM-212HN) manufactured by Sharp Oil & Fats Co., Ltd. T INOTEX FS A) etc. can be used.

 When a solid resin such as wax is blended with the liquid softener composition of the present invention, the blending amount is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 0.1% by mass or less based on the total amount of the composition. 1-5% by mass.

 In order to control the viscosity of the composition, inorganic or organic water-soluble salts can be used. Inorganic or organic water-soluble salts include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, aluminum chloride, sodium sulfate, magnesium sulfate, potassium sulfate, sodium nitrate, magnesium nitrate, sodium p-toluenesulfonate, and glycol. Examples include sodium acid, sodium acetate, potassium acetate, sodium glycolate, sodium acetate, potassium acetate, potassium glycolate, sodium lactate, and the like. Preferred are calcium chloride, magnesium chloride and sodium chloride. The amount is preferably 3% by mass or less, more preferably 0.01 to 2% by mass, and particularly preferably 0.05 to 1% by mass based on the total amount of the composition. The salt may be added at any step in the production of the emulsion composition.

 However, when the concentration of the components (a) and (b) in the liquid detergent composition is high, it is preferable to add the salt in two or more portions by increasing the salt concentration in order to keep the viscosity low. More preferably, the amount is 0.5% by mass or less during the production of the composition, and 0.5% by mass or less after the production. The viscosity of the composition can be reduced by increasing the amount added after the production compared to the amount added during the production.

 An alcohol having 1 to 10 carbon atoms can be blended for the purpose of improving the handleability of the production of the liquid detergent composition, stabilizing at a low temperature, and making the composition transparent. In particular, it may be used as a reaction solvent, a slurry solvent, or a diluting solvent for the components (a) and (b) in order to improve the handleability of the components (a) and (b). May be carried in.

Specific examples of alcohols having 1 to 10 carbon atoms include ethanol, isopropano Propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-pentanediol, hexylene glycol, trimethylpentenediol, benzyl alcohol, diethylene glycol monobutyl ether, glycerin, 2-phenoxyethanol , 2-phenylethanol, and the like.

 The alcohol having 1 to 10 carbon atoms is generally contained in an amount of 0 to 15% by mass, preferably 0.5 to 10% by mass, based on the total amount of the composition. As the lower alcohol, those modified with a denaturant such as sodium benzoate, 8-acetylated sucrose, brucine, orange, citrus can be used.

 In order to make the composition transparent, monools, C6 diols, C7 diols, octanediol isomers, and butanediol derivatives described in Japanese Patent Application Laid-Open No. 2000-50055 may be used. , Trimethylpentanediol isomer, ethylmethylpentanediol isomer, propylpentanediol isomer, dimethylhexanediol isomer, ethylhexanediol isomer, methylheptanediol isomer, octanediol isomer, nonane Diol isomers, alkyl glyceryl ethers, di (hydroxyalkyl) ethers, aryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols and derivatives, C3-C7 diol alkoxylation derivatives, aromatic diols, and Unsaturated diols and the like can be used. Particularly preferred main solvents are hexanediols such as 1,2-hexanediol and 2-ethyl-1,3-hexanediol, and 2,2,4-trimethyl-1,3 —Pentangdiol, such as diol, can be used. The compounding amount is preferably 40% by mass or less, more preferably 10 to 35% by mass, and particularly preferably 12 to 25% by mass based on the total amount of the composition.

Further, by blending an antioxidant or a reducing agent, it is possible to improve the aroma and color stability of the liquid detergent composition. Specific examples include ascorbic acid, a mixture of ascorbic acid palmitate, propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citrate. Mixtures, tertiary butyl hydroquinone, natural tocopherols, long chain esters of gallic acid (C8-C22), such as dodecyl gallate, chivasudi Irganox compounds available from Altichemical Co., Ltd., preferably Irganox 3125, Irganox 1425, Irganox 3114, and mixtures thereof, isopropyl citrate, 4,5-dihydroxy-m-benzenesulfone available from Kodak Also included are the acids and their sodium salts, which are the chemical name for evening iron.

 The content of the antioxidant is preferably 1% by mass or less, more preferably 0.0001 to 0.5% by mass, based on the total amount of the composition. The reducing agent can be used in an amount of preferably 3% by mass or less, more preferably 0.0001 to 2% by mass. At the time of use, the component (a) may be added in any number of times during the production of the component, after the production, before and after the production of the composition, etc. within a range that does not impair the effects of the present invention.

 Further, the compounds described in the following 1) to 4) can be used singly or in combination of two or more kinds for the purpose of enhancing the preservative power and the bactericidal power.

 1) As the isothiazolone-based organic sulfur compound, a compound containing a 3-isothiazolone group is preferable. These compounds are disclosed in Lewis et al., U.S. Pat. No. 4,265,899, issued May 5, 1981. Examples include 5-chloro-2-methyl-4-1-isothiazolin-3-one, 2-n-butyl-3 ^^ sothiazolone, 2-benzyl-13-isothiazolone, 2-phenyl-3-isothiazolone, 2 _Methyl_4,5-dichroic isothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. More preferred preservatives' fungicides are 5-black

It is a water-soluble mixture of 2-methyl-4-isothiazolin-3-one and 2-methyl-1-isothiazoline-3-one, and more preferably about 77% by mass of 5-methyl-2-methyl-14. It is a water-soluble mixture of -isothiazolin-3-one and about 23% by mass of 2-methyl-4-isothiazolin-3-one. Commercially available products can be used, such as Rohm & Haas Caisson CGZI CP (approximately 1.5% by mass aqueous solution) and Junsei Chemical's Jyunside 5 series such as Jyunside 5.

2) Benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazoline-3-one, 2-methyl-4,5-trimethylene-1-41-isothiazolyl. And dithio-2,2-bis (benzmethylamide) can also be used as an analogous compound, and they can be used in any mixing ratio. Examples of such compounds include Proxel series manufactured by Avicia Co., Ltd. [BDN (active component: 33% by mass), BD20 (active component: 20% by mass), XL-2 (active component: 10% by mass), GXL ( Commercially available products such as effective component 20% by mass), LV (effective component 20% by mass), TN (effective component 60% by mass), and denicide BIT / NI PA can be used.

3) 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-5-nitro-1,3-dioxane, or 2-chloro For example, 2-nitropropane-1,3-diol and the like can be used. Examples of such compounds include BronidoxL manufactured by Henke 1 Company, Bronopo manufactured by Ino1ex Co., Ltd., Bronopol manufactured by Yoshitomi Pharmaceutical Co., Ltd., Myside BT manufactured by Boots, and Miaside manufactured by BASF. Commercial products such as Side Pharma BP and Protect BN manufactured by BASF can be used.

 4) Benzoic acids or phenolic compounds include benzoic acid or a salt thereof, salicylic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl parahydroxybenzoate, ethyl ethyl paraoxybenzoate, propyl paraoxybenzoate, parapropyl benzoate Acid butyl, benzyl paraoxybenzoate, 3-methyl-3-isopropylphenol, o_phenylphenol, 2-isopropyl-15-methylphenol, resorcinol, cresol, 2,6-ditert-butyl-p_crezo Can be used.

The compounding amount of the compounds 1) to 3 ′) is preferably 0.1% by mass or less, more preferably 0.00001 to 0.03% by mass, and particularly preferably 0.00005 to 100% by mass based on the total amount of the composition. 0.02% by mass. The compounding amount of the compound (4) is preferably 3% by mass or less, more preferably 0.01 to 1.5% by mass, based on the total amount of the composition. Also, by using two or more of the above compounds 1) to 4) in combination, the antiseptic and bactericidal activities can be enhanced, and the amount of the expensive compound used can be reduced. Among them, it is especially preferable to use two or more selected from Caisson CGZ ICP, Proxel series BDN, Myaside BT, Protect BN and benzoic acid. Preferably, the amount is 0.001 to 2% by mass, more preferably 0.001 to 1% by mass, and still more preferably 0.005 to 0.5% by mass. is there. The compounds of 1) to 3) above are used for stabilization in the presence of metal ions such as zinc, copper, calcium, and magnesium, or added to the composition as a solution of ethylene glycol, propylene glycol, or dipropylene dalycol. Preferably. The liquid softener composition of the present invention further comprises a dimethylpolysiloxane other than the component (b) for the purpose of further improving the water absorbency of the fiber, iron-slip property, anti-wrinkle property, and color of a faded garment. Silicones selected from modified dimethylpolysiloxanes having various organic functional groups can be used alone or in any proportion as a mixture of two or more.

 When the silicone is a modified dimethylpolysiloxane, the organic functional groups are polyester, amino, amide, alkyl, aralkyl, carboxyl, fluoroalkyl, higher alcohol esters, epoxy, carbinol, mercapto, phenol, methacrylic or amidoboryl. Modified silicones such as mono-ter and alkyl alcohol can be used, and those modified by two or more types can also be used. The bonding position of the organic functional group may be either a side chain or a terminal with respect to the main chain of dimethylpolysiloxane, and may be at one terminal or both terminals when bonding to the terminal. In addition, the mass ratio of the organic functional group to dimethylpolysiloxane can be arbitrary, and is not particularly limited. Further, as the modified dimethylpolysiloxane, hydrogenated dimethylpolysiloxane or dimethylpolysiloxane hydroxide, which is a precursor for introducing an organic functional group, may be used alone or with a modified dimethylpolysiloxane having an organic functional group. You may mix and use.

 Various silicones may be used as an oil or an emulsion, and when a silicone elastomer powder is used, it may be used as a dispersion. The refractive index of these silicones is between 1.30 and 1.55. These silicone compounds can be used in an amount of preferably 10% by mass or less, more preferably 0.1 to 10% by mass, and particularly preferably 0.2 to 8% by mass, based on the total amount of the composition.

Further, for the purpose of improving the appearance of the liquid softener composition, an arbitrary dye and / or pigment can be blended. Preferably, acid dye, direct dye, basic dye, reaction And one or more water-soluble dyes selected from the group consisting of a water-soluble dye and a mordant / acid mordant dye. Specific examples of dyes that can be added are described in Handbook of Dyes (edited by The Society of Synthetic Organic Chemistry, Japan, published on July 20, 1945, Maruzen Co., Ltd.). From the viewpoint of the storage stability of the liquid softener composition and the dyeing property to fibers, acid dyes having at least one type of functional group selected from a hydroxyl group, a sulfonic acid group, an amino group, and an amide group in the molecule.

Preferred are direct dyes and reactive dyes. The compounding amount is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the total amount of the composition. Dyes used in the liquid softener composition of the present invention include JP-A-2001-348784 and JP-A-20-348784.

JP-A-01-181972, JP-A-11-43865, JP-A-10-77576, JP-A-9-1250085, JP-A-8-27669, JP-A-7-18573, Dyes described in JP-A-6-123082 and JP-A-6-123081 can also be used.

 Perfume ingredients can be added for the aroma of the composition. A list of perfume raw materials used as perfumes can be found in various publications, such as "Perfume and F1 avor Chemicals", Vol. I and II, Steffen Act and er, Allured Pub. Co. (1994 ) And "Synthetic Fragrance Chemistry and Product Knowledge", Motoichi Indo, Kagaku Kogyo Nipponsha (1996) and "Perfume and Flavor Materials of Natura 1 Origin", Steffen Arc and er, A llured Pub. Co. (1 994) and "Encyclopedia of Fragrance", edited by Japan Fragrance Association, Asakura Shoten (

1989) and "Perfumery Material Mathematics Perfourmance V. 3.3", Boelens Armoma Chemical Informates Service (1996) and "F1oweroils and Floral Compounds I" n Perfume r yj, Danuette Lajaujis Anon is, Allured Pub. Co. (1993), etc., and each of them is incorporated herein by reference.

The liquid softener composition of the present invention preferably has a pH in the range of 1.0 to 6.0, more preferably pH 1.5 to 4.5, for the purpose of suppressing hydrolysis of the ester group. It is particularly preferable that the pH be in the range of 2.0 to 4.0. For the pH adjustment, any inorganic or organic acid and alkali can be used. Hydrochloric acid, sulfuric acid, phosphoric acid, alkylsulfuric acid, benzoic acid, p-toluenesulfonic acid, acetic acid, citric acid, malic acid, carboxylic acid such as succinic acid, lactic acid, glycolic acid, sodium hydroxide, diethanolamine, triethanol Examples include amines. Of these, hydrochloric acid, methyl sulfate, sodium hydroxide, diethanolamine, and triethanolamine are preferred. In addition to the above-mentioned compounds, viscosity control and stabilizers, polymer compounds, hydrotropes, fragrance time control agents such as cyclodextrins, polystyrene emulsion emulsions such as emulsion, opacifiers, shrinkage inhibitors as function improvers , Laundry anti-wrinkle agent, shape retention agent, drape retention agent, ironing improver, oxygen bleach inhibitor, whitening agent, whitening agent, fabric softening clay, antistatic agent, polyvinylpyrrolidone, etc. , A polymeric dispersant, a stain release agent, a scum dispersant, a fluorescent whitening agent such as 4,4-bis (2-sulfostyryl) biphenyl disodium (Tinopearl CBS-X manufactured by Ciba Specialty Chemicals Co., Ltd.), Ciba Specialty Chemicals Co., Ltd. Ciba (registered trademark), TI NOSORB (registered trademark), FR, FD, CI BAFAST (registered trademark), Ben Zothiazole-based UV absorbers, dye fixatives, anti-fading agents such as 1,4-bis (3-aminopropyl) piperazine, stain removers, and cellulase, amylase, protease, lipase, Enzymes such as latinases, foam inhibitors, silk protein powders that can impart functions and textures of silk such as moisture absorption / release properties, surface modified products thereof, and emulsified dispersions can be mixed. Specific examples of these include K-50, K-30, K-10, A-705, S-702, L-710, FP series (made by Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution ( Non-ionic polymer compound composed of polyoxyalkylene units and alkylene terephthalate and / or alkylene isophthalate units, for example, compatible with silk hair G) Soluble S (manufactured by Maru-Farucos Co., Ltd.) A re-contamination inhibitor such as FR 627 manufactured by Chemical Industry Co., Ltd. and SRC-1 manufactured by Clariant Japan Co., Ltd. can be suitably incorporated in an amount of 0.01 to 5% by mass based on the total amount of the composition.

The method for preparing the softener is not particularly limited, and various methods can be used. However, in particular, Japanese Patent Application Laid-Open Nos. 2-681337, 5-32,788, 5-32,789 and 10-237,762 The described method is preferred. That is, a part of the water phase is added to the oil phase containing the components (a) and (b) and the fragrance component, or the oil phase is added to a part of the water phase to form a cationic surfactant. The liquid softener composition of the present invention can be prepared by a method in which the liquid crystal phase is formed, and then the liquid crystal phase is mixed with the remaining aqueous phase to invert the liquid crystal phase.

 The alcohol ethoxylate, which is the component (C), can be in either the aqueous or oily phase. Salts, which are viscosity control agents, can be added in several portions during production. When the aqueous phase is divided and used, it may be added to each aqueous phase or may be added after the production is completed. The above optional components (e and f components to be described later) are selected from an aqueous phase and an oil phase from the viewpoint of handling properties such as solubility. However, those with poor solubility can be added to either phase by using them together with an emulsifier or a solvent. In general, it is preferable to put those with high water solubility in the aqueous phase and those with low water solubility in the oil phase.

 The container for containing the liquid softener composition of the present invention is not particularly limited, but is generally contained in a bottle container made of polyethylene, polypropylene, or polyethylene terephthalate, or a vouch container made of polyethylene or nylon. is there. In recent years, polyethylene or polyethylene terephthalate film on which aluminum or alumina has been deposited has been used as the material of the patch in order to suppress moisture evaporation of the composition and to suppress changes in properties such as viscosity, color tone, and aroma. There is also. Further, it may contain a pigment, an antistatic agent, an ultraviolet absorber, and a slipping agent.

Further, the liquid softener composition of the present invention is used for rinsing after washing is completed in ordinary washing. However, the liquid softener composition may be used alone without a washing step. The detergent in the washing process may be a detergent mainly composed of anionic surfactants, a detergent mainly composed of nonionic surfactants, and may contain other surfactants and function improvers, and is commercially available in Japan and overseas. All detergents can be used. From the viewpoint of imparting flexibility to the textile product, the concentration of the component used in finishing the textile product is based on the amount of the component (a) with respect to the amount of water used to finish the textile product filled in the rinsing bath in the rinsing step. It is preferable to use an amount such that the total concentration is 10 to 100 ppm. More preferred Or 20-: L 00 ppm. However, it is most preferable that the user adjusts to the desired amount in consideration of the washing machine, the amount of textiles, the amount of water, and the like.

 The liquid softener composition of the present invention can be used in all commercially available products such as a two-layer washing machine, a fully automatic washing machine, and a washing machine with a drying function. Washing machines with a drying function are available from various washing machine manufacturers, including “Washing and Drying White Promise NW—D8BX Co., Ltd., manufactured by Hitachi, Ltd.” and “Homelandry Rapid Rapid Galaxy 21 TW-741 EX” "Made by Toshiba", "Lab NA-FD 8002 made by Matsushita Electric Industrial Co., Ltd.", "Mat-dried carat MAW-V8TP made by Mitsubishi Electric Corporation", "Aqua whitening washing AW-801HVP made by Toshiba", "Top open drum AWD-A845 Z manufactured by Sanyo Electric Co., Ltd.".

 ADVANTAGE OF THE INVENTION According to the liquid softening agent composition of this invention, the viscosity stability after the soft base material containing an ester group is hydrolyzed by aging or high temperature storage can be ensured, it is excellent in imparting flexibility, It is possible to obtain a liquid softener composition which improves the slipperiness and gives a smooth wearing comfort.

 [Examples 1 to 25, Comparative Examples 1 to 8]

(A) Components heated and dissolved at 60 ° C are as shown in Tables 6 to 8, and (b) Components heated at 60 ° C are as shown in Tables 6 to 8. Then, add the amount shown in Tables 6 to 8 of the perfume of the component (e) shown in Table 3 to a glass container having an inner diameter of 120 mm, and stir at 1000 rpm for 30 seconds using Sriwanmo overnight. did. As the stirring blade, a paddle blade having three 100 mm long blades at 30 mm intervals was used. Next, an aqueous solution containing the component (c) dissolved in the liquid softener composition in the amounts shown in Tables 6 to 8 was prepared, and 40% by mass of the aqueous solution was added to the container, and 1000 r Stirred at pm for 3 minutes. Then, the remaining 60% by mass aqueous solution was further added and stirred for 2 minutes. Once the sandbox was stopped once, 2% by mass of a 10% by mass calcium chloride solution was added and stirred for 30 seconds. If necessary, adjust the pH to 3.0 with 5 mol ZL hydrochloric acid (Kanto Chemical Co., Ltd.) and 5 mo 1 / L sodium hydroxide (Kanto Chemical Co., Ltd.). Ion-exchanged water was added to the mixture, and the mixture was further stirred for 30 seconds to prepare 1000 g of a liquid softener composition. Further, when the component (d) is added in Example 4 or later, the amount shown in Tables 6 to 8 should be changed to ( c) It was added to the aqueous solution together with the components. The components (f) to be blended in Examples 16 to 25 described in Tables 8 and 9 are (f-1) to (ί25), (f-31) to (f-33) are components of (c) (F-41)-(f-49), (f-61)-(: f_68) are added at the same timing as the components (a) and (b), and (51) to (f-57) were added at the same timing as the calcium chloride aqueous solution. The amounts of the components (a) to (f) are as shown in Tables 6 to 9.

 With respect to the obtained liquid softener composition, the flexibility and the viscosity of the liquid softener composition after hydrolysis were evaluated. The results are shown in Tables 6-9. The following (a) to (d) components were used.

 (a) Synthesis of components

 Synthesis of (a-1)

a— 1— 1. Synthesis of methyl ester

 2.5 kg of commercially available methyl fatty acid consisting of 75% by mass of methyl oleate, 16% by mass of methyl linoleate and 9% by mass of methyl stearate (manufactured by Lion Corporation, pastel Ml 82, molecular weight 296) 2.5 g of nickel catalyst (0.1% by mass! Methyl fatty acid) was charged into a 4 L autoclave, and nitrogen gas exchange was performed three times. Then, the rotation speed was adjusted to 800 rpm, and about 77 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was completely consumed, the mixture was cooled, the catalyst was removed using a filter aid, and hydrogenated palm fatty acid methyl was obtained. The molecular weight determined from the saponification value was 297. The composition of methyl fatty acid determined by gas chromatography (GC) was 36% by weight of methyl stearate, 36% by weight of methyl elaidate (trans form), 28% by weight of methyl oleate (cis form), and linoleic acid. The methyl content was 0% by mass, and the trans-isomer ratio of the unsaturated fatty acid methyl ester was 56/44 (mass ratio). The unsaturated alkyl group was measured by GC (gas chromatography) according to the following method.

Model: Hitachhi FID Gas chroma G-3000, Column: GL Science TC-70 (0.25 mm I. Dx 30)

Temperature: Column 150 ° C to 230 ° C, Zmin at heating rate 10; Injector and detector 24 Ot :, Column pressure: 1. O kg fZcm ² a- 1-2. Synthesis of alkanolamine esters and their quaternary compounds

 To 489 g (1.65 mol) of hydrogenated palm fatty acid methyl prepared in (a-1-1) above, 137 g (0.46 mol) of methyl stearate and 156 g (0.58 mol) of methyl palmitate were added. ) Mixed with fatty acid methyl ester (unsaturated fatty acid methyl Z saturated fatty acid methyl 40Z60), triethanolamine 250 g (1.67 mol), magnesium oxide 0.51 g, 14% sodium hydroxide aqueous solution 3 69 g was placed in a 2 L four-necked flask equipped with a stirrer, condenser, thermometer and nitrogen inlet tube, and after purging with nitrogen, nitrogen was allowed to flow at a flow rate of 0.52 LZmin. . 1. The temperature was raised to 190 ° C at a rate of 5 ° CZmin, and the reaction was performed for 6 hours. After confirming that the unreacted methyl ester was 1% by mass or less, the reaction was stopped. The fatty acid salt derived from the catalyst was removed by filtration from the obtained product to obtain an intermediate alkanolamine ester. The amine value was measured and the molecular weight was determined to be 582.

270 g (0.46 mol) of the obtained alkanolamine ester was placed in a four-necked flask equipped with a thermometer, a dropping funnel, and a condenser, and was purged with nitrogen. Then, the mixture was heated to 85 ° C, and 57.4 g (0.45 mol) of dimethyl sulfate was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was maintained at 90 ° C, and the mixture was stirred for 1 hour. After the completion of the reaction, when the temperature becomes 70 ° C or less, about 62 g of undenatured ethanol (manufactured by Nippon Ethanol Co., Ltd.) is dropped to prepare an ethanol solution having a solid content of about 85% by mass. Ox CY-115 (manufactured by Lion Corporation) and dibutylhydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd.) were added to a concentration of 10 ppm, respectively. The obtained reaction product contains 70% by mass of a cationic compound containing an ester group in the molecule of the component (a), and is composed of a monoester ammonium salt, a diester ammonium salt, and a Ztriester ammonium salt. Salt was contained at 28 53-19 (mass ratio). This compound corresponds to the compounds represented by the general formulas (11), (10) and (12). This ethanol solution contains a total of 9.0% by mass of non-quaternized monoesteramine, diesteramine and triesteramine, and the ratio is 1Z9 / 90 (mass ratio). I was This compound corresponds to the compounds represented by the general formulas (6), (5) and (7). In addition, two by-products 0.0% by mass.

 Synthesis of (a-2)

a-2- 1. Synthesis of methyl ester

 75% by weight of methyl oleate, 16% by weight of methyl linoleate and 9% by weight of methyl stearate Methyl palm fatty acid (manufactured by Lion Corporation, pastel Ml 82, molecular weight 296) 2.5 kg, 2.5 kg of commercially available stabilized nickel 1.9 g (0.075% by mass / fatty acid methyl) of the catalyst was charged into a 4 L autoclave, and the atmosphere was replaced with nitrogen gas three times. Next, the rotation speed was adjusted to 800 rpm, and about 40 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was completely consumed, the mixture was cooled, the catalyst was removed using a filter aid, and hydrogenated palm fatty acid methyl was obtained. The molecular weight determined from the saponification value was 296. The fatty acid methyl composition determined by GC was 14% by weight of methyl stearate, 26% by weight of methyl elaidate (trans form), 60% by weight of methyl oleate (cis form), and 0% by weight of methyl linoleate. The trans / cis ratio of the saturated fatty acid methyl ester was 30/70 (mass ratio). The unsaturated alkyl group was measured by GC in the following manner.

Model: Hitachhi FID Gas chroma G-3000 Column: GL Science

TC— 70 (0.25 mm I. Dx 30)

Temperature: Column 150 ° C to 23 O: Heating rate 10 ° CZmin, Injector and detector 240 ° C, Column pressure: 1. O kg fZcm ²

a-2-2. Synthesis of alkanolamine esters and their quaternary compounds

Fatty acid methyl ester (unsaturated fatty acid methyl / saturated fatty acid methyl) prepared by mixing 489 g (1.65 mol) of hydrogenated palm fatty acid methyl prepared in the above (a_2-1) with 352 g (1.18 mol) of methyl stearate Mass ratio of 50/50) and 468 g (3.14 mol) of triethanolamine, 0.65 g of magnesium oxide, 4.68 g of 14% aqueous sodium hydroxide solution with a stirrer, cooler, thermometer and The flask was placed in a 2 L four-necked flask equipped with a nitrogen inlet tube and purged with nitrogen, and then nitrogen was allowed to flow at a flow rate of 0.52 LZmin. The temperature was increased to 190 ° C at a rate of 1.5 CZmin, and the reaction was performed for 6 hours. After confirming that unreacted methyl ester was 1% by mass or less, the reaction was stopped. From the resulting product, a fatty acid salt derived from the catalyst After filtration, an intermediate alkanolamine ester was obtained.

 300 g of the obtained alkanolamine ester was placed in a four-necked flask equipped with a thermometer, a dropping funnel, and a condenser, and was purged with nitrogen. Then, the mixture was heated to 85 ° C., and 0.98-fold mol of dimethyl sulfate was added dropwise to the alkanolamine over 1 hour. After completion of the dropwise addition, the temperature was maintained at 90 ° C, and the mixture was stirred for 1 hour. After the completion of the reaction, when the temperature becomes 70 ° C or lower, ethanol is added dropwise to prepare an ethanol solution having a solid content of 85% by mass. Toluene (manufactured by Sumitomo Chemical Co., Ltd.) was added to a concentration of 100 ppm. The obtained reaction product contains 72% by mass of a cationic compound containing an ester group in the molecule of the component (a), and is composed of a monoester ammonium salt, a nodiester ammonium salt, and a Z triester ammonium salt. Salt was contained at 53/41/6 (mass ratio). This compound corresponds to the compounds represented by the general formulas (11), (10) and (12).

 Synthesis of (a-3)

a— 3-1: Synthesis of alkanolamine esters and their quaternary compounds

 489 g (1.65 mol) of hydrogenated palm fatty acid methyl prepared above in (a-1_1), 98 g (0.66 mol) of triethanolamine, 0.29 g of magnesium oxide, 14% sodium hydroxide Aqueous solution (2 lg) was placed in a 2 L four-necked flask equipped with a stirrer, condenser, thermometer and nitrogen inlet tube, and after purging with nitrogen, nitrogen was allowed to flow at a flow rate of 0.52 LZmin. . 1.5 at the speed of 5 in 1

The temperature was raised to 90 ° C, and the reaction was performed for 6 hours. After confirming that the unreacted methyl ester was 1% or less, the reaction was stopped. The fatty acid salt derived from the catalyst was removed by filtration from the obtained product to obtain an intermediate alkanolamine ester.

300 g of the obtained alkanolamine ester was placed in a four-necked flask equipped with a thermometer, a dropping funnel, and a condenser, and was purged with nitrogen. The mixture was then heated to 85, and 0.98 moles of dimethyl sulfate was added dropwise to the alkano-lamine ester over 1 hour. After completion of the dropwise addition, the temperature was maintained at 90 ° C, and the mixture was stirred for 1 hour. After the reaction was completed, when the temperature reached 70 ° C or less, ethanol was added dropwise to prepare an ethanol solution having a solid content of 85% by mass. Finally, Ferriox CY-115 (manufactured by Lion Corporation) and Butyl hydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd.) was added so that each had a concentration of 100 ppm. The obtained reaction product contains 70% by mass of the component (a), and the monoester ammonium salt Z the diester ammonium salt notrietresterammonium salt is 12/54/34 (mass ratio). ). This compound corresponds to the compounds represented by the general formulas (11), (10) and (12).

 (b) Ingredient

b—1: SH200—100, OOO cs (manufactured by Dow Corning Toray Co., Ltd., viscosity: 100,000 mm ² / s, specific gravity: 0.98)

b-2: TS F 4704 (GE Toshiba Silicone Co., Ltd., viscosity: 40,000 mm ² Zs, specific gravity: 0.98)

b-3: TSF4705 (GE Toshiba Silicone Co., Ltd., viscosity: 70,000 mm ² Zs, specific gravity: 0.98)

b—4: FZ—2109 (manufactured by Nippon Tunicer Co., Ltd., viscosity 5,500 mm ² / s, specific gravity: 1.00)

b-5: XF42-B 5371 (GE Toshiba Silicone Co., Ltd., viscosity: 50,000 mm ² Zs, specific gravity: 1.01)

b-6: FZ-2222 (manufactured by Nippon Uniriichi Co., Ltd., viscosity: 250,000 mm ² Zs, specific gravity: 1.01)

b-7: FZ-2101 (manufactured by Nippon Tunicer Co., Ltd., viscosity: 7,600 mm ² s, specific gravity: 1.05)

b-8: CF 1188HV (manufactured by Toray Dow Corning Co., Ltd., viscosity: 6,000 mm ² / S, specific gravity: 1.01)

b-9: TSF4730 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 8,000 mm ² Z s, specific gravity: 0 · 98)

b-10: L-9300 (manufactured by Nippon Rikiichi Co., Ltd., viscosity: 6,000 mm ² / s, specific gravity: 0.98)

 b— 11 to 15

Also, a silicone having a structure represented by the general formula (1) was used as the component (b).

[table 1]

b- 16 : TSF451-5A (GE東芝シリコーン （株） 製、 粘度： 5mm² Z s、 比重： 0 · 92) ：比較品

b-16: TSF451-5A (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 5mm ² Z s, specific gravity: 0 · 92): Comparative product

b-17: SH3771 (manufactured by Dow Corning Toray Co., Ltd., viscosity: 400 mm ² s, specific gravity: 1.07): comparative product

 [Table 2]

 (c) component

エマレックス 730 (日本ェマルジヨン （株） 製）

Emarex 730 (manufactured by Nippon Emulsion)

Emarex 550 (manufactured by Nippon Emulsion)

Emalgen 130 (manufactured by Kao Corporation)

Emarex 1625 (manufactured by Nippon Emulsion, Inc.)

Emarex 1825 (manufactured by Nippon Emulsion)

Softanol 300 (Nippon Shokubai Co., Ltd.)

ΤΑ400-75 (manufactured by Lion Corporation) Emu l an To 4070 (BASF)

 (d) Ingredient

 d-1: quaternary compound of triethanolamine with dimethyl sulfate (compound of general formula (13))

 d-2: quaternary compound of methylgenolamine with methyl chloride (compound of general formula (14))

In Examples and Comparative Examples, flavors shown in Table 3 were blended as component (e).

3]

 * Benzyl benzoate 50% by weight solution

The components blended in the liquid softener composition as optional components are shown in Tables 4 and 5 as component (f). [Table 4]

f-1 C.I. Acid Noto 52 (Hoshinaga Chemical Industry Co., Ltd.

 2 C.I. Acidlet '138 (Rikkanol Milling Red BW, manufactured by Nippon Kayaku Co., Ltd.)

f-3 C 丄 Direct File 86 (Sumitomo Chemical Co., Ltd. Sumilight Supra Turquoise Blue G cone.)

C 丄 Acid Fleur 112 (Nippon Kayaku Co., Ltd., Riki Yarn Milling Ultrasky SE) f-5 C.I. Acid Fleur 62 (Nippon Kayaku Co., Ltd., Ryashiru Kasui Ful®)

6 CI Acid Full 9 (Rakuto Kagaku Kogyo Co., Ltd.) Outside—Lilyant Full—FCF f-7 C 丄 Acid Y P—3 (Chuo Synthetic Chemical quinoline yellow WG—G CONC) f "8 CI Acid II mouth 17 (Nippon Kayaku Co., Ltd. Riki Yasui Peru GG)

U 9 I. Hessic Yellow 36 (Dai Nippon Ink Chemical Industry Co., Ltd., Simulon Meta-Niruille-guchi) f-10 I. Food Fur-2 (Hodogaya Chemical Industry Co., Ltd. No.)

 To Ml 1,2. Tansole (Tokyo Kasei Kogyo Co., Ltd.)

f-12 propylene glycol (made by Asahi Denka Kogyo Co., Ltd.)

 M3 ethylene glycol (Mitsubishi Chemical Corporation)

f-14 2,2,4-trimethyl-1,3-pentane (Kanto Chemical Co., Ltd.)

 M5 ethylene ethylene glycol monobutyl ether (Kyowa Hakko Kogyo Co., Ltd.)

 M6 hair alcohol (JUNSEI CHEMICAL CO., LTD.)

 M72-Phenoxyethanol (manufactured by Sanyo Chemical Industries, Ltd.)

 M8 Isoprosol (manufactured by Tokyo Chemical Industry Co., Ltd.)

f-19 2-Phenoxybutanol (manufactured by Sanyo Chemical Industry Co., Ltd.)

 20 Hexylene glycol (Mitsui Petrochemical Co., Ltd.)

 21 Protect BN (BASF)

f-22 Shi'yunsa Me "5 (Junsei Chemical Co., Ltd.)

f ^ 23 Caisson CG (Rohm & Haas)

 24 Neron (Rohm & Haas)

 25 1,2-Hensisothiazo'phosphin-3-one (manufactured by Ahisha Co., Ltd.

 31 Trietano-lamine (manufactured by Mitsui Chemicals, Inc.)

f-32 Methyl sulfate of triethano-amine

f-33 Shi 'etano-lamine (manufactured by Mitsui Chemicals, Inc.)

[Table 5]

柔軟性及びすベり性の評価方法

Evaluation method for flexibility and slipperiness

 (1) Softening treatment with softener

A commercially available cotton towel and polyester satin are washed with a washing machine with dryer (washing and drying white promise NW-D8BX vertical type, manufactured by Hitachi, Ltd.) using a commercially available detergent “Top” (manufactured by Lion Corporation). The pre-treated cloth was used as a test cloth (standard amount of detergent used, bath ratio 30 times, tap water at 45 ° C, 10 minutes after washing, and water rinsing 10 times twice). The polyester satin was dried and then ironed to make the surface smooth, and then used as a test cloth. About 1000 g of pretreated cotton towel and polyester satin (Cotton Olu: Polyester Satin = 7: 3 (mass ratio)) is used in an electric washing machine (washing and drying white promise NW-D8BX vertical type manufactured by Hitachi, Ltd.). Washed with a commercial detergent "TOP" (manufactured by Lion Corporation) (standard amount, bath ratio 30 times, using tap water at 25 ° C, 10 minutes). Rinse Second time, add the softener composition to 30 L of water so that the component (a) becomes 40 ppm, and soften each cloth (bath ratio 30 times, using tap water at 25 ° C, 3 Minutes). After that, 24 hours at 20 ° C, 40% 111 After drying naturally, the cotton wool was evaluated for flexibility and the polyester satin was evaluated for slipperiness.

 (2) The evaluation of flexibility and slipperiness was performed using a cloth treated with the liquid detergent composition described in Comparative Example 1 as a control, and a sensory pair comparison was conducted by 10 expert panelists. Was evaluated. Results are shown as an average of 10 expert panelists

<Flexibility evaluation criteria>

 +2: clearly softer than the control

 + 1: slightly softer than the control

 0: almost the same as the control

 One 1: the control is slightly softer

 -2: the control is clearly softer

<Slipperiness evaluation criteria>

 +2: Clearer than control

 +1: easier than control

 0: almost the same as the control

 -1: Control is easier

 -2: The control slips more clearly

Stability evaluation method (viscosity of flexible substrate after hydrolysis)

 The compositions shown in Tables 6 to 9 were emulsified by the above method to prepare liquid softener compositions. 80 mL of the solution was poured into a wide-mouth bottle (PS No. 11), the cap was closed, and the container was left in a constant temperature room at 50 for 60 days. After cooling to 25 ° C, the viscosity after 20 seconds was measured with a B-type viscometer (TOK 1 ^ [£ (: 81 ^ viscometer, 30 rpm, No. 2 rotor used)). The following evaluation criteria were used for evaluation.

Evaluation criteria>

Viscosity after storage

 20 OmP as or less ◎

 Over 20 OmP as to 50 OmP as or less 〇

Over 500 to 100 OmP a Over 100 OmP a · s X Using the liquid softener compositions shown in Tables 6 to 9, wash 1 kg of 100% green cotton T-shirt (made by UNICLO) under the same conditions as the softening treatment in (1). The degree of wrinkling after finishing with a washing machine with a drying function until the drying process (washing and drying white promise NW-D8BX, manufactured by Hitachi, Ltd.) was confirmed, but T was treated with the liquid softener composition of the present invention. In each case, the shrinkage was decreasing.

6]

[表 8 ] [¾7]

[Table 8]

 方 Example

 Composition (%) 16 17 18 19 20 21 22 23 24 25

, A no sword Type a— 1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 Compounding amount (%) 20 15 10 5 20 15 10 5 20 15 b-4 b-5 b-6 b-4 b-5 b-6 b-11 b-12 b-13 b-14

(b) ingredient

 Amount (%) 5 3 1 1 5 7 5 0.5 3 7 types c-4 c-5 c-4 c-5 c-4 c-5 c-4 c-5 c-4 c-5

(c) component

 Amount (%) 2.5 2 1.5 0.5 5 5 1.5 0.5 5 5 d-1 d-1 d-1 d-1 d-1 d-1 d-1 d-1 d-1 d-1

(d) ingredient

 Amount (%) 2.0 1.5 1.0 0.5 2.0 1.5 1.0 0.5 1.0 1.0 e-1 e-2 e-3 e-4 e-1 e-2 e-3 e-4 e-1 e-2

(e) component

 Amount (%) 0.5 0.5 0.5 0.3 0.5 0.5 0.5 0.3 0.5 0.5

(f) component

 Amount (%)

Flexibility 1.4 1.2 1.3 1.4 1.2 1.3 1.2 1.3 1.2 1.3 Slipperiness 1.2 1.1 1.1 1.3 1.2 1.3 1.8 1.8 1.9 1.8 Stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[Table 9] ω component

Uru 1

Described.

f-51 f-68 indicates the amount of the active ingredient.

Claims

The scope of the claims  1. (a) 1-30% by mass of a cationic compound containing an ester group in the molecule, (b) 25 ° specific gravity of C is 0. 96 to: L. 10, viscosity 5, 000 mm beyond the ^{2 / s 500, 000mm 2 /} s or less silicone 0.5 to 20% by weight, (c) Alcohol ethoxylate in which the ratio (mass ratio) that the monovalent hydrocarbon group is a linear Z-branched chain is 5/95 to 95/5 0.1 to 10% by mass A liquid softener composition comprising:  2. The liquid softener composition according to claim 1, further comprising (d) 0.4 to 10% by mass of a quaternary alkanolamine having a total carbon number of 4 to 10. 3. The liquid softener composition according to claim 1, wherein the silicone as the component (b) is a polyoxyalkylene-modified silicone represented by the following general formula (1) or (2). .  丄 3 Si-CH ₃ (1)

CH ₃ (CH ₂ ) _L -0- (C ₂ H ₄₀ ) _p- (C ₃ H ₆₀ ) _q -X (Where n is 50 to 10,000, m is a number represented by 1 to 100, L is 1 to 5, p is 1 to 50, q is a number represented by 0 to 50, X is a hydrogen atom or It is an alkyl group having 1 to 3 carbon atoms.) X- R- (OC ₂ H ₄ ) _p- (OC ₃ H ₆ ) _q -OR- X (2)

 "T (In the formula, s is 1 to 10,000, t is a number of 1 to 1,000, p, Q and X have the same meaning as described above. R is an alkylene group having 1 to 5 carbon atoms.) 4. The silicone according to claim 3, wherein the silicone as the component (b) is a polyoxyalkylene-modified silicone represented by the general formula (1), wherein X is a methyl group or an ethyl group. 6. The liquid softener composition according to item 1. 5. The silicone according to claim 3, wherein the silicone as the component (b) is a polyoxyalkylene-modified silicone represented by the general formula (1), wherein n is from 160 to 10,000. Item 5. The liquid softener composition according to Item 4.  6. The component (a) is a cationic compound obtained by quaternizing an esteramine obtained by a condensation reaction of triethanolamine with a fatty acid or a fatty acid methyl ester with dimethyl sulfate. 6. The liquid softener composition according to any one of items 1 to 5.