JP4381306B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener used for textile products such as clothing. In particular, the present invention can provide excellent flexibility, smoothness, draping properties, and quick-drying properties not only to natural fibers such as cotton but also to various textile products and clothing made from chemical fibers such as polyester. The present invention relates to a liquid softener composition mainly composed of silicone that is mild to the skin.

  Conventionally, softeners containing various quaternary ammonium salts as main components have been used for the purpose of adding flexibility during rinsing after washing and imparting flexibility to textiles. As the quaternary ammonium salt, a di-long-chain quaternary ammonium salt is generally used. However, the softener mainly composed of a di-long chain type quaternary ammonium salt has a good softness-imparting effect for cotton products, but it may cause a slimy feeling or may be chemically treated with polyester or the like depending on conditions. The softening effect on textiles is small, and the effect of imparting smoothness and draping to various textiles is also small.

  In addition, softeners using di-long-chain cationic surfactants are generally emulsion-based, but attempts have been made to obtain highly transparent compositions in order to increase commercial value (Japanese Patent Laid-Open No. 8- 505906 publication). However, since the di-long-chain cationic surfactant is hardly soluble in water, a large amount of organic solvent must be present in order to obtain a transparent composition. For this reason, there is an unpleasant organic solvent odor, and it is uneconomical to add a large amount of an organic solvent having no flexibility imparting effect.

  On the other hand, silicone compounds are known to impart unique flexibility, flexibility, and smoothness to fiber products, particularly chemical fibers. However, silicone is poor in adsorptivity to fibers in the finishing treatment in a water bath, and must be treated from a high concentration bath in order to obtain a sufficient effect. In order to remedy such drawbacks, the present inventors have previously proposed a small amount of cationic surface activity as a means for efficiently adsorbing silicone from fibers in a water bath as described in JP-A No. 2000-154476. A fashionable finish composition using a combination with an agent was proposed. However, this finish composition exhibits excellent performance when used after a fashionable nonionic detergent, but when used after an anionic detergent used in normal laundry, the anion remaining in the rinse bath There is a problem that the performance is lowered due to the influence of the activator.

  Japanese Patent Application Laid-Open No. 10-183472 discloses a finish for clothing containing a water-insoluble / non-cured silicone mainly composed of a water-soluble polymer compound that has been used for the purpose of imparting elasticity to clothing. An agent composition is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 2000-129777 and Japanese Patent Application Laid-Open No. 2000-129578 mainly include a water-soluble polymer compound that has been used for the purpose of imparting elasticity to clothing, and includes a silicone compound and a nonionic interface. Disclosed is a textile treatment composition comprising an active agent. However, when a textile product is processed using these compositions, the rigidity value is increased, which is not preferable as a softening agent that requires flexibility.

  Furthermore, Japanese Patent Application Laid-Open No. 2000-239970 proposes a fiber product treating agent mainly composed of a water-soluble polymer compound that has been used for the purpose of imparting elasticity to clothing and containing amino-modified silicone. . However, when a textile product is treated with this composition, not only is it not preferable as a softening agent to increase the rigidity value, but the textile product may be yellowed by amino-modified silicone depending on storage conditions.

  The present invention can provide excellent flexibility, smoothness, drape and quick drying, is mild to the skin, has good storage stability, and further improves the added value of the appearance of the product. An object of the present invention is to provide a water-based liquid softener composition having a highly transparent liquid appearance and good water absorption. In addition, this liquid softener composition can be used not only for non-ionic detergents such as fashionable wear, but also for finishing treatment in rinse baths after washing with general-purpose anionic detergents, not only natural fibers such as cotton It aims at being able to be used for various textile products, such as clothing made from chemical fibers such as polyester.

  The present inventor imparts excellent flexibility, smoothness, drape, and quick drying properties to the skin while being mild by using a silicone compound and a cationic polymer compound in a specific ratio. Furthermore, by using a nonionic surfactant and a water-soluble solvent in combination, the storage stability is improved, and by using a silicone having a polyether group as the silicone compound, a water-absorbing and highly transparent liquid is obtained. The liquid softening agent which has an external appearance was obtained, and it discovered that the said subject could be achieved by these and came to complete this invention.

That is, the present invention
[1] (A) One to two or more dimethyl silicones, 6 to 40% by mass of a silicone compound selected from epoxy-modified silicones and polyether-modified silicones , and (B) one or more cationic compounds A liquid softening agent composition comprising 0.1 to 30% by mass of a water-soluble polymer compound in a ratio of (A) :( B) (mass ratio) of 95: 5 to 60:40,
[2] It further comprises (C) a nonionic surfactant, and (D) one or more water-soluble solvents selected from lower alcohols and glycol ether solvents, 5 to 30% by mass. And [1] a liquid softener composition,
[3] The liquid softener composition according to [1] or [2], wherein the component (A) is a polyether-modified silicone , and the composition is transparent,
[4] The liquid softener composition according to any one of [1] to [3], wherein the component (B) is a polymer of dimethyldiallylammonium salt;
[5] The liquid softener composition according to any one of [1] to [4], which is for mild skin.

The component (A) of the present invention is a silicone compound selected from dimethyl silicone, epoxy-modified silicone and polyether-modified silicone . The silicone compound is not particularly limited as long as it can impart flexibility, smoothness, and drapeability when adsorbed on the fiber product. Silicone compounds generally used for fiber treatment include dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy Examples thereof include 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. In particular, a silicone compound that does not contain an amino group is preferable in terms of preventing yellowing of a textile product that has been softened. Furthermore, the silicone compound of the component (A) is nonionic because it enhances the effect of adsorbing the silicone compound of the component (A) on the fiber by the component (B) described later, and improves flexibility, smoothness, and drapeability. is preferably, in the present invention, dimethyl silicone, a silicone compound selected from d epoxy-modified silicones and polyether-modified silicone is used.

  Among these, particularly preferable silicone compounds include polyether-modified silicones from the viewpoints of flexibility, imparting water absorption, and making the liquid softener composition transparent and increasing the commercial value. Compared to dimethyl silicone that does not have a polyether group, this silicone has less squeaking and good flexibility, and also has good water absorption for natural fibers such as cotton and synthetic fibers such as polyester. In addition, it is suitable for obtaining a transparent liquid softener composition. 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). Of these, a copolymer of dimethylsiloxane and polyoxyalkylene is preferred. In addition, polyoxyalkylene shows the random or block polymer of polyoxyethylene, polyoxypropylene, polyoxyethylene, and polyoxypropylene. Examples of such a compound include compounds represented by the following general formula (I).

（式中、Ｍ、Ｎ、ａ及びｂは平均重合度であり、Ｒは水素又はアルキル基を表す。）

(In the formula, M, N, a and b are average polymerization degrees, and R represents hydrogen or an alkyl group.)

  Here, M is preferably 10 to 10,000, N is preferably 1 to 1000, and M> N, more preferably M is 10 to 1000, N is 1 to 50, and M> N. a is preferably 2 to 100, and b is preferably 0 to 50. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.

  From the viewpoint of mildness, it is preferable that M + N is larger within the above range. Moreover, it is preferable that low molecular weight compounds such as unreacted substances inevitably mixed during production are removed by a purification step such as stripping as much as possible.

  The compound represented by the general formula (I) is generally composed of a methyl hydrogen polysiloxane having a Si-H group and a polyoxyalkylene having a carbon-carbon double bond at the terminal, such as a polyoxyalkylene allyl ether. It can be produced by addition reaction with an alkyl ether.

  Methyl hydrogen polysiloxane can be produced by the following conventional method. As a specific production method, first, methylchlorosilanes are obtained by a direct method in which metal silicon and methyl chloride are heated in the presence of a copper catalyst. Next, dimethyldichlorosilane (boiling point 70.2 ° C.), trimethylchlorosilane (boiling point 57.3 ° C.), and methyl hydrogen dichlorosilane (boiling point 40.4 ° C.) fractionated from the methylchlorosilanes at a predetermined ratio. By mixing and hydrolyzing by adding a large amount of water, a mixture of cyclic and linear dimethylsiloxane and methylhydrogensiloxane copolymer is obtained. Further, the obtained mixture of cyclic and linear dimethylsiloxane and methylhydrogensiloxane copolymer was separated from the cyclic (tetramer, pentamer) having a low polymerization degree by distillation. Used for polymerization of polysiloxane. The organohydrogenpolysiloxane can be obtained by heating a cyclic product having a low polymerization degree using an alkali or a strong acid as a catalyst, and a polymerization reaction including cleavage and recombination of siloxane bonds. Polymerization of the cyclic product with an alkali catalyst is carried out at a high temperature of about 150 ° C. using an alkali metal hydroxide as a catalyst, but lithium hydroxide and sodium hydroxide are not dissolved in the cyclic product with a low polymerization degree even at this temperature. Since a cyclic body cannot be polymerized, it is not preferable. Polymerization of the cyclic product with an acid catalyst can be carried out at room temperature or with heating using sulfuric acid, hydrochloric acid, phosphoric acid, activated clay, iron chloride, boric acid, trifluoroacetic acid or the like as a catalyst. However, in the case of dimethylpolysiloxane, either acid or base can be polymerized, but in the case of organohydrogenpolysiloxane having Si-H group, if a basic catalyst is used, Si-H group is decomposed during the polymerization. This is not preferable because it gels. Such polymerization of methyl hydrogen polysiloxane is stopped by neutralizing the catalyst, and then the by-produced cyclic product is removed by stripping to complete the production of the desired methyl hydrogen polysiloxane.

  Specific examples of the polyether-modified silicone oil used in the present invention include SH3772M, SH3775M, SH3748, SH3749, SF8410, SH8700, BY22-008, SF8421, Shin-Etsu Chemical (manufactured by Toray Dow Corning Silicone) KF352A, KF6008, KF615A, KF6016, KF6017, GE Toshiba Silicone Co., Ltd. TSF4450, TSF4452, Nippon Unicar Co., Ltd. SILWET L-7002, SILWET L-7602, SILWET L-7602, SILWET L -7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SIL ETFZ-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, and the like. Among these, SH3775M, BY22-008, KF6017, SILWET FZ-2171, ABN SILWET FZ-F1-009-54, ABN SILWET FZ- in terms of flexibility, smoothness, drape, mildness and quick drying Silicone such as 2222 is preferred. These can be used singly or as a mixture of two or more.

The blending amount of the silicone compound of the component (A) used in the present invention is not particularly limited. However, from the viewpoint of flexibility, smoothness, drapeability, mildness, quick drying, water absorption and viscosity of the composition, it is 6 40 mass% in the composition. If the blending amount is less than 3% by mass, the effects such as flexibility, smoothness, drape, mildness, quick drying, water absorption may be insufficient, and if it exceeds 70% by mass, the viscosity of the composition is high. Therefore, usability may be reduced.

  The component (B) of the present invention has an effect of adsorbing the silicone compound of the component (A) to the fiber. As the water-soluble polymer compound having a cationic property, those having a cationic property when dissolved in water can be used. The water-soluble polymer compound having a cationic property is preferably a water-soluble polymer compound having one or more cationic groups selected from an amino group, an amine group, and a quaternary ammonium group. In the present invention, the water-soluble polymer compound means that when 1 g of the water-soluble polymer compound is added to 100 g of water at 25 ° C., the liquid is not turbid and transparent.

  The cationic water-soluble polymer compound (B) preferably has a degree of cationization of 0.1% or more, particularly preferably 2.5% or more. If the degree of cationization is less than 0.1%, the effect of adsorbing the coexisting silicone compound to the fiber becomes small, and a large amount of compounding is required, which may not be economical. In addition, when the polymer compound itself has a property of imparting rigidity to the fiber product, if it is blended in a large amount, the softening effect may be lowered.

Here, the degree of cationization means that a polymer compound is a polymer of a cationic monomer, a copolymer of a cationic monomer and a nonionic monomer, and a part of a nonionic polymer modified or substituted with a cationic group. In the case of (cationized cellulose, etc.), the polymer compound is a copolymer of a cationic monomer and an anionic monomer, and a copolymer of a cationic monomer, an anionic monomer and a nonionic monomer. In the case of coalescence, it is defined as a value calculated by the following formula (2).
Cation degree (%) = X × Y × 100 (1)
(X: atomic weight of a cationized atom (such as nitrogen) in the cationic group of the polymer compound Y: mole number of the cationic group contained in 1 g of the polymer compound)
Degree of cationization (%) = X × (Y−Z) × 100 Formula (2)
[X: atomic weight of a cationized atom (such as nitrogen) in a cationic group of a polymer compound Y: number of moles of a cationic group contained in 1 g of the polymer compound Z: anion contained in 1 g of the polymer compound The number of moles of the functional group (an anionic group of Z includes a carboxyl group, a sulfonic acid group, etc. contained in the monomer unit in the polymer compound chain. Specific examples include a carboxylic acid in acrylic acid, etc. However, the counter ion of the cationic group is not included.)]

As an example of calculating the degree of cationization, the case of MERQUAT280 (made by calgon) represented by the following formula is shown.
X: 14 (atomic weight of nitrogen atom)
Y: 4.95 × 10 ⁻³ (weight per 1 g of the cationic group: calculated from 0.8 g and the molecular weight of the cationic group)
Z: 2.78 × 10 ⁻³ (weight per 1 g of anionic group: calculated from 0.2 g and molecular weight of the anionic group)
From equation (2)
Cation degree (%) =
14 × (4.95 × 10 ⁻³ −2.78 × 10 ⁻³ ) × 100 = 3.0
It is.

（ＭＥＲＱＵＡＴ２８０）
塩化ジメチルジアリルアンモニウムとアクリル酸との質量比＝８０：２０

(MERQUAT280)
Mass ratio of dimethyldiallylammonium chloride to acrylic acid = 80: 20

  Therefore, according to the cationization degree calculation method described above, the cationization degree of the nonionic monomer polymer or the anionic monomer polymer is zero.

  The water-soluble polymer compound (B) preferably has a weight average molecular weight of 1,000 to 5,000,000, more preferably measured by gel permeation chromatography using polyethylene glycol as a standard substance. It is 3,000-1,000,000, More preferably, it is 5,000-500,000. If it is less than 1,000, it may be unpreferable in terms of odor, and if it exceeds 5,000,000, the viscosity of the composition increases, and the usability may decrease.

  Further, from the viewpoint of mildness, the weight average molecular weight is preferably large within the above range, and it is preferable that the number of low molecular weight compounds such as unreacted substances inevitably mixed during production is as small as possible.

  Examples of the component (B) include MERQUAT100 (manufactured by Calgon), Adeka thioace PD-50 (manufactured by Asahi Denka Kogyo Co., Ltd.), DAIDOL EC-004, DAIDOL HEC, and DAIDOL EC (manufactured by Daido Kasei Kogyo Co., Ltd.). ) Dimethyldiallylammonium chloride polymer such as MERQUAT550 JL5 (manufactured by Calgon), dimethyldiallylammonium chloride / acrylic acid copolymer such as MERQUAT280 (manufactured by Calgon), and Leogard Cationized cellulose such as KGP (manufactured by Lion), imidazolium chloride / vinylpyrrolidone copolymer such as LUVIQUAT-FC905 (manufactured by BASF), and polyethylene such as LUGALVAN-G15000 (manufactured by BASF) Copolymerization with cationized polyvinyl alcohols such as Nimine and Poval CM318 (manufactured by Kuraray Co., Ltd.), natural polymer derivatives having amino groups such as chitosan, and vinyl monomers having hydrophilic groups with addition of diethylaminomethacrylate / ethylene oxide, etc. Polymers and the like can be mentioned, but any polymer compound that is cationic when dissolved in water may be used, and the present invention is not limited to this example.

Among these, from the viewpoint of not hindering the texture such as flexibility imparted by the silicone, those having low rigidity imparted to the fiber when adsorbed by the component (B) alone are preferable.
Particularly preferred polymer compounds include cationic polymer compounds obtained by polymerizing dimethyldiallylammonium salts represented by the following general formula (II). The structure of this polymer compound is usually represented by the following general formula (III-1) or the following general formula (III-2). Moreover, both the structural unit of general formula (III-1) and the structural unit of general formula (III-2) may be contained.

（式中Ｘ^-は、塩化物イオン、臭化物イオン等の任意のマイナスイオンを示す。）

(In the formula, X ⁻ represents an arbitrary negative ion such as a chloride ion or a bromide ion.)

（式中、ｃ、ｄは、各々平均重合度であり、各々６〜３００００の範囲であることが好ましく、より好ましくは２０〜６０００、さらに好ましくは３０〜３０００の範囲である。）

(In the formula, c and d are average polymerization degrees, respectively, preferably in the range of 6 to 30000, more preferably in the range of 20 to 6000, still more preferably in the range of 30 to 3000.)

Examples of such polymer compounds include MERQUAT100 (Calgon), Adeka thioace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidol EC-004, Daidoru HEC, Daido Kasei Co., Ltd. )) And the like.
As the component (B) of the present invention, the above water-soluble polymer compound having a cationic property may be used singly or as a mixture.

  (B) Although the compounding quantity of a component is not specifically limited, 0.1-30 mass% is mix | blended in a composition in the range which does not provide rigidity to a fiber product, Preferably it is 0.5-10. It is blended by mass%. If the amount is less than 0.1% by mass, the effect of promoting the adsorption of silicone becomes small, so the effects such as flexibility, smoothness and drape are insufficient, and if it exceeds 30% by mass, the viscosity of the composition increases and the usability is increased. It is not preferable.

In the liquid softener composition of the present invention, (A) component: (B) weight ratio of the component 95: 5-60: in the range of 40, good Mashiku 90: 10-70: 30 range Within this range, excellent functions such as flexibility, smoothness, and drapeability can be obtained for clothing such as polyester and cotton. When the ratio of (B) component exceeds this range, textures, such as a softness | flexibility and a smoothness which a silicone compound provides, are impaired, and it is not preferable. In particular, in the case of a polymer compound that imparts rigidity to the fiber by component (B) alone, the flexibility and smoothness imparted by the silicone compound are not impaired, so the proportion of component (B) can be within this range. As few as possible is preferable. On the other hand, when the proportion of the component (B) is less than this range, the adsorptivity of silicone to fibers is lowered, which is not preferable.

  Further, the liquid softener composition of the present invention is used in such an amount that the concentration of the component (A) is 5 ppm to 0.5% by mass with respect to the total amount of water used when the textile product is actually subjected to soft finishing. More preferably, it is used in such an amount that it becomes 10 ppm to 300 ppm, and it is preferable to use it in such an amount that the concentration of the component (B) becomes 0.5 ppm to 100 ppm, more preferably 3 ppm to 30 ppm. Is used in such an amount.

  Furthermore, in the present invention, in order to ensure the storage stability of the liquid softener composition, in addition to the above components, the nonionic surfactant (C) component, the lower alcohol (D) component, and the glycol ether solvent And one or more water-soluble solvents selected from the group consisting of polyhydric alcohols.

As the nonionic surfactant of component (C), for example, polyoxyalkylene alkyl ethers having at least one alkyl group or alkenyl group having 8 to 20 carbon atoms are preferable, and in particular, an average of 2 to 50 moles of oxyalkylene group is added. Are preferred. Furthermore, the nonionic surfactant represented by the following general formula (IV) is preferable.
^{R 1 -T - [(R 2} O) p -H] q (IV)
(In the formula, R ¹ is an alkyl or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R ² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. Is the average number of moles added, and represents a number of 2 to 50, preferably 5 to 30, particularly preferably 5 to 20. T represents —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 In the case of —CON (C ₂ H ₄ OH) —, q is 1, and in the case where T is —N— or —CON—, q is 2.)
Specific examples of the compound of the general formula (IV) include compounds represented by the following general formulas (V) and (VI).
R ¹ —O— (C ₂ H ₄ O) _r —H (V)
(In the formula, R ¹ has the same meaning as described above, and r is the average number of added moles, which is 2 to 50, preferably 5 to 30.)
R ¹ —O— (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t —H (VI)
(Wherein R ¹ has the same meaning as described above, s and t are average added mole numbers, s is a number of 2 to 40, preferably 5 to 30, and t is 1 to 20, preferably 1) The number is from 10. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts.

  (C) The compounding quantity of a component is 0.5-20 mass% in a composition, Preferably it is 1-15 mass%, More preferably, it is 2-10 mass%. If the amount is less than 0.1% by mass, the effect of improving the storage stability may be reduced. Even if the amount exceeds 20% by mass, the effect of improving the storage stability is constant. It is uneconomical and may be undesirable from the standpoint of foaming during flexible processing.

Component (D) is one or more water-soluble solvents selected from the group consisting of lower (C1-4) alcohols, glycol ether solvents, and polyhydric alcohols. Specifically, a solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the following general formula (VII) It is preferable to blend the components.
R ³ —O— (C ₂ H ₄ O) _y — (C ₃ H ₆ O) _z —H (VII)
(In the formula, R ³ is an alkyl 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 O (C ₃ H ₆ O) (C ₂ H ₄ O) ₂ H] and the like. It is done.

  These components (D) are blended in the composition in an amount of 2 to 30% by mass, preferably 5 to 20% by mass.

  The liquid softener composition of the present invention can be blended with additives and the like used in ordinary household finishes within a range that does not interfere with the effects of the present invention. Specific examples of such additives include cationic surfactants, partially esterified products of hexanoic acid and glycerin or pentaerythritol, and water-soluble salts such as sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, and potassium chloride. Oils such as liquid paraffin and higher alcohol, urea, bactericides, antibacterial agents, antiseptics, antioxidants, dyes, pigments, hydrocarbons, nonionic cellulose derivatives, UV absorbers, fluorescent whitening agents, fragrance compositions , PH adjusters, antifoaming agents, colloidal silica, and the like described later.

  Although the pH of the liquid softening agent composition of this invention is not specifically limited, It is preferable that it is the range of 3-10, and it is more preferable that it is the range of 4-7. 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, alkali metal silicates An agent can be used.

  The liquid softening agent composition of the present invention contains the above components (A) to (D) and optional components, and the balance is usually water. In addition, the liquid softener composition of the present invention is used after being diluted to an appropriate concentration. The method of use is not particularly limited, but the laundry is usually washed, and the composition of the present invention is dissolved in the rinse water at the rinsing stage, and the composition of the present invention is used using a container such as a tub. Examples include a method in which an object is dissolved in water, and further, clothing is added to perform immersion treatment. The fiber product may be treated by any method, but the bath ratio (the ratio of the treatment liquid to the fiber product) is preferably 3 to 100 times, particularly preferably 5 to 50 times.

  The liquid softener composition of the present invention is not only less irritating to the skin of the composition itself, but also provides physical irritation (friction) when the textile treated with the liquid softener composition rubs against the skin. Can be lowered. Therefore, it can also be used as a method for reducing irritation to the skin with a textile product. For this reason, it is preferable to use for mild skin. In particular, it can be suitably used for people with sensitive skin, such as for sensitive skin, for atopy, for dry skin, and for baby.

  According to the present invention, a combination of a silicone compound and a cationic polymer compound in a specific ratio is excellent in various fiber products made from chemical fibers such as polyester and natural fibers such as cotton and silk. A softness, smoothness, drape, quick-drying and absorbability can be imparted, and a mild liquid detergent composition can be obtained on the skin. Furthermore, by using a nonionic surfactant and a water-soluble solvent in combination, the storage stability is improved. By using a silicone having a polyether group as a silicone compound, a liquid softening agent having a liquid appearance with a high transparency can be obtained. can get.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to this. In the following examples, “%” of the composition not particularly specified indicates mass%.

Example 1～8,11～2 3, 26-41, Comparative Examples 2-6]
(Preparation of softener composition)
Components (A) to (D) shown in Tables 1 to 4 are based on the compositions shown in the following Tables 5 to 8 (pure component conversion,%), (A), (C), (D) components and the following: The described common components were placed in a 500 mL beaker and sufficiently stirred using a stirring blade. Next, ion-exchanged water was added with stirring, and component (B) was added with further stirring, and the mixture was sufficiently stirred until uniform to prepare 300 g of a liquid softener composition. The obtained liquid softening agent composition was evaluated for softness and smoothness, drape, mildness, quick drying, absorption, liquid appearance, and storage stability. The results are also shown in Tables 5-8.

[Examples 9, 10, 24 , 25 ]
Based on the composition shown in the following Tables 5 and 7 (in terms of pure content, mass%), the component (C), the component (D) and the following common components were placed in a 500 mL beaker and sufficiently stirred using a stirring blade. Next, ion-exchanged water was added while stirring, components (A) and (B) were added while stirring, and the mixture was sufficiently stirred until uniform to prepare 300 g of a liquid softener composition. The obtained liquid softening agent composition was evaluated for softness and smoothness, drape, mildness, quick drying, absorption, liquid appearance, and storage stability. The results are also shown in Tables 5 and 7.

[Comparative Example 1]
Based on the composition shown in Table 6 below, distearyldimethylammonium chloride and the component (D) were placed in a 500 mL beaker, sufficiently stirred using a stirring blade, and then ion-exchanged water was added while stirring to prepare 300 g of liquid flexible An agent composition was prepared. The resulting liquid softener composition was evaluated for softness and smoothness, drape, mildness, quick drying, and absorbability. The results are also shown in Table 6.

The components, common components, and evaluation methods used in Examples and Comparative Examples are shown below.
[Silicone compound]
Silicone (A-1 to 8) having the structure shown in Table 1 was used.

[Water-soluble polymer compound having cationic properties]
Water-soluble polymer compounds having a cationic property described in Table 2 (compounds B-1 to 6) were used. The comparative products-1 and 2 are also shown.

[Nonionic surfactant]
The nonionic surfactant compounds (C-1 to 4) shown in Table 3 were used.

(Water-soluble solvent)
Water-soluble solvents (D-1 to 3) described in Table 4 were used.

(Common ingredient 1)
The following components were added in the amount shown in [] (the amount in solid form).
1-1: C.I. I. Direct Red 225 (Nippon Kayaku Co., Ltd., Kayafect Red B) [3ppm]
1-2: Caisson CG-ICP (Rohm & Haas) [100 ppm]
1-3: Fragrance composition A (showing the fragrance composition A described in Tables 2 to 11 of JP-A-2003-89979) [0.3%]
(Common component 2)
The following components were added in the amount shown in [] (the amount in solid form).
2-1: C.I. I. Acid Blue 112 (Nippon Kayaku Co., Ltd., Kayanol Milling Ultra Sky SE) [2ppm]
2-2: Caisson CG-ICP (Rohm & Haas) [100ppm]
2-3: Fragrance composition B (shows the fragrance composition B described in Tables 2 to 11 of JP-A-2003-89979) [0.3%]
(Common component 3)
The following components were added in the amount shown in [] (the amount in solid form).
3-1: C.I. I. Acid Blue 9 (manufactured by Pingtung Chemical Co., Ltd., lacto brilliant blue FCF) [3 ppm]
3-2: Caisson CG-ICP (Rohm & Haas) [100 ppm]
3-3: Fragrance composition C (showing the fragrance composition C described in Tables 2 to 11 of JP-A-2003-89979) [0.3%]
(Common component 4)
The following components were added in the amount shown in [] (the amount in solid form).
4-1: C.I. I. Acid Yellow 3 (manufactured by BASF, quinoline yellow WS) [3 ppm]
4-2: Caisson CG-ICP (Rohm & Haas) [100 ppm]
4-3: Fragrance composition D (showing fragrance composition D described in Tables 2 to 11 of JP-A-2003-89979) [0.3%]
(Common component 5)
The following components were added in the amount shown in [] (the amount in solid form).
5-1: Caisson CG-ICP (Rohm & Haas) [100ppm]
5-2: Fragrance composition A (showing the fragrance composition A described in Tables 2 to 11 of JP-A-2003-89979) [0.3%]

Flexibility and smoothness evaluation method (preparation of test cloth)
Commercial cotton knit (100% cotton) and polyester jersey (100% polyester), commercial detergent “Top” [manufactured by Lion Co., Ltd., component: surfactant (alpha olefin sulfo fatty acid ester sodium, fatty acid sodium, direct Chain alkylbenzene, polyoxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent, the same shall apply hereinafter) for 15 minutes using a household two-tub washing machine (detergent is the standard amount used, The bath ratio was 30 times, 45 ° C. tap water) → The process of dehydration for 5 minutes was repeated 2 cycles. Thereafter, a test cloth was obtained by naturally repeating the process of rinsing with running water for 15 minutes and dehydrating for 5 minutes 5 times.
(Treatment with softener composition)
700 g of cotton knit and 300 g of polyester jersey obtained by the preparation of the test cloth were washed with a commercial clothing detergent “Top” for 15 minutes (detergent was used in standard amount, bath ratio 30 times, using tap water at 25 ° C.). Thereafter, 10 g of the softening agent composition with respect to 30 liters of water (however, Example 35 was 20 g, Example 36 was 6.6 g, Example 37 was 5 g, and Examples 38 to 41 were 20 g in the second rinse. ) With the added liquid, clothing was softened (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). Then, it air-dried on conditions of 20 degreeC and 45% RH, and performed the following evaluation.

(Evaluation of flexibility and smoothness)
A sensory pair comparison was performed by 10 professional panelists using cotton knit and polyester jersey treated without using a softener as a control, and evaluation was performed according to the following evaluation criteria.
<Evaluation criteria>
+2: Clearly better than the control +1: Slightly better than the control 0: Almost the same as the control -1: Slightly better than the control -2: Clearly better than the control 1.5 to 2.0 Points were marked with ◎, 1.0-1.4 points were marked with ○, 0.5-0.9 points were marked with Δ, and 0.4 points or less were marked with ×.

Drapability Evaluation Method A commercial fleece (SP No. 6A018 polyester 100% manufactured by UNIQLO) was treated with the following method. One piece of this fleece was washed with a commercially available laundry detergent “Top” (manufactured by Lion Corporation) for 15 minutes using a commercial fully automatic washing machine together with three commercially available long-sleeved shirts (made by UNIQLO, 100% cotton) ( Standard amount of detergent used, bath ratio 30 times, 25 ° C tap water). Thereafter, in the second rinsing, 15 g of the softening agent composition was added to 45 liters of water (however, Example 35 was 30 g, Example 36 was 10 g, Example 37 was 7.5 g, and Examples 38 to 41 were 30 g. ) With the added liquid, clothing was softened (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). After this washing to softening process was repeated 7 times, it was naturally dried at 20 ° C. and 45% RH. The fleece was actually worn and the drape at that time was visually determined according to the following evaluation criteria.

Drapability refers to the 2nd edition Textile Handbook (edited by the Textile Society of Japan, published on March 25, 1994, Maruzen Co., Ltd.), Encyclopedia of textiles (edited by Tatsuya Motomiya et al., Published on March 25, 2002) As described generally in documents such as Maruzen Co., Ltd.), it is the ability to form a deformed state (drape) of the fabric due to its own weight, etc., but there are a wide variety of evaluation methods. Here, the beauty of clothing silhouettes when worn was evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: A beautiful silhouette equal to or greater than that of a new product △: A new product has a slightly beautiful silhouette (approximately the same as Comparative Example 1)
×: The new one has a clear and beautiful silhouette (almost the same as that processed without using a softener)

Liquid Appearance and Storage Stability Evaluation Method The liquid softener composition was placed in a glass container and sealed, and the liquid appearance (transparency) and storage stability were evaluated. In addition, the storage stability was evaluated by the following evaluation criteria by observing changes in appearance after leaving it to stand at 25 ° C., 40 ° C., and 5 ° C. for one month while sealed in a glass container.
<Evaluation criteria for liquid appearance>
◎: Transparent ○: There is no transparency, but it is uniformly dispersed △: Slightly tilted ×: Precipitation or separation occurs <Storage stability evaluation criteria>
○: Transparent, uniformly or uniformly dispersed Δ: Slightly or slightly separated ×: Precipitated or separated

Mildness evaluation method In order to increase the mildness of the softener composition on the skin, the softness composition itself should be less irritating to the skin, and the physical irritation when the treated clothing and the skin rub against each other. It is important to reduce (such as friction). Therefore, the mildness evaluation comprehensively determined these two types of stimuli according to the following evaluation criteria.
(1) Evaluation method of irritation of composition Using Hartley guinea pig as sample (n = 3), softening agent composition is 100% (however, Example 36 is 70%, Example 37 is 50%, and Example 40 is 50%, 30% in Example 41 ) (diluted with water), and 30 μL was applied to the back surface in a 2 × 2 cm ² range once a day for 3 days. The irritation level 24 hours after the final application was visually determined for erythema / crust and edema according to the following evaluation criteria according to the Draize method. The average value of the sum of both scores was used as the skin irritation score.
<Evaluation criteria for erythema and crust>
Score 0: No erythema 1: Very mild erythema (barely discernable)
2: Clear erythema 3: Moderate to severe erythema 4: From severe erythema to slight crust formation (deep damage) <Evaluation criteria for edema>
Score 0: No edema 1: Very mild edema (barely discernable)
2: Mild edema (the edges can be clearly identified by clear swelling)
3: Moderate edema (bulge of about 1 mm)
4: Severe edema (bulge of 1 mm or more and spread beyond the exposure range)

(2) Evaluation of physical irritation of clothing treated with softener composition (Preparation of test cloth)
Commercially available polyester satin (100% polyester) was washed with a commercial clothing detergent “Top” using a household two-tank washing machine for 15 minutes (detergent is standard usage, bath ratio 30 times, 45 ° C. tap water) → The process of dehydration for 5 minutes was repeated 2 cycles. Thereafter, the process of rinsing with running water for 15 minutes → dehydration for 5 minutes was repeated 5 times, and after natural drying, the surface was flattened by ironing to obtain a test cloth.
(Treatment with softener composition)
20 g of polyester satin obtained by the preparation of the test cloth was washed with a commercial clothing detergent “Top” for 6 minutes (detergent was used in standard amount, bath ratio 30 times, using 25 ° C. tap water). Thereafter, in the second rinsing, 1 g of the softening agent composition per 3 liters of water (however, Example 35 was 2 g, Example 36 was 0.7 g, Example 37 was 0.5 g, Examples 38 to 41) 2g) With the added solution, the test cloth was softened (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). After repeating this washing | cleaning-softening process 3 times, it dried naturally on 20 degreeC and 45% RH conditions, and performed the following evaluation.
(Method for evaluating physical irritation of cloth)
An average friction coefficient (MIU) between polyester satin softened as described above and artificial model skin (Bioplate, manufactured by Beaulux Co., Ltd.) was measured under the conditions of 25 ° C. and 30% RH (KES-SE). , Manufactured by Kato Tech Co., Ltd.) and measured by attaching artificial model skin to a piano wire friction piece and fixing the treatment cloth to the sample table with double-sided tape (load 50 g, sample table moving speed 10 mm / second). ).
The skin irritation score obtained above and the average coefficient of friction (MIU) were comprehensively evaluated, and mildness was evaluated based on the following evaluation criteria.
<Skin irritation evaluation criteria>
○: Skin irritation score of composition less than 2 points Δ: Skin irritation score of composition 2 points or more and less than 5 points x: Skin irritation score of composition 5 points or more <MIU evaluation criteria>
○: MIU is less than 0.6 △: MIU is 0.6 or more and less than 1.2 ×: MIU is 1.2 or more <mildness evaluation criteria>
A: Both skin irritation evaluation and MIU evaluation are ○
○: One of skin irritation evaluation and MIU evaluation is ○, and the other is Δ
Δ: Both skin irritation evaluation and MIU evaluation are Δ, or either one is ○ or Δ and the other is ×
×: Both skin irritation evaluation and MIU evaluation ×

Water absorption evaluation method (preparation of test cloth)
Wash with a commercial cotton towel (100% cotton) and polyester satin (100% polyester) using a commercial laundry detergent "Top" using a household two-tub washing machine (detergent is standard usage, bath ratio) 30 times, 45 ° C. tap water) → The process of dehydration 5 minutes was repeated 2 cycles. Thereafter, a test cloth was obtained by naturally repeating the process of rinsing with running water for 15 minutes and dehydrating for 5 minutes 5 times.
(Treatment with softener)
80 g of cotton towel and 20 g of polyester satin obtained by the preparation of the above test cloth, 1 g of softener composition with respect to 3 liters of water (however, 2 g in Example 35 , 0.7 g in Example 36 , Example 37) Was 0.5 g, and Examples 38 to 41 were 2 g). The test cloth was softened (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). Then, it air-dried on conditions of 20 degreeC and 45% RH, and performed the following evaluation.
(Water absorption evaluation method)
The water absorption of cotton towel and polyester satin was measured by the following methods, and evaluated according to the following evaluation criteria.
(1) Water absorbency of cotton towel From the cotton towel treated as described above, a piece of cloth cut into a size of 2.5 cm x 20 cm is hung vertically under conditions of 20 ° C and 45% RH, and tap water is poured from the lower end. Raised using capillary action. The water absorption height 10 minutes after the moment when the lower end was brought into contact with tap water was measured. Higher water absorption height means better water absorption (equivalent to JIS, bi-leg method).
(2) Water Absorption of Polyester Satin (Chemical Fiber) One drop of ion-exchanged water was dropped on the polyester satin cloth treated as described above, and the time until it was completely soaked visually was measured.
<Water absorption evaluation criteria>
A: The water absorption length of the cotton is 80 mm or more and the water absorption time of the synthetic fiber is less than 10 seconds. ○: The water absorption length of the cotton is 80 mm or more and the water absorption time of the chemical fiber is 10 seconds or more. Δ: The water absorption length of the cotton is 50 mm. Or more and less than 80 mm ×: water absorption length of cotton is less than 50 mm

Quick-drying evaluation method (preparation of test cloth)
In order to improve the quick drying property, two points of increasing the evaporation rate of water and decreasing the water after dehydration are considered. In order to increase the evaporation rate of water, it is conceivable to azeotrope with an organic solvent that easily azeotropes with water, such as ethanol. For example, it is unrealistic to perform at home because an organic solvent such as Therefore, it was decided to evaluate quick-drying by focusing on reducing the moisture content after dehydration.
Wash a commercially available cotton towel (100% cotton) with a commercial clothing detergent “Top” using a household two-tank washing machine for 15 minutes (detergent is the standard amount used, 30 times the bath ratio, 45 ° C tap water) → The process of dehydration for 5 minutes was repeated 2 cycles. Thereafter, the process of rinsing with running water for 15 minutes and dehydration for 5 minutes was repeated 5 times, and the fabric sufficiently dried at 20 ° C. and 60% RH was used as a test cloth. In addition, the mass (Wd) of the towel after drying was measured and used for the following moisture content calculation.
(Treatment with softener composition)
Two cotton towels obtained by the preparation of the above test cloth, 2.4 g of softener composition with respect to 4.8 liters of water (however, 4.8 g in Example 35 , 1.6 g in Example 36 , Example 37 was 1.2 g, and Examples 38 to 41 were 4.8 g). The test cloth was softened (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). Then, dehydration was performed for 1 minute with a washing machine (CW-C30A1-H) manufactured by Mitsubishi Electric Corporation.
(Quick-drying evaluation method)
The weight (Ww) of the cotton towel immediately after dehydration in the softener treatment was measured, and the moisture content was calculated from the following formula (3) from this value and the weight (Wd) of the towel after drying before the softener treatment. Moreover, the moisture content (Bl) of the cotton towel which performed the said process without using a softening agent was also calculated by the following formula (3), the relative moisture content was calculated by the following formula (4), and the following evaluation criteria, The quick drying property was evaluated.

<Evaluation criteria for quick drying>
A: Relative moisture content is less than 88% B: Relative moisture content is 88% or more and less than 94% Δ: Relative moisture content is 94% or more and less than 100% ×: Relative moisture content is 100% or more

  The cotton knit / polyester fabric treated with the product of the present invention has no sliminess and softness compared to that treated with distearyldimethylammonium chloride (Comparative Example 1) conventionally used as a softening agent. , Smoothness, drape and mild finish.

適切なノニオン性界面活性剤及び水溶性溶剤を組み合わせることで、低温から高温まで保存安定性が良好になり、シリコーン化合物としてポリエーテル基を有するシリコーンを用いることにより、天然繊維にも化学繊維にも良好な吸水性を有し、さらに透明な液外観を有し、かつ低温から高温まで透明な液外観を維持する柔軟剤組成物を得ることができた。

Combining appropriate nonionic surfactants and water-soluble solvents improves storage stability from low to high temperatures. By using silicones with polyether groups as silicone compounds, both natural and chemical fibers can be used. A softener composition having good water absorption, a transparent liquid appearance, and maintaining a transparent liquid appearance from low to high temperatures could be obtained.

Claims (5)

(A) 6 to 40% by mass of a silicone compound selected from one or more dimethyl silicones, epoxy-modified silicones and polyether-modified silicones , and (B) one or more water-soluble highly cationic compounds A liquid softening agent composition comprising 0.1 to 30% by mass of a molecular compound in a ratio of (A) :( B) (mass ratio) of 95: 5 to 60:40. Furthermore, (C) a nonionic surfactant and (D) one or more water-soluble solvents selected from lower alcohols and glycol ether solvents, 5 to 30% by mass are contained. Item 2. A liquid softener composition according to Item 1. The liquid softener composition according to claim 1 or 2, wherein the component (A) is a polyether-modified silicone , and the composition is transparent.   The liquid softener composition according to any one of claims 1 to 3, wherein the component (B) is a polymer of dimethyldiallylammonium salt.   The liquid softener composition according to any one of claims 1 to 4, which is for mild skin.