KR20050089079A - Liquid softener composition - Google Patents

Abstract

(a) 1-30 mass% of cationic compounds containing an ester group in a molecule, (b) 0.5-20 mass% of specific gravity in 25 degreeC with 0.96-1.10 and the viscosity more than 5,000mm <2> / s and 500,000mm <2> / s or less and (c) 0.1-10 mass% of alcohol ethoxylates whose ratio (mass ratio) whose monovalent hydrocarbon group is linear / branched is 5 / 95-95 / 5, The viscosity stability of a composition can be ensured and it is flexible. The liquid softener composition which is excellent in provision, improves the slipperiness | lubricacy of a chemical fiber, and gives a soft wearing feeling can be obtained.

Description

Liquid Softener Composition {LIQUID SOFTENER COMPOSITION}

The present invention relates to liquid softener compositions, in particular liquid softener compositions for textile products.

In recent years, the flexible base material used for the home softening agent has become the mainstream to use the biodegradable base material which contains ester group in a molecule | numerator. However, in cationic flexible base materials containing ester groups in the molecule, ester groups are hydrolyzed by long-term storage or storage at high temperatures, and as a result, the viscosity increases as a softening agent composition, resulting in an undesirable state in use. .

As a solution for this, Japanese Patent Laid-Open No. 2003-105669 proposes a technique for limiting the proportion of the sheath to 90% or more in the flexible base material containing an unsaturated group, but under certain preservation conditions, the fragrance of the softening agent composition deteriorates. In some cases, new improvements are required.

Moreover, the combination example of the ester group containing cationic compound, a silicone compound, and a specific nonionic surfactant (Japanese Unexamined-Japanese-Patent No. 2000-64179), or the combination example of an ester group containing cation and a specific structure silicone compound (Japanese Patent Laid-Open No. 2000-64180) Publication), but it is still insufficient to secure the viscosity stability after hydrolysis of the flexible base material which the present invention intends to solve. In addition, a combination of an ester group-containing cation and a silicone having a specific viscosity has been proposed (Japanese Patent Application Laid-open No. Hei 9-510263), but the viscosity of the silicone is low, and the flexibility may be lowered, and the viscosity stability after hydrolysis is ensured. It was still insufficient.

The present invention can secure the viscosity stability after the flexible base material including the ester group is hydrolyzed by time or high temperature storage, excellent in softening, improve the slipperiness of the chemical fiber, and has a smooth fit An object of the present invention is to provide a liquid softener composition.

MEANS TO SOLVE THE PROBLEM This inventor contains the cationic compound which contains an ester group in the molecule | numerator, the silicone which has a specific specific gravity and viscosity, and the alcohol ethoxylate which the ratio which has the linear / branched chain of an alkyl group are specific ratios, respectively at a specific ratio. By setting it as a liquid softener composition, it discovered that the said objective could be achieved.

Thus, the following invention is provided.

[One]. (a) 1-30 mass% of cationic compounds containing an ester group in a molecule | numerator,

(b) 0.5-20 mass% of silicon whose specific gravity in 25 degreeC is 0.96-1.10, and a viscosity exceeds 5,000mm <2> / s and 500,000mm <2> / s or less,

(c) The liquid softener composition containing 0.1-10 mass% of alcohol ethoxylates whose ratio (mass ratio) whose monovalent hydrocarbon group is a linear / branched chain is 5 / 95-95 / 5.

[2]. (D) The liquid softener composition as described in [1] containing 0.4-10 mass% of quaternary compounds of the alkanolamine of 4-10 total carbons.

[3]. (b) Component silicone is polyoxyalkylene modified silicone represented by following General formula (1) or (2), The liquid softener composition as described in [1] or [2] characterized by the above-mentioned.

(Wherein n is 50 to 10,000, m is 1 to 100, L is 1 to 5, p is 1 to 50, q is 0 to 50, X is a hydrogen atom or 1 to 3 carbon atoms) Is an alkyl group.)

(2)

(Wherein s is 1 to 10,000, t is 1 to 1,000, p, q and X have the same meaning as above. R is an alkylene group having 1 to 5 carbon atoms.)

[4]. (b) Component silicone is polyoxyalkylene modified silicone represented by the said General formula (1), and X is a methyl group or an ethyl group, The liquid softener composition as described in [3] characterized by the above-mentioned.

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

[6]. (a) Component is cationic compound obtained by quaternizing ester amine obtained by condensation reaction of triethanolamine with fatty acid or fatty acid methyl ester with dimethyl sulfuric acid, Any of [1]-[5] The liquid softener composition as described in one.

Best Mode for Carrying Out the Invention

(A) component of this invention is a cationic compound which contains an ester group in a molecule | numerator, If it is a cationic compound which contains an ester group in a molecule | numerator, it will not specifically limit, It can be used individually by 1 type or in combination of 2 or more types suitably. have. As (a) component, the tertiary amine represented by following General formula (3)-(9), the neutralization by the organic or inorganic acid, and its quaternary compound can be illustrated. It is preferable that (a) component is a quaternary compound obtained by quaternizing the ester amine obtained by condensation reaction of triethanolamine with a fatty acid or fatty acid methyl ester with dimethyl sulfuric acid.

Here, in formula, R <^1> is a C9-23, especially 11-21 linear or branched alkyl group or alkenyl group, and may be same or different. Examples of the acid used for neutralization of the tertiary amine include hydrochloric acid, sulfuric acid, and methyl sulfuric acid.

The tertiary amine used in the present invention is preferably used in the form of an amine salt neutralized by hydrochloric acid, sulfuric acid or methyl sulfuric acid. In the neutralization step, the neutralized tertiary amine may be previously dispersed in water, or the tertiary amine may be introduced into the aqueous solution in liquid or solid form. Of course, tertiary amine and acidic component may be added simultaneously. Moreover, methyl chloride and dimethyl sulfate are mentioned as a quaternization agent used for quaternization of the said tertiary amine.

As what quaternized the tertiary amine represented by said general formula (5)-(7) with dimethyl sulfuric acid, what is represented by the following general formula (10)-(12) is mentioned.

R <^1> which comprises (a) component is a residue remove | excluding the carboxyl group from C10-C24 fatty acid, and is group derived from any of saturated fatty acid, unsaturated fatty acid, linear fatty acid, and branched fatty acid. In the case of unsaturated fatty acids, cis and trans forms are present. The mass ratio is preferably cis / trans body = 25/75 to 80/20, and particularly preferably 40/60 to 80/20. As a fatty acid used as the raw material of R ¹ , stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partially hydrogenated fatty acid (iodine value 10) 60) etc. are mentioned. Among them, preferred is a combination of plant-derived stearic acid, palmitic acid, myristic acid, oleic acid, and elide acid in a predetermined amount, and a saturation / unsaturation ratio of 95/5 to 50/50 (mass ratio), cis / trans body. The mass ratio is 40/60 to 80/20, the iodine value is 10 to 50, and the ratio of 18 carbon atoms is 80 mass% or more, and the fatty acid having 20 carbon atoms is adjusted to 2 mass% or less and the fatty acid having 22 carbon atoms to 1 mass% or less. Preference is given to using one fatty acid composition.

The compounds of the general formulas (3) and (4) can be synthesized by the condensation reaction of the fatty acid composition or the fatty acid methyl ester composition with methyldiethanolamine. In that case, it is preferable to synthesize | combine so that the abundance ratio of the compound of (3) and (4) may be 99/1-50/50 by mass ratio. Furthermore, when the quaternary compound is used, it is quaternized with methyl chloride, and the abundance ratio of the quaternary compound and the unquaternized ester amine is quaternary compound / unquaternized ester amine (mass ratio) = 99/1 to It is preferable to synthesize | combine to be 50/50.

The compounds of the general formulas (5), (6) and (7) can be synthesized by the condensation reaction of the fatty acid composition or the fatty acid methyl ester composition with triethanolamine. In that case, based on the whole quantity of (5), (6), and (7), (5) is 1-60 mass%, (6) is 0.5-98 mass%, (7) is 0.1-95 mass% It is preferable to exist in a ratio, It is especially preferable to exist in the ratio of 5-20 mass%, (6) 0.5-30 mass%, and (7) 70-95 mass%. In addition, when using the quaternary compound, it is made into the compound of (10), (11), and (12) by quaternizing with dimethyl sulfuric acid. The abundance ratios of (10), (11), and (12) are based on the total amount of (10), (11), and (12). It is preferable that 25-98 mass% and (12) exist in the ratio of 0.1-40 mass%, (10) is 30-60 mass%, (11) is 10-55 mass%, (12) is 5- It is more preferable to exist in the ratio of 35 mass%. In addition, the abundance ratio of a quaternary compound and the non-quaternized ester amine may be 70/30-99/1 of quaternary compound / unquaternized ester amine (mass ratio). However, in order to suppress the hydrolysis of the ester group contained in (10)-(12), it is preferable to make small the abundance ratio of (5)-(7) which is not quaternized.

Compounds of the general formulas (8) and (9) are known methods from the adducts of the fatty acid composition, N-methylethanolamine and acrylonitrile. Org. Chem., 26, 3409, (1960)] can be synthesized by condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine. In that case, it is preferable to synthesize | combine so that the abundance ratio of the compound of (8) and (9) may be 99/1-50/50 by mass ratio. In addition, when using the quaternary compound, although it is quaternized with methyl chloride, the abundance ratio of a quaternary compound and the unquaternized ester amine is quaternary compound / unquaternized ester amine (mass ratio) = 99/1. It is preferable to synthesize | combine so that it may become -50/50.

The compounding quantity of (a) component is 1-30 mass% with respect to a composition whole quantity, Preferably it is 4-20 mass%. When there is too much compounding quantity, it becomes difficult to maintain the viscosity after hydrolysis at low viscosity. Moreover, when it is less than 1 mass%, in order to ensure a flexible performance at the time of use, it is necessary to use a large amount of softening agent composition.

(B) component used by this invention is silicone whose specific gravity in 25 degreeC is 0.96-1.10, and a viscosity exceeds 5,000mm <2> / s and 500,000mm <2> / s or less, 1 type individually or in combination of 2 or more types suitably Can be used.

The specific gravity of the silicone used in the present invention is an important factor in order to maintain the viscosity after hydrolysis of the flexible substrate at a low viscosity, and it is necessary to be in the range of 0.96 to 1.10 at 25 ° C, preferably 0.97 to 1.07, more preferably Is 0.98 to 1.05.

Moreover, it is preferable that the viscosity in 25 degreeC of silicone exceeds 50 mm <2> / s and is 500,000 mm <2> / s or less, and it is preferable that it exceeds 20 mm <2> / s and 200,000 mm <2> / s or less. If the viscosity is 5,000 mm 2 / s or less, the flexibility may be lowered. If the viscosity exceeds 500,000 mm 2 / s, the viscosity of the liquid softener composition may increase. Although the viscosity of silicone itself is more than 5,000 mm <2> / s and 500,000 mm <2> / s or less, in order to improve the practical handling property, low viscosity silicone, ethanol, isopropanol, butyl carbitol, 1,3-butanediol, ethylene glycol, di You may use what diluted with solvents, such as propylene glycol, phenoxy ethanol, and hexanediol. In addition, the viscosity of silicone used the numerical value as it is described in the catalog of a manufacturer. About the thing which was not described, the value measured using the B-type clay meter (BL clay meter from TOKIMEC company) at 25 degreeC was made into the value multiplied by specific gravity, and the numerical value less than 1,000 was cut off and displayed. The refractive index of the silicon used in the present invention is preferably in the range of 1.35 to 1.44.

Examples of the silicone include dimethyl polysiloxane, amino modified silicone, amide modified silicone, polyether modified silicone, epoxy modified silicone, carboxy modified silicone, amino polyether modified silicone, amido polyether silicone and the like. In order to suppress the yellowing of the treated fabric, an amino modified silicone having an amino equivalent of 10,000 or less, preferably 5,000 or less is preferable, and an epoxy equivalent of 4,000 or less, preferably 1,000 or less, in order to maintain a good texture of the treated fabric. Modified silicone is preferred, and in order to maintain the texture of the treated fabric well, carboxy modified silicone having a carboxy equivalent of 3,000 or less, preferably 2,000 or less is preferred. In addition, amido modified silicone and polyether modified silicone are preferable, and polyether modified silicone is particularly preferable.

As polyether modified silicone, what is represented by following General formula (1), (2) is preferable.

(In formula, n is 50-10,000, Preferably it is 100-10,000, More preferably, it is 160-10,0O0, m is the number represented by 1-100, L is 1-5, p is 1-50, q Is a number represented by 0-50, X is a hydrogen atom or a C1-C3 alkyl group.)

(2)

(Wherein s is 1 to 10,000, t is 1 to 1,000, p, q and X have the same meaning as above. R is an alkylene group having 1 to 5 carbon atoms.)

As silicone, the polyether modified silicone and amino modified silicone which are represented by the said General formula (1), (2) from a viewpoint of flexibility are preferable. Since the amino modified silicone has the possibility of yellowing the treated fabric, the polyether modified silicone represented by the general formulas (1) and (2) is more preferable.

The most preferable silicone is silicone represented by General formula (1), and among these, n is 160-10,000, m is 1-20, p is 1-20, and q is 0-10. And silicone in which X is represented by a methyl or ethyl group is preferable.

In the silicone represented by the general formula (1), in order to improve the flexibility and the slipperiness of the polyether-modified silicone to the fabric, it is necessary to increase the degree of polymerization of the dimethyl silicone portion (n) to make high molecular weight. When X is hydrogen, the viscosity of polyether modified silicone increases remarkably and handling property falls. As an improvement, the increase of the viscosity of polyether modified silicone can be suppressed by making X into a methyl or ethyl group. Therefore, handling property improves and it becomes low viscosity, and also the ease of mix | blending with a softening agent improves.

The following are mentioned as a specific example of the silicone used by this invention.

Examples of the dimethylpolysiloxanes include the following.

TSF451-6000 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 6,000 mm2 / s, specific gravity: 0.98)

TSF451-1M (GE Toshiba Silicone Co., Ltd. make, viscosity: 10,000 mm2 / s, specific gravity: 0.98)

TSF451-3M (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 30,000 mm2 / 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. make, viscosity: 60,000 mm2 / s, specific gravity: 0.98)

TSF451-10M (GE Toshiba Silicone Co., Ltd. make, viscosity: 100,000mm2 / s, specific gravity = 0.98)

TSF451-20M (GE Toshiba Silicone Co., Ltd., viscosity: 200,000 mm2 / s, specific gravity: 0.98)

TSF451-30M (GE Toshiba Silicone Co., Ltd. make, viscosity: 300,000 mm2 / s, specific gravity = 0.98)

TSF451-50M (GE Toshiba Silicone Co., Ltd., viscosity: 500,000 mm2 / s, specific gravity: 0.98)

TSF456-1M (GE Toshiba Silicone Co., Ltd., viscosity: 10,000 mm2 / s, specific gravity: 0.97)

YF33-1M (GE Toshiba Silicone Co., Ltd. make, viscosity: 10,000 mm2 / s, specific gravity: 0.98)

SH200-10,000cs (manufactured by Toray Dow Corning, Inc., viscosity: 10,000 mm2 / s, specific gravity: 0.97)

SH200-12,500cs (manufactured by Toray Dow Corning Co., Ltd., viscosity: 1.250,000 mm2 / s, specific gravity: 0.98)

SH200-30,000cs (manufactured by Toray Dow Corning, Inc., viscosity: 30,000 mm2 / s, specific gravity: 0.98)

SH200-60,000cs (manufactured by Toray Dow Corning, Inc., viscosity: 60,000 mm2 / s, specific gravity: 0.98)

SH200-100,000cs (made by Toray Dow Corning Co., Ltd., viscosity: 100,000 mm2 / s, specific gravity: 0.98)

SH200-200,000cs (manufactured by Toray Dow Corning Co., Ltd., viscosity: 200,000 mm2 / s, specific gravity: 0.98)

BY11-014 (manufactured by Toray Dow Corning, Inc., viscosity: 130,000 mm2 / s, specific gravity: 0.96)

BY11-026 (manufactured by Toray Dow Corning, Inc., viscosity: 100,000 mm2 / s, specific gravity: 0.98)

As amino modified silicone, the following are mentioned.

TSF4704 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 40,000 mm2 / s, specific gravity: 0.98)

TSF4705 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 70,000 mm2 / s, specific gravity: 0.98)

As polyether modified silicone, the following are mentioned.

XF42-B5370 (GE Toshiba Silicone Co., Ltd. make, viscosity: 20,000 mm2 / s, specific gravity: 1.02)

XF42-B5371 (GE Toshiba Silicone Co., Ltd. make, viscosity: 50,000 mm2 / s, specific gravity: 1.01)

FZ-2222 (manufactured by Nippon Unica Co., Ltd., viscosity 25,000 mm 2 / s, specific gravity: 1.01)

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

FZ-2108 (manufactured by Nippon Unica Co., Ltd., viscosity 20,000 mm2 / s, specific gravity: 1.00)

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

As epoxy modified silicone

TSF4730 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 8,000 mm 2 / s, ratio: 0.98)

L-9300 (manufactured by Nippon Unica Co., Ltd., viscosity 6,000 mm2 / s, specific gravity: 0.98)

The compounding quantity of (b) component is 0.5-20 mass% with respect to composition whole quantity, Preferably it is 0.5-8 mass%. Even if a compounding quantity is too large at least too much, the viscosity after storage will become high.

(C) component used by this invention is alcohol ethoxylate whose ratio (mass ratio) whose monovalent hydrocarbon group is linear / branched chain is 5 / 95-95 / 5. Two or more types can be used in combination suitably so that it may become such a ratio. In order to stabilize the viscosity of the liquid softener after the decomposition of the flexible substrate, the monohydric hydrocarbon group (alkyl, alkenyl group) is linear (also referred to as mass ratio) of alcohol ethoxylate and branched alcohol ethoxylate. It is necessary to make branched chain into 5/95-95/5, Preferably it is the range of 5/95-50/50, More preferably, it is the range of 10/90-50/50.

As a monovalent hydrocarbon group, an alkyl group and an alkenyl group are mentioned, These carbon number is 8-20 in both a straight chain and a branched chain, You may use the thing of single carbon number, or you may use combining several types of carbon number. In the case of using an alkenyl group, either the cis body or the trans body may be mixed, or the cis body is preferable.

The alcohol ethoxylate used in the present invention may be a mixture of a linear alcohol ethoxylate and a branched alcohol ethoxylate, respectively, or an alkylene oxide after mixing a linear higher alcohol and a branched higher alcohol. A predetermined mole number may be added. Moreover, you may prepare the trimer and tetramer as a raw material for butylene and propylene, and may add alkylene oxide to what was made into alcohol by the oxo method.

As the alkylene oxide added to the higher alcohol having a linear or branched monovalent hydrocarbon group, ethylene oxide, propylene oxide and butylene oxide are suitable, and the mass ratio of ethylene oxide in the alkylene oxide is 50 to 100% by mass. desirable. In the case where ethylene oxide, propylene oxide and butylene oxide are added in combination, they may be added randomly or added in blocks. As for the addition mole number of the ethylene oxide to add, 10-100 mol is preferable, More preferably, it is 20-80 mol, Especially preferably, it is 30-60 mol.

Specific examples of the higher alcohol to be used as raw materials include Exal Chemical Co., Ltd., Exal Chemical Co., Ltd. Lutensol Series, BASF Co., Ltd. Oxocol C13, Genapol Series (C Series, T Series), Hoechst AG, Shell Dobanol series, ISOFOL series by CONDEA (SASOL) company, etc. can be used. The raw material alcohol may be either a primary alcohol or a secondary alcohol, but the dispersibility of the composition is better when the primary alcohol is used.

Specific examples of alcohol ethoxylates include the Emalex series manufactured by Nihon Emulsion Co., Ltd., the Emalmine series manufactured by Sanyo Kase Co., Ltd., the TDA series manufactured by Lion Kagaku Co., Ltd., TA series, and Nihon Sho Co., Ltd. Soaptanol series, such as Soaptanol 300 by Cuba, Lutensol series by BASF, Emulan series, etc. are mentioned. These alcohol ethoxylates can be used so that the mass ratio of the said linear / branched chain may be 5 / 95-95 / 5. Moreover, the said compound may contain polyalkylene glycol, such as alcohol, polyethyleneglycol, polypropylene glycol, polybutylene glycol, etc. as a raw material in an alcohol ethoxylate within 10 mass% as a reaction byproduct.

The compounding quantity of (c) component is 0.1-10 mass% with respect to composition whole quantity, Preferably it is 0.5-5 mass%. When the amount is too small, the viscosity after storage is high, and when too large, the initial viscosity immediately after production is high.

In order to suppress the viscosity of the liquid softening agent composition after hydrolysis to low viscosity in the liquid softening agent composition of this invention, it is preferable to include the quaternary compound of the alkanolamine of 4-10 total carbons, Or 2 or more types can be used suitably in combination. Examples of the (d) component alkanolamine include methyl diethanolamine, triethanolamine, diethanolamine and the like. Moreover, methyl chloride and dimethyl sulfuric acid are mentioned as a quaternization agent of alkanolamine, The compound represented by following General formula (13), (14) can be illustrated as a specific example.

As a compounding quantity of the quaternary compound of (d) component alkanolamine, in order to maintain the viscosity after hydrolysis of a flexible base material at low viscosity, 0.4-10 mass% is preferable with respect to composition whole quantity, and 0.5-5 mass% is especially preferable. Do. If the blending amount is less than 0.4% by mass, the low viscosity effect may be reduced. If the blending amount is more than 10% by mass, the casting performance may decrease.

In addition, in the liquid softener composition of the present invention, the following compounds and ordinary softeners are used for the purpose of stabilizing viscosity, improving performance, adding functionality, improving manufacturability, improving appearance, improving fragrance, and the like, without impairing the object of the present invention. The following various components mix | blended with a composition can be mix | blended as (f) component. These various components can be used individually by 1 type or in combination of 2 or more types.

Cationic surfactants are 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, a long-chain alkyl trimethylammonium chloride containing one C10-22 long chain alkyl group, an alkenyl group, a long-chain alkyl group having 10 to 22 carbon atoms, a di-chain alkyldimethylammonium chloride containing two alkenyl groups, or a C8-22 carbon atom And a long-chain alkyl group, an alkenyl group, and three long-chain alkylmethylammonium chlorides.

When mix | blending a cationic surfactant with the liquid softening agent composition of this invention, 10 mass% or less is preferable with respect to a composition whole quantity, and 0.1-10 mass% is more preferable.

As amphoteric surfactant, sulfobetaine and carboxybetaine which have one or two long chain groups can be used. The long chain group is a hydrocarbon group and may contain an ester group, an amido group, or an ether group in the hydrocarbon group. Moreover, the ratio of the saturated type / unsaturated type of hydrocarbon group, carbon chain length distribution, the cis body / trans body mass ratio of unsaturated group, etc. are not specifically limited. The hydrocarbon group derived from the fatty acid or fatty acid methyl ester which is a raw material of the said (a) component may be sufficient. Amphoteric surfactants specifically include betaines such as N, N-diaxyloyloxyethyl-N-methylammonioethyl sulfate and ethyl carboxylate, and N-acyloxyethyl-N-hydroxyethyl-N-methyl Ammoniobetaines, N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N'-dimethyl-N'-β-hydroxypropylammoniobetaines and the like can be used. Can be. Moreover, the long chain group has 1 type and 2 type, and can also be used individually or in mixture. The compound may contain some amino betaine such as a compound in which the nitrogen atom is not quaternized, an alkanolamine as a raw material, a neutralized product thereof, and a quaternary compound, and these may be included. You may use these individually by 1 type or in mixture of 2 or more types.

When mix | blending an amphoteric surfactant with the liquid softening agent composition of this invention, 10 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 0.1-5 mass%, Especially preferably, it is 0.1-3 mass%. .

Moreover, as a hydrocarbon, it is a liquid at normal temperature, such as fluidized paraffin, and 10 mass% or less, Preferably 0.1-3 mass% can use paraffin of melting point 70-30 degreeC in a composition.

Solid fats, such as a wax, and polyurethane can be used as a texture, smoothness improvement, and a water absorptive control agent. As the wax, one kind or a mixture of two or more kinds of hydrocarbons selected from alkanes, alkenes, petroleum waxes, and animal-based waxy materials can be used.

When the solid phase fat is alkanes, carbon atoms are most preferably 22 or more, and specifically, decoic acid, tricoic acid, tetracoic acid, pentacoic acid, heptacoic acid, heptacoic acid, octacoic acid, nonacoic acid, triacontane and hen Triacontane, dotriacontane, tritriacontane, tetratricontane, pentatricontane, hexatriacontane, heptatricontane, octatriacontane, nonatricontane and the like. In addition, the alkanes may have a three-dimensional hydrocarbon bond such as linear, branched, or polyalkylene.

When the solid-phase fats and oils are alkenes, it is preferable that carbon number is 24 or more, Specifically, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacecene, 1-dotriacontene, 1-tetratriacontene , 1-hexatria content, 1-octatria content, 1- tetra content, etc. are mentioned. In the case where the solid fat or oil is petroleum wax, paraffin wax, microcrystalline wax, petrolatum having a melting point of 40 ° C. or higher is most preferred, and specific examples of commercially available petroleum wax include HNP-3, HNP-12, HNP-14G, SP-0160, SP-1035, Hi-Mic-1045, Hi-Mic-2045, JP-1500, JP-105, JP-131T (all are manufactured by Nippon Shiro Co., Ltd.) and the like.

In the case where the solid fat or oil is a plant or animal wax, specific examples thereof include candelilla wax, carnauba wax, hydrogenated jojoba wax, wax, beeswax, and wax. The compound can also be used in the form of an emulsion. Specifically, the high melting point polyethylene emulsion (Eponol 900), the copper emulsion (UPM-212HN), the emulsion made from Chiba Specialty Chemicals, Inc. (TINOTEX FSA), etc. are specifically, made. Can be used.

When mix | blending solid resin, such as a wax, with the liquid softening agent composition of this invention, 20 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 10 mass% or less, Especially preferably, it is 0.1-5 mass % to be.

Moreover, an inorganic or organic water-soluble salt can be used for the purpose of controlling the viscosity of a composition. As inorganic or organic water-soluble salts, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, aluminum chloride, sodium sulfate, magnesium sulfate, potassium sulfate, sodium acetate, magnesium acetate, sodium p-toluenesulfonate, sodium glycolate, sodium acetate And potassium acetate, sodium glycolate, sodium acetate, potassium acetate, potassium glycolate, sodium lactate and the like. Preferably, calcium chloride, magnesium chloride, sodium chloride. 3 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 0.01-2 mass%, Especially preferably, it is 0.05-1 mass%. Addition of the salt may be carried out in any step during the preparation of the emulsion composition.

However, when the density | concentration of (a) and (b) component in a liquid detergent composition is high, in order to suppress a viscosity low, it is preferable to add a salt concentration high and dividing it twice or more. More preferably, 0.5 mass% or less is added during manufacture of a composition, and 0.5 mass% or less is added after manufacture. By making the addition amount after manufacture more than the addition amount during manufacture, the viscosity of a composition can be reduced.

Alcohols having 1 to 10 carbon atoms can be blended for the purpose of improving handling properties, low temperature stabilization, and clearing of the composition related to liquid detergent composition production. Moreover, especially in order to improve the handling property of (a) and (b) component, it may be used as a reaction solvent, a slurry solvent, and a dilution solvent of (a) and (b) component, and when it is included together at the time of preparation of a composition There is.

Specific examples of the alcohol having 1 to 10 carbon atoms include ethanol, isopropanol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-pentanediol, hexylene glycol, trimethylpentanediol, benzyl alcohol, diethylene glycol Monobutyl ether, glycerin, 2-phenoxyethanol, 2-phenylethanol and the like.

The C1-C10 alcohol is normally 0-15 mass% with respect to composition whole quantity, Preferably 0.5-10 mass% is contained. For lower alcohols, those modified with modifiers such as sodium benzoate, 8-acetylated sucrose, brucin, orange and citrus can be used.

For the clarification of the composition, the monool, C6 diol, C7 diol, octanediol isomer, butanediol derivative, trimethylpentanediol isomer, ethylmethylpentanediol isomer, propylpentanediol isomer, and the like described in Japanese Patent Application Laid-Open No. 2000-505155 Dimethyl hexanediol isomer, ethyl hexanediol isomer, methylheptanediol isomer, octanediol isomer, nonanediol isomer, alkylglyceryl ether, di (hydroxyalkyl) ether, arylglyceryl ether, aromatic glyceryl ether, alicyclic diol or Derivatives, C3 to C7 diol alkoxylated derivatives, aromatic diols, unsaturated diols and the like can be used. As a particularly preferred main solvent, hexanediol such as 1,2-hexanediol or 2-ethyl-1,3-hexanediol, and pentanediol such as 2,2,4-trimethyl-1,3-pentanediol can be used. have. 40 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 10-35 mass%, Especially preferably, it is 12-25 mass%.

Moreover, stability of the fragrance and color tone of a liquid detergent composition can be improved by mix | blending an antioxidant and a reducing agent. Specific examples include ascorbic acid, ascorbic palmitate, a mixture of propyl gallic acid, BHT (butylated hydroxy toluene), BHA (butylated hydroxy anisole), propyl gallate, and a mixture of citric acid, tertiary butylhydroquinone, Natural tcopherol, long-chain esters of gallic acid (C8 to C22), for example Irganox-based compounds available from Gallic acid dodecyl, Chivas Specialty Chemical Co., Ltd., preferably Irganox 3125, Irganox 1425, Ir Ganox 3114, and mixtures thereof, isopropyl citrate, 4,5-dihydroxy-m-benzenesulfonic acid available from Kodak, tyrone whose chemical name is its sodium salt, and the like.

As for the compounding quantity of antioxidant, 1 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 0.0001-0.5 mass%. The reducing agent is preferably 3 mass% or less, more preferably 0.0001 to 2 mass%. At the time of use, you may add it divided arbitrarily as many times as the range which does not prevent the effect of this invention, such as at the time of manufacture of (a) component, after manufacture, and before and after manufacture of a composition.

In addition, the compounds described in the following 1) to 4) may be used alone or in combination of two or more in order to enhance antiseptic and bactericidal properties.

1) As an isothiazolone type organic sulfur compound, the compound containing 3-isothiazolone group is preferable. These compounds are disclosed in US Pat. No. 4,265,899 to Lewis et al., Issued May 5, 1981. Examples thereof include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-nbutyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothia Zolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof are mentioned. have. More preferred antiseptic and disinfectant is an aqueous mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, still more preferably about 77 A water-soluble mixture of 5% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one with about 23% by weight of 2-methyl-4-isothiazolin-3-one. Commercially available ones such as Cayson CG / ICP (approximately 1.5% by mass aqueous solution) of Rohm and Hers Corporation, and quasi-side series such as Quasi-Side 5 manufactured by Junsei Chemical Co., Ltd. can be used.

2) Examples of the benzisothiazoline-based organic sulfur compound include 1,2-benzisothiazolin 3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and the like. As the flexible compound, dithio-2,2-bis (benzmethylamide) and the like can also be used, and these can be used at arbitrary mixing ratios. As such a compound, the proxy cell series [BDN (effective mass 33 mass%), BD20 (effective mass 20 mass%), XL-2 (effective mass 10 mass%), GXL (effective mass 20 mass) made by Abisia %), LV (effective mass 20 mass%), TN (active mass 60 mass%)], and dendritic BIT / NIPA 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-2-nitropropane-1,3-diol and the like can be used. As such a compound, commercial items, such as BronidoxL by Henkel, Bronopol by Inolex, Bronopol by Yoshitomi Seiyaku Co., Maia BT by Boots Corporation, Myaide Pharma BP by BASF, and Protect BN by BASF, can be used.

4) As benzoic acid or a phenol compound, benzoic acid or its salt, salicylic acid or its salt, parahydroxy benzoic acid or its salt, methyl paraoxybenzoate, ethyl paraoxybenzoic acid, propyl paraoxybenzoic acid, butyl paraoxybenzoic acid, paraoxybenzoic acid Benzyl, 3-methyl-3-isopropyl phenol, o-phenylphenol, 2-isopropyl-5-methylphenol, resorcin, cresol, 2,6-di-tert-butyl-p-cresol and the like can be used. .

As for the compounding quantity of the compound of 1) -3), 0.1 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 0.00001-0.03 mass%, Especially preferably, it is 0.00005-0.02 mass%. As for the compounding quantity of the compound of 4), 3 mass% or less is preferable with respect to composition whole quantity, More preferably, it is 0.01-1.5 mass%. Moreover, by using 2 or more types of the compounds of said 1) -4) together, antiseptic power and bactericidal power can be strengthened, and the usage-amount of the said expensive compound can also be reduced. Among them, it is particularly preferable to use two or more kinds selected from Keyson CG / ICP, ProxyCell series BDN, Maiside BT, Protect BN and benzoic acid in combination, and the amount thereof is 0.00001 to 2% by mass, more preferably 0.00001. It is -1 mass%, More preferably, it is 0.00005-0.5 mass%.

The compounds of 1) to 3) above preferably coexist with metal ions such as zinc, copper, calcium and magnesium, or are added to the composition as an ethylene glycol, propylene glycol or dipropylene glycol solution.

In addition, the liquid softener composition of the present invention is modified to have dimethylpolysiloxanes other than the component (b) and various organic functional groups for the purpose of further improving the absorbency of the fibers, iron slipperiness, anti-wrinkle properties, and color fading of the faded clothes. Silicone selected from dimethylpolysiloxane can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratios.

When the silicone is a modified dimethylpolysiloxane, the organofunctional group may be polyether, amino, amido, alkyl, aralkyl, carboxyl, fluoroalkyl, higher alcohol ester, epoxy, carbinol, mercapto, phenol, methacryl or amyl. Also, modified silicones such as polyether and alkyl alcohol may be used, and two or more kinds of modified silicones may be used. In addition, the coupling | bonding position of an organic functional group may be any of a side chain or a terminal with respect to the main chain of dimethylpolysiloxane, and when it couple | bonds with an terminal, one terminal or both terminal may be sufficient. In addition, the mass ratio of the organic functional group to dimethylpolysiloxane can be arbitrarily selected, and it is not specifically limited. As the modified dimethylpolysiloxane, hydrogenated dimethylpolysiloxane or hydroxide dimethylpolysiloxane, which is a precursor for introducing an organic functional group, may be used alone or in combination with a modified dimethylpolysiloxane having an organic functional group.

Various silicones may be used as an oil, may be used as an emulsion, and when using powder of a silicone elastomer, you may use as a dispersion liquid. The refractive index of these silicon is 1.30-1.55. These silicone compounds are 10 mass% or less suitably with respect to composition whole quantity, More preferably, it is 0.1-10 mass%, Especially preferably, 0.2-8 mass% can be used.

Moreover, arbitrary dyes and / or pigments can be mix | blended in order to improve the external appearance of a liquid softening agent composition. Preferably, 1 type, or 2 or more types of water-soluble dye chosen from acid dye, direct dye, alkaline dye, reactive dye, and mordant and acid mordant dye is mentioned. Specific examples of the dye that can be added are described in the dye handbook (Organic Synthetic Chemical Society edition, issued July 20, 1970, Maruzen Co., Ltd.). From the viewpoint of storage stability of the liquid softener composition and dyeing property to fibers, an acidic dye, a direct dye, and a reactive dye having at least one functional group selected from a hydroxyl group, a sulfonic acid group, an amino group, and an amido group in the molecule are preferable. 1-50 ppm is preferable with respect to the composition whole quantity, More preferably, it is 1-30 ppm. As a dye used for the liquid softening agent composition of this invention, Unexamined-Japanese-Patent No. 2001-348784, Unexamined-Japanese-Patent No. 2001-181972, Unexamined-Japanese-Patent No. 11-43865, Unexamined-Japanese-Patent No. 10-77576, Japanese Patent Laid-Open No. 9 The dyes described in -2,8585, Japanese Patent Laid-Open No. 8-27669, Japanese Patent Laid-Open No. 7-18573, Japanese Patent Laid-Open No. 6-123082, and Japanese Patent Laid-Open No. 6-123081 can also be used.

Perfume ingredients may be added for the orientation of the composition. A list of fragrance raw materials to be used as fragrances is described in various literatures such as "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and Synthetic Fragrance Chemistry and Merchandise Knowledge, Into One-I, Chemical Daily (1996) and Perfume and Flavor Materials of Natural Origin, Steffen Arctallder, Allured Pub. Co. (1994) and Encyclopedia of Fragrances, Japan Spice Association, Asakura Bookstore (1989) and Perfumery Material Performance V.3.3, Boelens Aroma Chemical Information Service (1996) and Flower oils and Floral Compounds In Perfumery , Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., each of which is part of the disclosure herein.

In order to suppress the hydrolysis of an ester group, the liquid softening agent composition of this invention makes it preferable to make pH into the range of 1.0-6.0, pH 1.5-4.5 are more preferable, The range of pH2.0-4.0 is especially desirable. Arbitrary inorganic or organic acids and alkalis can be used for pH adjustment. Carboxylic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, paratoluene sulfonic acid, acetic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, sodium hydroxide, diethanolamine, triethanolamine, and the like. Of these, hydrochloric acid, methyl sulfuric acid, sodium hydroxide, diethanolamine and triethanolamine are preferable.

In addition to the above-mentioned base compound, as a viscosity control and stabilizer, a fragrance time control agent such as a polymer compound, hydrotropes and cyclodextrins, an emulsion such as a polystyrene emulsion, an opaque agent and a functional enhancer, an anti-wrinkle agent, an anti-wrinkle agent, and a shape Oil retainer, Drape oil retainer, Iron improver, Oxygen bleaching agent, Brightener, Whitening agent, Fabric softening clay, Antistatic agent, Anti-inflammatory agent such as polyvinylpyrrolidone, Polymeric dispersant, Contaminant remover, Scum dispersant, 4,4 Fluorescent whitening agents such as bis (2-sulphostyryl) biphenyldisodium (Chinopal CBS-X manufactured by Chiba Specialty Chemicals Co., Ltd.), Ciba (registered trademark) manufactured by Chiba Specialty Chemicals Co., Ltd., TINOSORB ( Trademarks), FR, FD, CIBAFAST (registered trademark), benzothiazole-based ultraviolet absorber, dye fixer, 1,4-bis (3-aminopropyl) piperazine and other anti-fading agents, stain removers, fiber surface modifiers Cell It is capable of imparting silk texture and function such as enzymes such as amylase, protease, lipase, keratinase, antifoaming agent, and water absorption and release property, and includes silk protein powder, surface modifications thereof, emulsion dispersion, and the like. can do. As these specific examples, K-50, K-30, K-10, A-705, S-702, L-710, FP series (made by Idemitsu Seki Yukagaku Co., Ltd.), hydrolyzed silk liquid (Co., Ltd.) Coarse agent), Silken G Soluble S (manufactured by Ichimaruparcos Co., Ltd.), alkylene terephthalate and / or nonionic polymer compound composed of alkylene isophthalate units and polyoxyalkylene units, for example, Recontamination prevention agents, such as Okagaku Kogyo Co., Ltd. FR627 and Clariant Co., Ltd. SRC-1, etc., Preferably 0.01-5 mass% can be mix | blended with respect to composition whole quantity.

The preparation method of the softening agent is not particularly limited, and various methods can be used. In particular, Japanese Patent Application Laid-Open No. 2-68137, Japanese Patent Laid-Open No. 5-32788, Japanese Patent Laid-Open No. 5-32789 and Japanese Patent Laid-Open No. 10-237762 The method described in is preferred. That is, a part of an aqueous phase is added to the oil phase containing (a), (b) component, and a fragrance component, or this oil phase is added to a part of an aqueous phase, and the liquid crystal phase of a cationic surfactant is formed, Subsequently, the liquid softening agent composition of this invention can be prepared by the method of mixing this liquid crystal phase and the remaining water phase, and making a liquid phase change phase.

The alcohol ethoxylate as the component (c) may be added to either an aqueous phase or an oil phase. Salts which are viscosity control agents can be added by dividing several times at the time of manufacture. When dividing and using an aqueous phase, you may add to each aqueous phase and may add after completion of manufacture. In addition, from the viewpoint of handling properties such as solubility, the optional components (e and f components to be described later) are selected in the aqueous phase and the oil phase. However, inferior solubility can also be put into either phase by combined use with an emulsifier and a solvent. Generally, it is preferable to put a high water solubility in an aqueous phase and a low water solubility in an oil phase.

Although the container which accommodates the liquid softening agent composition of this invention is not specifically limited, It is common to accommodate in a bottle container made of polyethylene, a polypropylene, and a polyethylene terephthalate, and a polyethylene and a pouch container made of nylon. In recent years, in order to suppress the evaporation of the moisture of the composition, and to suppress the change in the properties such as viscosity, color tone, fragrance, etc., a film of polyethylene or polyethylene terephthalate on which aluminum or alumina is deposited may be used as the material of the pouch. Furthermore, it may contain a pigment, an antistatic agent, a ultraviolet absorber, and a sleeping agent.

Moreover, the liquid softening agent composition of this invention is used at the time of rinsing after completion | finish of washing in normal washing | cleaning. However, you may use independently a liquid softening agent composition, without a washing process. The detergent in the washing step may be a detergent of an anionic surfactant or a detergent of a nonionic surfactant, or may contain other surfactants and functional enhancers, and both of the detergents commercially available at home and abroad can be used. . Concentration of the total amount of (a) component with respect to the quantity at the time of finishing the fibrous product filled in a washing bath in a rinse process from a viewpoint of the flexibility to a fibrous product from the viewpoint of providing flexibility to a fibrous product It is preferable to use it in the quantity which becomes 10-100 ppm. More preferably, it is 20-100 ppm. However, it is most preferable for the user to adjust the desired amount in consideration of the washing machine type, the quantity of the textile product, the quantity, and the like.

The liquid softener composition of this invention can be used for all commercially available, such as a two-layer washing machine, a fully automatic washing machine, and a washing machine with a drying function. Washing machine with drying function is marketed by various washing machine makers, and "Senkan Shiroi Yakusoku NW-D8BX" Hitachi Sesaku Shoze Co., Ltd., "Home London Kaisuku Kinka 21 TW-741EX" Toshiba Corporation "," Lab NA-FD8002 Matsushita Denki Sangyo Co., Ltd., "Made in Heyaboshi Karato MAW-V8TP Mitsubishi Denki Co., Ltd.", "Aqua Baku Senjo AW-801HVP Co., Ltd.", "Top Open Drum AWD-A845Z" Sanyo Denki Corporation "etc. are mentioned.

According to the liquid softener composition of the present invention, it is possible to ensure the viscosity stability after the flexible base material containing an ester group is hydrolyzed over time or at high temperature storage, excellent in softness, improve the slipperiness of chemical fibers, A liquid softener composition can be obtained that gives a soft fit.

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

(A) The components described in Tables 6 to 8 in which the component (a) was heated and dissolved at 60 ° C, the amounts described in Tables 6 to 8 for the component (b) heated to 60 ° C, and (e) shown in Table 3 The quantity described in Tables 6-8 of the fragrance | flavor of a component was added to the glass container of internal diameter 120mm, and it stirred for 30 second at 1000 rpm using the Three-one motor. As a stirring blade, the paddle blade which has three wings of length 100mm by 30 mm space | interval was used. Next, the aqueous solution containing (c) component which melt | dissolved in the liquid softening agent composition so that it might become the quantity of Tables 6-8 was prepared, 40 mass% of this aqueous solution was added to the container, and it stirred at 1000 rpm for 3 minutes. Subsequently, the remaining 60 mass% aqueous solution was further added and stirred for 2 minutes. The three-one motor was stopped once, and 2 mass% of 10 mass% calcium chloride solution was added, and it stirred for 30 second. If necessary, it is adjusted to pH3.0 with 5 mol / L hydrochloric acid (Kanto-Kagaku Co., Ltd.) and 5 mol / L sodium hydroxide (Kanto Chemical Co., Ltd.), and finally ions so as to be 100% by mass in total. Exchange water was added and the mixture was further stirred for 30 seconds to prepare 1000 g of a liquid softener composition. In addition, when adding (d) component after Example 4, the quantity used as the quantity of Tables 6-8 was added to aqueous solution with (c) component. About (f) component mix | blended in Examples 16-25 described in Table 8, 9, (f-1)-(f-25), (f-31)-(f-33) are (c) component In the same manner as in the above solution, (f-41) to (f-49), (f-61) to (f-68) are added at the same timing as the components (a) and (b), and (f- 51) to (f-57) were added at the same timing as the calcium chloride aqueous solution. In addition, the compounding quantity of (a)-(f) component is the quantity of Tables 6-9.

About the obtained liquid softener composition, the softness and the viscosity after hydrolysis of a liquid softener composition were evaluated. The results are written together in Tables 6-9. (A)-(d) component used below is shown.

Synthesis of (a) Component

Synthesis of (a-1)

a-1-1. Synthesis of Methyl Ester

2.5 kg of palm fatty acid methyl (Lion Co., Ltd., pastel M182, molecular weight 296) consisting of 75 mass% of methyl oleate, 16 mass% of linoleate, and 9 mass% of methyl stearate, and 2.5 g (0.1 mass% of commercially available stabilizing nickel catalyst) / Methyl fatty acid) was charged into a 4L autoclave and subjected to nitrogen gas substitution three times. Next, the rotation speed was set at 800 rpm, and about 77 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was consumed completely, it was cooled, the catalyst was removed using a filtration aid, and hydrogenated palm fatty acid methyl was obtained. The molecular weight determined from the saponification value was 297. Fatty acid methyl composition calculated | required by GC (gas chromatography analysis) is 36 mass% of methyl stearate, 36 mass% of methyl oleate (trans), 28 mass% of methyl oleate (cis), and 0 mass% of methyl linoleate, The trans / cis body ratio of unsaturated fatty acid methyl ester was 56/44 (mass ratio). In addition, an unsaturated alkyl group was measured by GC (gas chromatography) by the following method.

Model: Hitachi FID Gascro G-3000, Column: GL Science TC-70 (0.25mm I.Dx30)

Temperature: Column 150 ° C to 230 ° C, Heating rate 10 ° C / min, Injector and detector 240 ° C, Column pressure: 1.0kgf / cm ²

a-1-2. Synthesis of Alkanolamine Esters and Quaternary Compounds

Fatty acid methyl ester (unsaturated fatty acid methyl) in which 489 g (1.65 mol) of hydrogenated palm fatty acid methyl prepared in (a-1-1) was mixed with 137 g (0.46 mol) of methyl stearate and 156 g (0.58 mol) of methyl palmitic acid Mass ratio 40/60 of saturated / saturated fatty acid methyl, 250 g (1.67 mol) of triethanolamine, 0.51 g of magnesium oxide, and 3.69 g of 14% sodium hydroxide aqueous solution were equipped with a 2-liter four-necked flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen introduction tube. After nitrogen replacement, nitrogen was flowed at a flow rate of 0.52 L / min. It heated up to 190 degreeC at the speed | rate of 1.5 degreeC / min, and made it react for 6 hours. It confirmed that unreacted methyl ester was 1 mass% or less, and stopped reaction. The fatty acid salt derived from the catalyst was filtered off from the obtained product to obtain an intermediate alkanolamine ester. It was 582 when the amine value was measured and molecular weight was calculated | required.

270 g (0.46 mol) of the obtained alkanolamine esters were placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and nitrogen-substituted. Subsequently, it heated at 85 degreeC and dripped the dimethyl sulfuric acid 57.4g (0.45 mol) over 1 hour. After completion of the dropwise addition, the temperature was maintained at 90 ° C and stirred for 1 hour. After the completion of the reaction, when the temperature was 70 ° C. or less, approximately 62 g of unmodified ethanol (manufactured by Nippon Ethanol Co., Ltd.) was added dropwise to prepare an ethanol solution having a solid content of about 85% by mass, and finally Peliox CY-115 ( Lion Co., Ltd. and dibutylhydroxytoluene (manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) were added at a concentration of 100 ppm each. The obtained reaction product contained 70 mass% of cationic compounds containing an ester group in the molecule | numerator of (a) component, and the monoester anmonium salt / diester ammonium salt / triester anmonium salt is 28/53/19 (mass ratio). Included. This compound is corresponded to the compound represented by General formula (11), (10), (12). In this ethanol solution, 9.0 mass% of unquaternized monoester amine, diester amine, and triesteamine were contained in total, and the ratio existed at 1/9/90 (mass ratio). This compound is corresponded to the compound represented by General formula (6), (5), (7). Moreover, 2.0 mass% of amphoteric compounds were contained as a by-product.

Synthesis of (a-2)

a-2-1. Synthesis of Methyl Ester

2.5 kg of palm fatty acid methyl (Lion Co., Ltd., pastel M182, molecular weight 296) consisting of 75 mass% of methyl oleate, 16 mass% of methyl linoleate, and 9 mass% of methyl stearate and 1.9 g of commercially available stabilized nickel catalyst (0.075 mass%) / Methyl fatty acid) was charged into a 4L autoclave and subjected to nitrogen gas substitution three times. Next, the rotation speed was set at 800 rpm, and about 40 L of hydrogen gas was introduced at a temperature of 185 ° C. When the introduced hydrogen was consumed completely, it was cooled, the catalyst was removed using a filtration aid, and hydrogenated palm fatty acid methyl was obtained. The molecular weight determined from the saponification value was 296. Fatty acid methyl composition calculated | required by GC is 14 mass% of methyl stearate, 26 mass% of methyl oleate (trans form), 60 mass% of methyl oleate (cis), and 0 mass% of linoleate methyl, and trans of unsaturated fatty acid methyl ester The / cis ratio was 30/70 (mass ratio). In addition, an unsaturated alkyl group was measured by GC by the following method.

Model: Hitachi FID Gascro G-3000 Column: GL Science TC-70 (0.25mm I.Dx30)

Temperature: Column 150 ° C to 230 ° C, Heating rate 10 ° C / min, Injector and detector 240 ° C, Column pressure: 1.0kgf / cm ²

a-2-2. Synthesis of Alkanolamine Esters and Quaternary Compounds

489 g (1.65 mol) of hydrogenated palm fatty acid methyl prepared in (a-2-1) mixed with 352 g (1.18 mol) of methyl stearate (mass ratio of unsaturated fatty acid methyl / saturated fatty acid methyl = 50/50) ) And 468 g (3.14 mol) of triethanolamine, 0.65 g of magnesium oxide, and 4.68 g of an aqueous 14% sodium hydroxide solution were placed in a 2-liter four-necked flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen introduction tube. Was flown at a flow rate of 0.52 L / min. It heated up to 190 degreeC at the speed | rate of 1.5 degreeC / min, and made it react for 6 hours. It confirmed that unreacted methyl ester was 1 mass% or less, and stopped reaction. The fatty acid salt derived from the catalyst was filtered off from the obtained product to obtain an alkanolamine ester of an intermediate.

300 g of the obtained alkanolamine ester was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and nitrogen-substituted. Subsequently, it heated at 85 degreeC and dripped 0.98 times mole of dimethyl sulfate with respect to an alkanolamine ester over 1 hour. After completion of dropping, the temperature was maintained at 90 ° C and stirred for 1 hour. After the completion of the reaction, when the temperature became 70 ° C. or lower, ethanol was added dropwise to prepare an ethanol solution having a solid content of 85% by mass, and finally, Peliox CY-115 (manufactured by Lion Co., Ltd.) and dibutylhydroxytoluene ( Sumitomo Kagaku Kogyo Co., Ltd. product was added so as to have a concentration of 100 ppm each. The obtained reaction product contains 72 mass% of cationic compounds containing an ester group in the molecule | numerator of (a) component, and monoester anmonium salt / diester ammonium salt / triester ammonium salt is 53/41/6 (mass ratio). Included. This compound is corresponded to the compound represented by General formula (11), (10), (12).

Synthesis of (a-3)

a-3-1: Synthesis of alkanolamine ester and quaternary compound thereof

489 g (1.65 mol) of hydrogenated palm fatty acid methyl prepared in (a-1-1), 98 g (0.66 mol) of triethanolamine, 0.29 g of magnesium oxide, and 2.1 g of 14% sodium hydroxide aqueous solution were mixed with a stirrer, a cooler, a thermometer, The mixture was placed in a two-liter four-necked flask equipped with a nitrogen introduction pipe, and after nitrogen replacement, nitrogen was flowed at a flow rate of 0.52 L / min. It heated up to 190 degreeC at the speed | rate of 1.5 degreeC / min, and made it react for 6 hours. It was confirmed that unreacted methyl ester was 1% or less, and the reaction was stopped. The fatty acid salt derived from the catalyst was filtered off from the obtained product to obtain an alkanolamine ester of an intermediate.

300 g of the obtained alkanolamine ester was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and nitrogen-substituted. Subsequently, it heated to 85 degreeC, and 0.98 times mole of dimethyl sulfuric acid was dripped over 1 hour with respect to the alkanolamine ester. After completion of the dropwise addition, the temperature was maintained at 90 ° C and stirred for 1 hour. After the completion of the reaction, when the temperature became 70 ° C. or lower, ethanol was added dropwise to prepare an ethanol solution having a solid content of 85% by mass, and finally, Peliox CY-115 (manufactured by Lion Co., Ltd.) and dibutylhydroxytoluene ( Sumitomo Kagaku Kogyo Co., Ltd. product was added so as to have a concentration of 100 ppm each. 70 mass% of (a) component was contained in the obtained reaction product, and monoester ammonium salt / diester ammonium salt / triester ammonium salt was contained in 12/54/34 (mass ratio). This compound is corresponded to the compound represented by General formula (11), (10), (12).

(b) ingredients

b-1: SH200-100,000cs (made by Toray Dow Corning Co., Ltd., viscosity: 100,000mm2 / s, specific gravity: 0.98)

b-2: TSF4704 (GE Toshiba Silicone Co., Ltd. make, viscosity: 40,000 mm2 / s, specific gravity: 0.98)

b-3: TSF4705 (manufactured by GE Toshiba Silicone Co., Ltd., viscosity: 70,000 mm2 / s, specific gravity: 0.98)

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

b-5: XF42-B5371 (GE Toshiba Silicone Co., Ltd., viscosity: 50,000 mm2 / s, specific gravity: 1.Ol)

b-6: FZ-2222 (manufactured by Nippon Unica Co., Ltd., viscosity 25,000 mm 2 / s, specific gravity: 1.01)

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

b-8: CF1188HV (made by Toray Dow Corning Co., Ltd., viscosity: 6,000 mm <2> / s, specific gravity: 1.01)

b-9: TSF4730 (made by GE Toshiba Silicone Co., Ltd., viscosity: 8,000 mm <2> / s, specific gravity: 0.98)

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

b-11-15

Moreover, the silicone of the structure represented by General formula (1) was also used as (b) component.

b-16: TSF451-5A (GE Toshiba Silicone Co., Ltd. make, viscosity: 5mm <2> / s, specific gravity: 0.92): Comparative product

b-17: SH3771 (manufactured by Toray Dow Corning, Inc., viscosity: 400 mm 2 / s, specific gravity: 1.07): Comparative product

Emalex 730 (made by Nihon Emulsion Co., Ltd.)

Emalex 550 (made by Nihon Emulsion Co., Ltd.)

Emulgen 130 (product made by Kao Corporation)

Emalex 1625 (made by Nihon Emulsion Co., Ltd.)

Emalex 1825 (made by Nihon Emulsion Co., Ltd.)

Soaptanol 300 (made by Nihon Shokubai Co., Ltd.)

TA400-75 (product made by Lion Corporation)

Emulan To4070 (product made by BASF Corporation)

(d) component

d-1: Quaternary compound of dimethyl sulfuric acid of triethanolamine (compound of general formula (13))

d-2: quaternary compound by methyl chloride of methyldiethanolamine (compound of formula (14))

In addition, the perfume shown in Table 3 was mix | blended with the Example and the comparative example as (e) component.

As an optional component, the component mix | blended with the liquid softening agent composition was shown to Tables 4 and 5 as (f) component.

Evaluation method of flexibility and slippage

(1) Softening treatment with softening agent

Using a commercially available cotton towel and polyester satin in a washing machine with a dryer (made by Senkan Shiroiyaku Soku NW-D8BX Vertical Type Hitachi Sesaku Sho Co., Ltd.), using a commercially available detergent `` Top '' (made by Lion Corporation) What was pre-processed was used as a test fabric (standard detergent use, bath ratio 30 times, tap water at 45 ° C, 10 minutes after rinsing with water 10 minutes after washing). Polyester satin was used as a test fabric after ironing to smooth the surface after drying. Approximately 1,000 g of cotton towel and polyester satin which were pretreated (cotton towel: polyester satin = 7: 3 (mass ratio)) were put in an electric washing machine (product made by Senkan Shiroiyakusoku NW-D8BX vertical type Hitachise Corporation) It wash | cleaned using commercially available detergent "top" (product made from Lion Co., Ltd.) (standard use amount, bath ratio 30 times, use of 25 degreeC tap water, 10 minutes). In the second rinse, the softening agent composition was added so that the component (a) was 40 ppm with respect to 30 L of water, and the softening treatment (bath ratio 30 times, use of 25 ° C tap water, 3 minutes) of each fabric was performed. Then, it dried naturally for 24 hours on 20 degreeC and 40% RH conditions, the softness was evaluated about cotton towel, and the slipperiness | lubricacy was evaluated about polyester satin.

(2) Evaluation of flexibility and slipperiness was performed by comparing a pair of sensory performances by 10 expert panelists with the fabric treated using the liquid detergent composition described in Comparative Example 1 as a control, and evaluated according to the evaluation criteria shown below. Done. The results are expressed as the average of 10 professional panelists.

<Facility Evaluation Criteria>

+2: definitely softer than contrast

+1: slightly softer than contrast

0: almost the same as contrast

-1: slightly softer contrast

-2: contrast is quite soft

<Slipperity Evaluation Criteria>

+2: definitely slippery than contrast

+1: slightly slippery than contrast

0: almost the same as contrast

-1: contrast side is slightly slippery

-2: the contrast is quite slippery

Stability evaluation method (viscosity after hydrolysis of flexible substrate)

The composition shown in Tables 6-9 was emulsified by said method, and the liquid softening agent composition was prepared. 80 mL was poured into the specification bottle (PS-N0.11) with a large spout, the cap was closed, and it was left to stand to 50 degreeC constant temperature room for 60 days. Then, it cooled to 25 degreeC, the viscosity after 20 second was measured with the Brookfield viscometer (BL clay system by TOKIMEC Corporation, rotation speed 30 revolutions / minute, N0.2 rotor), and evaluated by the following evaluation criteria.

<Evaluation Criteria>

Viscosity after storage

200 mPas or less ◎

More than 200 mPa · s to 500 mPa · s or less

Over 500 to 1000 mPa · s or less

More than 1000 mPa · s ×

Using the liquid softener composition shown in Tables 6 to 9, 1 kg of insulating cotton 100% T-shirt (made of UNIQLO) was washed under the same conditions as the softening treatment of (1), and the washing machine with a drying function until the drying step (Senkanshiro). Wrinkle production after finishing with Iyakushoku NW-D8BX Co., Ltd. product made by Hitachi Sesaku Sho) was confirmed. Wrinkles were reduced in all T-shirts treated with the liquid softener composition of the present invention.

f-1 to f-25, f-31 to f-33, and f-41 to f-49 describe their own formulation.

f-51 to f-68 describe the compounding amounts of the active ingredients.

Claims (6)

(a) 1-30 mass% of cationic compounds containing an ester group in a molecule | numerator, (b) 0.5-20 mass% of silicon whose specific gravity in 25 degreeC is 0.96-1.10, and a viscosity exceeds 5,000mm <2> / s and 500,000mm <2> / s or less, (c) The liquid softener composition containing 0.1-10 mass% of alcohol ethoxylates whose ratio (mass ratio) whose monovalent hydrocarbon group is a linear / branched chain is 5 / 95-95 / 5. (D) 0.4-10 mass% of quaternary compounds of alkanolamine of 4-10 total carbons are contained, The liquid softening agent composition of Claim 1 characterized by the above-mentioned. (b) Component silicone is polyoxyalkylene modified silicone represented by following General formula (1) or (2), The liquid softener composition as described in [1] or [2] characterized by the above-mentioned. (Wherein n is 50 to 10,000, m is 1 to 100, L is 1 to 5, p is 1 to 50, q is 0 to 50, X is a hydrogen atom or 1 to 3 carbon atoms) Is an alkyl group.) (Wherein s is 1 to 10,000, t is 1 to 1,000, p, q and X have the same meaning as above. R is an alkylene group having 1 to 5 carbon atoms.) The liquid softener composition according to claim 3, wherein the silicone of component (b) is a polyoxyalkylene-modified silicone represented by the general formula (1), wherein X is a methyl group or an ethyl group. The liquid softener composition according to claim 3 or 4, wherein the silicone of component (b) is a polyoxyalkylene-modified silicone represented by the general formula (1), wherein n is 160 to 10,000. The component (a) is a cationic compound according to any one of claims 1 to 5, wherein the component (a) is a cationic compound obtained by quaternizing an ester amine obtained by condensation reaction of triethanolamine with a fatty acid or fatty acid methyl ester with dimethyl sulfuric acid. Liquid softener composition, characterized in that.