JP5396642B2 - Liquid finish composition for textile products - Google Patents

Description

  The present invention relates to a liquid finish composition for textile products. More specifically, the present invention relates to a liquid finish composition for textiles that can give and improve excellent antistatic properties and slipperiness especially for a synthetic fiber product.

Liquid finishes for textiles are now indispensable products for home use, such as various types of spray-type textile finishes that are applied directly to fibers and soft finishes used during washing. In addition, products with added value such as deodorant and antibacterial properties have been demanded.
Conventionally, softeners based on quaternary ammonium salt type cationic surfactants and tertiary amine salt type cationic surfactants have been the mainstream, but are not amphiphilic surfactants. A composition using silicone and a cationic polymer compound as a main base has also been proposed. Some of these softeners may lack antistatic properties.
In softener finishing compositions based on quaternary ammonium salt type cationic surfactants, attempts to improve antistatic properties by using anionic surfactants or water-soluble anionic polymers in combination with this have been hitherto. (Patent Document 1).
However, in the case of a soft finish composition mainly composed of silicone and a cationic polymer compound, the antistatic property may be insufficient particularly under extremely low humidity conditions. The present applicant has already proposed several softening agent compositions using one or more silicone compounds and a cationic polymer compound in combination, but they have a transparent liquid composition and a low sticking property to a container. It is intended to provide no discoloration or fading even when placed in a transparent container, deodorizing and deodorizing properties, etc. (Patent Documents 2 to 5). Sex has not reached a sufficient level. In addition to the silicone compound and the cationic polymer compound, there has also been proposed a treating agent composition that imparts a favorable texture by using a hydrophobic compound having a solubility in water of 1% by mass or less (Patent Document 6). ), A compound specifically disclosed as the hydrophobic compound is not anionic.
Therefore, the present inventors have a silicone and a cationic polymer compound as main bases, and while maintaining the softening effect of the level normally required for softeners for textile products, the slipperiness and antistatic properties, especially for synthetic fibers, Has led to the development of a liquid finish composition for textiles with enhanced strength.

JP 63-291999 A (Lion) International Publication No. 2004/025017 Pamphlet (Lion) JP 2004-131895 A (Lion) JP 2004-131896 A (Lion) Japanese Patent Laying-Open No. 2005-187773 (Lion) JP 2006-342459 A (Kao)

  Accordingly, the present invention provides a liquid finish composition for textiles that not only exhibits a softening effect substantially equivalent to that of conventional softening agents on textiles, but also has improved antistatic properties especially against chemical fiber. For the purpose.

As a result of intensive studies by the present inventors, an anionic interface has been established so that the charge molar ratio of the cationic polymer compound to the liquid finish composition mainly composed of silicone and the cationic polymer compound is within a specific range. It has been found that the above object can be achieved by adding an activator. These three components can form a composite and improve antistatic properties. The present invention has been made based on such findings.
That is, the present invention includes the following components (A), (B) and (C), and the charge molar ratio between (B) and (C) is (B) :( C) = 1.0: 0. Provided is a liquid finish composition for textiles, which is within the range of 1 to 1.0: 1.0.
(A) silicone compound,
(B) a water-soluble polymer compound having cationic properties,
(C) Anionic surfactant.

  The composition of the present invention not only exhibits a softening effect equivalent to or better than that of a conventional softening agent, but also has an effect of imparting better antistatic properties to a synthetic fiber product. The composition of the present invention also exhibits excellent slipperiness especially against synthetic fibers.

[(A) component: silicone compound]
(A) component of this invention is a silicone compound generally used for textiles processing. This silicone compound can impart slipperiness when adsorbed on a textile product. Silicone compounds commonly used in textile processing include dimethyl silicone, polyether modified silicone, methyl phenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, Examples thereof include carboxy-modified silicone, carbinol-modified silicone, and amino-modified silicone, and one of these can be used alone or as a mixture of two or more.
The molecular structure of the silicone compound may be linear or branched or cross-linked. The modified silicone compound may be modified with one kind of organic functional group or may be modified with two or more kinds of organic functional groups.
The silicone compound can be used as an oil or as an emulsion dispersed by any emulsifier. Furthermore, from the viewpoint of enhancing the effect of adsorbing the silicone compound of the component (A) on the fiber by the component (B) described later and enhancing the slipperiness, the silicone compound of the component (A) is preferably nonionic, More preferable examples include dimethyl silicone, carbinol-modified silicone, epoxy-modified silicone, polyether-modified silicone, and amino-modified silicone.

  Among these, particularly preferable silicone compounds include polyether-modified silicones from the viewpoint of making the liquid finish composition for textiles transparent and increasing the commercial value. This silicone is suitable for obtaining a transparent finish composition with less slipping and good slipperiness than dimethyl silicone having no polyether group. Preferred polyether-modified silicones include copolymers of alkyl (C1 to C3) siloxane and polyoxyalkylene (preferably having 2 to 5 carbon atoms of an alkylene group). Among these, a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and propylene oxide, etc.) is preferable. Examples of such compounds include compounds represented by the following general formula (II) or (III).

(In the formula, M, N, a and b are average polymerization degrees, and R represents hydrogen or an alkyl group.)
Here, M is 10 to 10000, preferably 100 to 300, N is 1 to 1000, preferably 1 to 100, and M> N, and a is 2 to 100, preferably 2 to 50, b. 0-50, preferably 0-10. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The polyether-modified silicone represented by the general formula (II) generally has a carbon-carbon double bond at the terminal, such as an organohydrogenpolysiloxane having a Si-H group and a polyoxyalkylene allyl ether, for example. It can be produced by addition reaction of polyoxyalkylene alkyl ether with a platinum catalyst. Accordingly, the polyether-modified silicone may contain a slight amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si-H group has high reactivity, depending on storage conditions, it may be cross-linked to form an insoluble precipitate, so that the amount present in the polyether-modified silicone is 30 ppm. It is preferably present below (as the amount of Si-H).

(In the formula, A, B, h, and i are average polymerization degrees, R represents an alkyl group, and R ′ represents hydrogen or an alkyl group.)
Here, A is preferably 5 to 10,000, B is preferably 2 to 10,000, h is preferably 2 to 100, and i is preferably 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
The linear polysiloxane-polyoxyalkylene block copolymer represented by the general formula (III) has a polyoxyalkylene compound having a reactive end group and an end group that reacts with the reactive end group of the compound. It can be produced by reacting with dihydrocarbylsiloxane.
Such polyether-modified silicone has a longer side chain polyoxyalkylene chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and blend into aqueous compositions. Therefore, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.

  Specific examples of the polyether-modified silicone oil used in the present invention include SH3772M, SH3775M, SH3748, SH3749, SF8410, SH8700, BY16-850, BY22-008, SF8416, SF8421, manufactured by Toray Dow Corning Co., Ltd. SH200C-5000CS, F8421, SILWET L-7001, SILWET L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-4162, SILWET FZ-2162 , SILWET FZ-2171, ABN SILWET FZ-F1-009-01, ABN SILWET FZ-F1-009-02 , ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13 ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222, Shin-Etsu Chemical KF352A, KF6008, KF615A, KF6016, KF6017, GE Toshiba Silicone TSF4450, TSF4452 etc. These can be used alone or as a mixture of two or more.

The silicone compound of component (A) used in the present invention preferably has a kinematic viscosity at 25 ° C. of 100 to 100,000,000 mm ² / s, and 1,000 to 10,000,000 mm ² / s. Is more preferable. When the kinematic viscosity is in the above range, good flexibility can be imparted to the fiber product.
The blending amount of the silicone compound of the component (A) used in the present invention is not particularly limited, but is preferably 3 to 40% by mass based on the total mass of the composition from the viewpoint of flexibility, slipperiness and composition viscosity. More preferably, it is 5-30 mass%, Most preferably, it is 6-20 mass%. Thereby, effects, such as a softness | flexibility and slipperiness, can be made excellent, and a usability can be made favorable by suppressing the raise of a viscosity.

[Component (B): Water-soluble polymer compound having cationic property]
In the present invention, the component (B) forms a complex with the silicone compound of the component (A) and the anionic surfactant of the component (C), and the adsorption of (A) and (C) on the surface of the fiber product The amount can be increased, and the slipperiness and antistatic property for the textile can be improved.
The cationic water-soluble polymer compound that can be used in the present invention is positively charged as a whole when dissolved in water. That is, the monomer constituting the water-soluble polymer compound having cationic property is not only a cationic monomer having only a cationic group, but also an anionic monomer having only an anionic group and a nonionic monomer having only a nonionic group. Can be used, but the total charge of the compound is positive. (B) As a component, the water-soluble high molecular compound which has 1 or more types of cationic groups chosen from an amino group, an amine group, and a quaternary ammonium group is preferable. In the present invention, the water-soluble polymer refers to a polymer that is transparent and not transparent when 1.0 g of a polymer compound is added to 100 g of water at 25 ° C.

  The cationic water-soluble polymer compound used in the present invention includes a polymer composed only of a cationic monomer, a binary copolymer of a cationic monomer and a nonionic monomer, and a part of a nonionic polymer. Examples include those modified or substituted with a cationic group (such as cationized cellulose), binary copolymers of cationic monomers and anionic monomers, and terpolymers of cationic monomers, anionic monomers, and nonionic monomers. be able to. The monomers constituting each polymer compound may be used alone or in combination of two or more. Examples of the anionic group include a carboxyl group and a sulfonic acid group contained in the monomer unit in the polymer chain. Specific examples include carboxylic acid in acrylic acid.

  The water-soluble polymer as component (B) preferably has a weight average molecular weight of 1,000 to 5,000,000, more preferably 3,000 to 5,000, as measured by gel permeation chromatography (GPC). 3,000,000, more preferably 5,000 to 2,000,000. This makes it possible to suppress the increase in viscosity and to improve the usability.

Examples of the component (B) include dimethyl diallyl such as MERQUAT100 (manufactured by NALCO), Adeka thioace PD-50 (manufactured by Asahi Denka Kogyo), Daidol EC-004, Daidol HEC, Daidol Kasei (manufactured by Daido Kasei Kogyo), etc. Polymer of ammonium, dimethyldiallylammonium chloride / acrylamide copolymer such as MERQUAT550 JL5 (manufactured by NALCO), dimethyldiallylammonium chloride / acrylic acid copolymer such as MERQUAT280 (manufactured by NALCO), Leogard MGP (manufactured by Lion), Cationized cellulose such as Leogard KGP (manufactured by Lion), imidazolinium chloride / vinylpyrrolidone copolymer such as LUVIQUAT-FC905 (manufactured by BASF), POGA such as LUGALVAN-G15000 (manufactured by BASF) Copolymers with cationized polyvinyl alcohols such as reethyleneimine and poval CM318 (manufactured by Kuraray), natural polymer derivatives having amino groups such as chitosan, and vinyl monomers having hydrophilic groups with addition of diethylaminomethacrylate / ethylene oxide, etc. Etc.
Of these, dimethyldiallylammonium chloride polymer, dimethyldiallylammonium chloride / acrylamide copolymer, dimethyldiallylammonium chloride / acrylic acid copolymer, cationized cellulose, and cationized polyvinyl alcohol are preferred.
From the viewpoint of not obstructing the texture such as slipperiness and flexibility imparted by the silicone, those that do not give much rigidity to the fiber when adsorbed by the component (B) alone are preferable.

  A particularly preferable polymer particularly preferable as the component (B) in the present invention is a cationic polymer obtained by polymerizing a dimethyldiallylammonium salt represented by the following general formula (IV). The structural unit of the polymer is usually represented by the following general formula (V) or the following general formula (VI). Moreover, both the structural unit of general formula (V) and the structural unit of general formula (VI) may be contained.

In the formula, each of c and d is an average degree of polymerization, and is preferably in the range of 6 to 30,000, more preferably in the range of 20 to 6000, and still more preferably in the range of 30 to 3000.
Examples of such a polymer include MERQUAT100 (Nalco), Adekathioace PD-50 (Asahi Denka Kogyo), Daidol EC-004, Daidol HEC, Daidoru EC (Daido Kasei Kogyo), MERQUAT550 (Nalco), etc. And dimethyldiallylammonium chloride-acrylic acid copolymer such as MERQUAT280 (Nalco).
As the component (B) of the present invention, one kind of the above water-soluble polymer compound having cationic property may be used alone or as a mixture.

  (B) Although the compounding quantity of a component is not specifically limited, It is preferable to set it as the thing of the range which does not provide rigidity to textiles, For example, it shall be 0.1-30 mass% on the basis of the total mass of a composition. More preferably, it is 0.5-10 mass%, Most preferably, it is 1-5 mass%. By making the blending amount of the component (B) within such a range, the effect of promoting the adsorption of silicone and anionic surfactant is enhanced, and the slipping property, flexibility and antistatic property are made sufficient. It is possible to improve the usability by suppressing the increase in viscosity.

  In the liquid finish composition for textiles of the present invention, the mass ratio of the component (A): component (B) is preferably in the range of 99: 1 to 1:99. More preferably, it is in the range of 99: 1 to 50:50. By setting the ratio within such a range, the slipperiness and antistatic property for the synthetic fiber such as polyester satin and the flexibility for the synthetic fiber and cotton can be further improved. In addition, when the ratio of (A) component and (B) component exists in this range, the adsorptivity to silicone fiber can be made favorable.

[(C) component: anionic surfactant]
Component (C) in the composition of the present invention is an anionic surfactant. (C) The anionic surfactant and the component (B) form a complex containing a large amount of water and adsorb to the fiber, thereby imparting an excellent antistatic effect to the fiber. By adding the component (C) to the component (B) at a constant charge molar ratio, compared to the case of using only the two components (A) + (B), especially the slipperiness against synthetic fibers The antistatic property can be further improved.

Examples of the component (C) include those shown in the following (1) to (12).
(1) Linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms, preferably 12 to 16 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, or 1 to 6 moles of alkylene oxide added on average, or a linear or branched alkenyl having 10 to 20 carbon atoms An alkenyl ether sulfate having a group (AES); however, the alkylene oxide is preferably any one of alkylene oxides having 2 to 4 carbon atoms, or a mixture of ethylene oxide (EO) and propylene oxide (PO). (EO / PO = 0.1 / 9.9 to 9.9 / 0.1 in molar ratio).
(6) Alkyl phenyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, having an average of 3 to 30 moles of alkylene oxide added thereto, or a linear or branched chain having 10 to 20 carbon atoms An alkenyl phenyl ether sulfate having an alkenyl group; however, the alkylene oxide is preferably any one of alkylene oxides having 2 to 4 carbon atoms or a mixture of EO and PO (EO / PO = molar ratio). 0.1 / 9.9 to 9.9 / 0.1).
(7) Alkyl ether carboxylate having a linear or branched alkyl group having 10 to 20 carbon atoms, having an average of 0.5 to 10 moles of alkylene oxide added thereto, or a linear or branched chain having 10 to 20 carbon atoms An alkenyl ether carboxylate having a alkenyl group in the form of an alkenyl group; however, the alkylene oxide is preferably one having 2 to 4 carbon atoms or a mixture of EO and PO (molar ratio EO / PO). = 0.1 / 9.9 to 9.9 / 0.1).
(8) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) α-sulfo fatty acid salt or ester salt thereof. Preferable examples include saturated or unsaturated α-sulfo fatty acid salts having 8 to 20 carbon atoms (preferably 12 to 18 carbon atoms) or ester salts thereof.
(10) Long chain monoalkyl phosphate, long chain dialkyl phosphate, or long chain sesquialkyl phosphate.
(11) Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate, or polyoxyethylene sesquialkyl phosphate.
(12) A higher fatty acid salt having 10 to 20 carbon atoms. Preferably, a C12-18 unsaturated fatty acid salt or a mixture of the unsaturated fatty acid salt and a C12-18 saturated fatty acid salt.

Among the above components (C), (1) linear or branched alkylbenzene sulfonate having a C12-16 alkyl group (LAS or (ABS), (5) an alkyl or alkenyl ether sulfate having 10 to 14 carbon atoms added with an average of 1 to 6 moles of ethylene oxide, (9) a saturated or unsaturated α-sulfo fatty acid salt having 12 to 18 carbon atoms, or The ester salt and (12) an unsaturated higher fatty acid salt having 12 to 18 carbon atoms or a mixture of the unsaturated fatty acid salt and a saturated fatty acid salt having 12 to 18 carbon atoms are more preferred. (5) and (12) are more preferable.
The component (C) can be used as alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like. Of these, alkali metal salts such as sodium and potassium are preferred.
As the component (C), a commercially available product can be used, or it can be produced by a production method known in the art.
Although the compounding quantity of (C) component is not specifically limited, For example, based on the total mass of a composition, it is good to set it as 0.05-10 mass%, More preferably, it is 0.2-5 mass%, Especially preferably Is preferably 0.5 to 3% by mass. By making the blending amount of the component (C) within such a range, it becomes possible to improve the antistatic property of the synthetic fiber while maintaining the softening effect.

[(B) :( C) Charge molar ratio]
The “charge molar ratio” in the present invention is a ratio between the net positive charge mole number of the component (B) and the net negative charge mole number of the component (C). The charge molar ratio is (B) :( C) = 1.0: 0.1 to 1.0: 1.0, preferably 1.0: 0.2 to 1.0: 0.8. When the charge molar ratio is within the above range, it is possible to exhibit excellent slipping property and antistatic property particularly for synthetic fibers while maintaining flexibility.
The component (B) may contain not only a cationic monomer but also an anionic monomer and a nonionic monomer as its structural unit. However, the positively charged mole number of the entire component (B) is derived from the cationic monomer. It can be calculated by subtracting the number of moles of negative charge derived from an anionic monomer from the number of moles of positive charge. Positive charges moles from cationic monomer, based on the following equation (1), cationic monomer 1, cationic monomer 2, by calculating the sum of the charged molar number corresponding to ... cationic monomer i Ask.

Number of positively charged moles = Wc × (M a ₁ × P a ₁ / Y ₁ + M a ₂ × P a ₂ / Y ₂ +... + M a _i × P a _i / Y _i ) (1 )

(Wc: blending amount of component (B) in the composition (mass%)
Ma ₁ : polymerization ratio of cationic monomer 1 in component (B), Ma ₂ : polymerization ratio of cationic monomer 2 in component (B),... Ma _i : cationic monomer i in component (B) Polymerization ratio of
Pa _1: number of cationic groups of the cationic monomer in 1, Pa _2: number of cationic groups of the cationic monomer in 2, ··· Pa _i: cationic groups in the cationic monomer i,
Y ₁ : Molecular weight of the cationic monomer 1, Y ₂ : Molecular weight of the cationic monomer 1,... Y _i : Molecular weight of the cationic monomer i)
Here, “the number of cationic groups” means the number of cationic groups in one monomer.
Next, the number of moles of negative charge derived from an anionic monomer is the sum of the number of moles of charge corresponding to anionic monomer 1, anionic monomer 2, ... anionic monomer i based on the following formula (1) '. It is obtained by calculating .

Number of moles of negative charge = Wc × (Mb ₁ × Pb ₁ / Z ₁ + Mb ₂ × Pb ₂ / Z ₂ +... + Mb _i × Pb _i / Z _i ) (1) '

( Wc: blending amount of component (B) in the composition (mass%)
Mb ₁ : Polymerization ratio of anionic monomer 1 in component (B) , Mb ₂ : Polymerization ratio of anionic monomer 2 in component (B) ,... Mb _i : Anionic monomer i in component (B) Polymerization ratio of
Pb ₁ : number of anionic groups in anionic monomer 1, Pb ₂ : number of anionic groups in anionic monomer 2,... Pb _i : number of anionic groups in anionic monomer i,
Z ₁ : molecular weight of anionic monomer 1, Z ₂ : molecular weight of anionic monomer 1, ... Z _i : molecular weight of anionic monomer i)
Here, the “number of anionic groups” means the number of anionic groups in one monomer.
(C) The negative charge mole number of a component is calculated | required by the following formula | equation (2).

Number of moles of negative charge = Wa / Xa (2)

(Wa: blending amount (mass%) of component (C) in the composition, Xa: molecular weight of component (C))

[Optional component: Nonionic surfactant]
Further, the liquid finish composition for textile products of the present invention contains a nonionic surfactant and a water-soluble solvent in order to keep the appearance of the composition transparent or to keep the emulsion in a stable state. Can be blended.

Nonionic surfactants include polyoxyalkylene alkyl ethers having one or more alkyl groups or alkenyl groups having 8 to 20 carbon atoms, alkylamines having 8 to 20 carbon atoms, or alkylene oxide adducts of alkylamides, carbon numbers. Examples thereof include mono-, di-, tri-, tetra-esters or mixtures thereof of 8 to 20 saturated or unsaturated fatty acids and glycerin, pentaerythritol, sorbitol, ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol. Among these, nonionic surfactants represented by the following general formula (VII) are preferable.
R ¹ —T — [(R ² O) _p —H] _q (VII)
(Wherein R ^{1 is} a hydrocarbon group having 10 to 20 carbon atoms, preferably an alkyl group or alkenyl group having 12 to 18 carbon atoms, and R ² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. P: The average number of moles added is 2 to 100, preferably an integer of 5 to 70. T is —O—, —N—, —NH—, —N (C ₂ H ₄ OH) —, —CON—, —. CONH- or _{CON (C 2 H 4 OH)} - and is, T is -O -, - NH -, - N (C 2 H 4 OH) -, - CONH-, or -CON (C ₂ H ₄ OH) In the case of-, q is 1, and when T is -N- or -CON-, q is 2.)

Specific examples of the compound represented by the general formula (VII) include compounds represented by the following general formulas (VIII) to (XI).
R ¹ —O— (C ₂ H ₄ O) _r —H (VIII)
(In the formula, R ¹ has the same meaning as described above, and r is the average number of moles added and is an integer of 2 to 100, preferably 5 to 70.
R ¹ —O— (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t —R ³ (IX)
Wherein R ¹ is the same meaning as described above, s, t is the average number of moles added, s is a number from 2 to 100, preferably 5 to 70, and t is 1 to 5, preferably 1 to 3. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be a random adduct or a block adduct. R ³ : H or an alkyl group having 1 to 3 carbon atoms.)
For example, polyoxyethylene alkyl ether having at least one alkyl group or alkenyl group having 12 to 18 carbon atoms is preferable, and an average of 30 to 70 moles of oxyethylene group added is particularly preferable.

(In the formula, R ¹ has the same meaning as described above, u and v are the average number of added moles, and the sum of u + v is a number of 2 to 60, preferably 2 to 40.

  The compounding amount of the nonionic surfactant is preferably 0.05 to 10% by mass, particularly 0.25 to 8% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the composition. preferable. By making such a lower limit compounding amount, the effect of improving the storage stability can be made sufficient, while by making it lower than the upper limit, the excessive addition when the effect reaches saturation is suppressed and economical. In addition, it can be preferable from the viewpoint of no foaming during the treatment.

[Optional ingredients: Water-soluble solvent]
On the other hand, it is preferable to use a water-soluble solvent in combination for the purpose of improving the handleability of the component (A) and for improving the emulsifying dispersibility of an oil-soluble additive such as a higher alcohol in an aqueous liquid. The water-soluble solvent is selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a compound represented by the following general formula (XII). Is preferable.
^{_{R 4 -O- (C 2 H 4}} O) y- (C 3 H 6 O) z-H (XII)
(Wherein R ⁴ is an alkyl group or alkenyl group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms. Y and z are average added mole numbers, and y is 2 to 50, preferably 2 to 30. Z represents a number of 0 to 50, preferably 0 to 20.)
Among them, preferred examples include ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol monopropylene glycol monobutyl ether [C ₄ H ₉ (C ₃ H ₆ O) ₁ (C ₂ H ₄ O) ₂ H] and the like. It is done.
The blending amount of the water-soluble organic solvent should be 0.05 to 15% by mass, preferably 1 to 10% by mass, more preferably 3 to 8% by mass, based on the total mass of the composition. Can do.

[Optional ingredient: Water]
The composition of the present invention is preferably an aqueous composition, and as the water used, any of tap water, ion-exchanged water, pure water, distilled water, etc. can be used, but calcium present in a trace amount in water, Water from which hardness components such as magnesium and heavy metals such as iron are removed is preferable, and ion exchange water is most preferable in consideration of cost.

[Optional ingredients: perfume composition]
In the present invention, a fragrance can be added for the fragrance of the composition. Although it does not specifically limit as a fragrance | flavor, The list | wrist of the fragrance | flavor raw material which can be used is various literature, for example, "Perfume and Flavor Chemicals", Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower Oils". , Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., each of which is incorporated herein by reference.

[Optional ingredients: Preservatives]
The liquid finish composition for textiles of the present invention is used by mixing one or more organic preservatives and inorganic preservatives for the purpose of maintaining antiseptic properties during storage. it can.
Of these, isothiazolone organic sulfur compounds, imidazole / thiazole organic sulfur compounds, benzoic acids, phenolic compounds, and cationic surfactants are preferred from the viewpoint of antiseptic sterilization effect and storage stability. 1 type (s) or 2 or more types can be mixed and used.

As an example of the isothiazolone organic sulfur compound, an organic preservative containing a 3-isothiazolone group is preferable. These compounds are disclosed in US Pat. No. 4,265,899, issued May 5, 1981.
Examples thereof include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone, 2-methyl- 4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. A more preferred preservative is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% by weight of 5 A water-soluble mixture of chloro-2-methyl-4-isothiazolin-3-one and about 23% by weight of 2-methyl-4-isothiazolin-3-one. Examples of isothiazolone-based organic sulfur compounds include Ron &Haas's Caisson CG / ICP (approximately 1.5% by mass aqueous solution) and Junsei 5 (approximately 5% by mass ethylene glycol solution) manufactured by Pure Chemical. Commercially available products exemplified in the series can be used.

  Examples of imidazole / thiazole organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithiols as related compounds. -2,2-bis (benzmethylamide) and the like can also be used, and they can be used in any mixing ratio. As such a compound, Avicia's Proxel series [BDN (33% by mass), BD20 (20% by mass), XL-2 (10% by mass), GXL (20% by mass) %), LV (effective mass 20% by mass), TN (effective mass 60% by mass)], and Denside BIT / NIPA.

  Examples of benzoic acids and phenol compounds include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, 3 -Methyl-3-isopropylphenol, o-phenylphenol, 2-isopropyl-5-methylphenol, resorcin, cresol, 2,6-di-tert-butyl-p-cresol, and the like can be used.

  As the cationic compound, benzalkonium chloride, benzethonium chloride, alkyltrimethylammonium salt, alkylquinolinium salt, alkylaminopropyldimethylbenzylammonium salt, alkylpyridinium salt, dialkyldimethylammonium salt, polyoxyalkylenetrialkylammonium salt, Examples thereof include alkylphenoxyethyldimethylbenzylammonium salt, alkylisoquinolinium salt, alkyldimethylbenzylammonium salt, polyoxyethylenetrimethylammonium salt, alkyldimethylphenoxyethylammonium salt, alkylimidazolium salt, chlorhexidine gluconate and the like.

  These antibacterial agents are preferably blended in an amount of 0 to 10% by weight, more preferably 0.00001 to 5% by weight, and more preferably 0.00005 to 3% by weight based on the composition.

[Optional component: Dye]
In the present invention, a dye can be added for coloring the composition. The dye is not particularly limited, but is preferably a water-soluble dye from the viewpoint of ease of addition, and among these, one or more water-soluble dyes selected from acidic dyes and direct dyes are preferable. Specific examples of dyes that can be added include, for example, the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, issued July 20, 1969, Maruzen Co., Ltd.), Dye Note 22nd Edition (Colored Co., Ltd.), Legal Dye Handbook (Japan Cosmetic Industry Federation edited, issued on November 28, 1988, Yakuho Nippo Co., Ltd.) and the like, which are incorporated herein by reference. The blending amount of the dye is preferably 0.005 to 25 ppm, more preferably 0.05 to 15 ppm, based on the total mass of the composition. By setting it as such a compounding quantity, a finisher composition can be colored moderately.

[Optional ingredients: Antioxidants]
In the present invention, an antioxidant can be added to improve the stability of the fragrance and color tone of the composition. As the antioxidant, generally known natural antioxidants and synthetic antioxidants can be used. Specifically, a mixture of ascorbic acid, ascorbyl palmitate, propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, hydroquinone, tertiary butylhydroquinone Natural tocopherol compounds, long-chain esters of gallic acid (C8 to C22) such as dodecyl gallate, irganox compounds available from Ciba Specialty Chemicals, citric acid and / or isopropyl citrate, 1-hydroxyethylidene -1,1-diphosphonic acid (etidronic acid), 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, furans, amino acids, etc.
Among these, BHT (butylated hydroxytoluene), methoxyphenol, tocopherol compounds, and the like are preferable from the viewpoint of the appearance and storage stability of the liquid finish composition.
The antioxidant is preferably used in the range of 0.005 to 0.5 mass%.

[Optional ingredients: Antifoaming agent, other additive ingredients]
An antifoaming agent can be mix | blended with the composition of this invention. Examples of the antifoaming agent include alcohol-based antifoaming agents, ester-based antifoaming agents, mineral oil-based antifoaming agents, vegetable oil-based antifoaming agents, and synthetic oil-based antifoaming agents. The blending amount of the antifoaming agent is not particularly limited, but can be 0.05 ppm to 0.5 mass%, more preferably 0.5 ppm to 0.05 mass%, based on the total mass of the composition. be able to.
In the composition of the present invention, additives that are used in ordinary household softeners or textile finishes can be used as long as the effects of the present invention are not impaired. Specific examples of such additives include cationic surfactants, plant extracts, liquid paraffin, higher alcohols, hydrocarbons, urea, nonionic cellulose derivatives, UV absorbers, fluorescent whitening agents, and the details will be described later. A pH adjuster, a viscosity adjuster, etc. are mentioned.

[PH and pH adjuster]
The pH of the liquid finish composition for textile products of the present invention is not particularly limited, but is preferably in the range of 2 to 10, more preferably in the range of 3 to 7. As necessary, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, paratoluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, PH adjustment of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, and alkali metal silicates An agent can be used.

[Viscosity and viscosity modifier]
The viscosity of the composition of the present invention is not particularly limited, but it is 5 to 100 mPa · s (25 ° C., B-type viscometer manufactured by TOKIMEC, No. 2 rotor) in the case of a product to be added to rinse water in the rinsing process of washing. On the other hand, in the case of a product that is filled in a trigger spray container or a dispenser container and sprayed directly onto a textile product, the usability is good when it is 40 mPa · s or less.
In order to control the viscosity of the liquid softening agent composition of the present invention, inorganic or organic water-soluble salts can be used. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, and the like can be used, among which calcium chloride and magnesium chloride are preferable. These water-soluble salts can be blended in the liquid finish composition in an amount of about 0 to 1%, and may be blended in any step of the liquid finish composition production.

[Basic manufacturing method]
The liquid finish composition for textiles of the present invention contains the above components (A) to (C) and optional components, and the balance is usually water. Although the manufacturing method in particular of the liquid finish composition for textiles of this invention is not restrict | limited, For example, it can mix | blend as follows. That is, a predetermined amount of the component (A) and optionally a water-insoluble optional component are stirred and mixed at room temperature in a blending container. Next, ion-exchanged water was added while stirring the resulting mixture, and water-soluble optional components were further added. Finally, the component (C) can be added with stirring, and then the mixture can be uniformly stirred and mixed.

[Target textile products]
Although it does not specifically limit as a textile product of the object which uses the composition of this invention, For example, a towel, sportswear, a T-shirt, a polo shirt, a blouse, a chinos, a suit, slacks, a skirt, etc. are mentioned. In addition, the material of the target textile product is not particularly limited, for example, natural fibers such as cotton, wool and hemp, synthetic fibers such as polyester, nylon and acrylic, semi-synthetic fibers such as acetate, rayon, tencel, Examples thereof include recycled fibers such as polynosic and blended products, blended fabrics, and blended products of these various fibers.

[how to use]
The method of using the composition of the present invention is not particularly limited, but the clothes are usually washed, and at the stage of rinsing, the composition of the present invention is dissolved in water and processed, or a container such as a tub is used. Examples include a method in which the composition of the present invention is dissolved in water, and further, a garment is added and immersion treatment is performed. The treatment of the textile product may be performed by any method, but the bath ratio (mass ratio of the treatment liquid to the textile product) in the case of rinsing treatment or immersion treatment is 3 to 100 times, particularly 5 to 50 times. preferable. The concentration of the finishing composition in the rinsing liquid is preferably 0.001 to 0.2% by mass, and particularly 0.01 to 0.15% by mass provides the best performance improvement effect.

[Preparation of liquid softener composition]
The composition of an Example and a comparative example was prepared using the component shown below with the compounding quantity shown to Table 5,6. Hereinafter, “mass%” is abbreviated as “%”.

note)
<C-2>
c-2 was obtained by neutralizing “extra olein” (a mixture of oleic acid: 92% and stearic acid: 8%) manufactured by NOF with an aqueous solution of sodium hydroxide (48%) equivalent to it.
<C-3>
c-3 has a mixing mass ratio of 80 sodium salt of α-sulfo fatty acid methyl ester having a fatty acid residue of 16 carbon atoms and sodium salt of α-sulfo fatty acid methyl ester having a fatty acid residue of 18 carbon atoms. : 20 aqueous solution. The active ingredient concentration is about 70% and the balance is water, unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate and the like.
MES usually contains α-sulfo fatty acid dialkali salt as a by-product in addition to α-sulfo fatty acid methyl ester salt. The α-sulfo fatty acid dialkali salt also has a function as a surfactant, like the α-sulfo fatty acid methyl ester salt. Therefore, AI concentration means the total concentration of α-sulfo fatty acid methyl ester salt and α-sulfo fatty acid dialkali salt which is one of by-products.
<C-4>
c-4 is a linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Corporation, Lipon LH-200 (LAS-H pure content 96 mass%), average molecular weight 323], equivalent to sodium hydroxide Obtained by neutralization with an aqueous solution (48%).
[Raw materials for optional components]

As optional components used in addition to the fragrance composition, a water-soluble solvent, an antifoaming silicone, a storage stabilizer, an antibacterial agent, a plant extract and ion-exchanged water were used. The detailed composition of the optional components is described below. In addition, the compounding quantity of an arbitrary component is shown on a solid basis.
[Arbitrary component composition]

  According to the following compounding method, 400 g of each of the compositions of Examples and Comparative Examples shown in Table 11 was prepared and used for evaluation.

[Mixing method]
In a 500 mL beaker, a predetermined amount of the component (A) and a water-insoluble optional component as necessary were stirred and mixed at room temperature. Next, ion-exchanged water and a water-soluble optional component were sequentially added while stirring the obtained mixture. Next, the component (B) and the component (C) were sequentially added while stirring, and then sufficiently stirred and mixed until uniform to prepare 400 g of a liquid finish composition. A magnetic stirrer was used for stirring.

[Finishing treatment and evaluation method]
(1) Pre-treatment method for evaluation cloth Commercial polyester satin (100% polyester) and cotton towel (100% cotton) commercial detergent “Top” [manufactured by Lion Corporation, component: surfactant (alpha olefin sulfo fatty acid Pretreatment with sodium 2-fatty washing machine for home use by using sodium ester, fatty acid sodium, linear alkylbenzene, polyoxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent)] After carrying out the test, what was naturally dried indoors was used as a test cloth.
Pretreatment conditions: Washing 15 minutes (standard amount of detergent: 20 g / 30 L, 30 times bath ratio, 45 ° C. tap water) → After repeating the process of dehydration 5 minutes twice, rinse with water for 15 minutes → dehydration 5 minutes This process was repeated 5 times.

(2) Finishing process in washing and rinsing process [Examples 1 to 15 and Comparative Examples 1 to 4]
1 kg each of the polyester satin and cotton towel subjected to the above pre-treatment are commercially available detergent “TOP” (manufactured by Lion Corporation, ingredients: surfactant (sodium alpha olefin sulfofatty acid ester, fatty acid sodium, linear alkylbenzene, polyoxy (Ethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent] for 15 minutes (detergent is 30% standard bath use, 25 ° C tap water is used). 20 g of the liquid finish composition for textiles shown in Examples and Comparative Examples was added to 30 liters of water to finish the textiles (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). . Then, it air-dried on 20 degreeC and 40% RH conditions, and evaluated (3).

(3) Evaluation of antistatic properties <Washing rinse process>
Using the cotton towel treated according to Comparative Example 3 as a control, a pair of sensory comparisons of flexibility was performed by 10 professional panelists, and evaluation was performed according to the following evaluation criteria.
<Evaluation criteria>
5 points: clearly better than the control.
4 points: Slightly better than the control.
3 points: equivalent to control.
2 points: Slightly worse than the control.
1 point: clearly worse than the control.
<Criteria>
The average of the scores of 10 panelists was taken and judged according to the following criteria. In terms of product value, ○ or more was considered acceptable.
◎: 4.0 points or more ○: 3.0 points or more and less than 4.0 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

<Evaluation method>
Polyester satin after finishing treatment and drying at 20 ° C-20 ± 5% RH for 24 hours is further conditioned for 48 hours under the same conditions, and then charged under the same conditions by JIS L1094-1997 (A) method (half-life measurement method). The prevention property was evaluated. About the washing rinse process, the polyester satin processed by the comparative example 3 was made into the comparison control sample, and evaluation was performed based on the following criteria. Incidentally, the half-life of the polyester satin subjected to the washing and rinsing process using Comparative Example 3 is unavoidably caused by fluctuations depending on the evaluation conditions such as the pretreatment of the test cloth and the humidity and humidity. Enter the range of seconds.
<Criteria>
A: Less than 1/5 of the half-life of the fabric treated with the control sample ○: More than 1/5 and less than 1/2 of the half-life of the fabric treated with the control sample Δ: Half-life of the fabric treated with the control sample 1/2 or more and 1/1 or less of ×: More than 1/1 of the half-life of the cloth treated with the comparative control sample

Claims (9)

The following (A), (B) and (C) components are included, and the charge molar ratio of (B) to (C) (B) :( C) = 1.0: 0.1 to 1.0: 1 A liquid finish composition for textiles characterized by being in the range of 0.0:
(A) silicone compound,
(B) a water-soluble polymer compound having cationic properties,
(C) Anionic surfactant.   The liquid finish composition for textiles according to claim 1, wherein the component (A) is a polyether-modified silicone. The liquid finish composition for textiles according to claim 2, wherein the polyether-modified silicone is a compound represented by the following formula (II).

(In the formula, M, N, a and b are average polymerization degrees, M is 10 to 10000, N is 1 to 1000, a is 2 to 100, and b is 0 to 50. R is hydrogen or carbon number. Represents 1 to 4 alkyl groups.) The liquid finish composition for textiles according to any one of claims 1 to 3 , wherein the content of the component (A) is 5 to 40% by mass based on the total mass of the composition.   The component (B) is a homopolymer of dimethyldiallylammonium chloride or a copolymer of the monomer and another monomer, The liquid finish for textiles according to any one of claims 1 to 4. Composition.   (B) The liquid finish composition for textiles of any one of Claims 1-5 whose content of a component is 0.1-30 mass% on the basis of the total mass of a composition. The component (C) is selected from the group consisting of polyoxyethylene (alkyl or alkenyl) ether sulfates represented by the following general formula (I), higher fatty acid salts having 10 to 20 carbon atoms, and mixtures thereof. The liquid finish composition for textiles according to any one of -6.
^{_{R 1 O- (CH 2 CH 2}} O) n 1 -SO 3 M ··· (I)
(R ¹ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, n ₁ represents the average number of moles added of the ethylene oxide group, and is in the range of 1 to 6. M is an alkali metal, an alkaline earth metal, Alkanolamine or ammonium.)   The liquid finish composition for textiles according to any one of claims 1 to 7, wherein the content of the component (C) is 0.05 to 10% by mass based on the total mass of the composition.   The liquid finish composition for textiles according to any one of claims 1 to 8, wherein the mass ratio of (A) to (B) is in the range of 99/1 to 50/50.