JP2009155751A - Textile treatment agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fabric product treating agent capable of achieving both excellent softness and water-absorption. <P>SOLUTION: The fabric product treating agent contains: (a) a (poly)glyceryl monoether expressed by general formula (I), R-O-(C<SB>3</SB>H<SB>6</SB>O<SB>2</SB>)<SB>n</SB>-H (I); (b) a silicone compound; (c) a polymer compound containing an alkylene terephthalate unit and/or an alkylene isophthalate unit and a polyoxyalkylene unit and having a weight-average molecular weight of 1,000-100,000; and (d) a specific tertiary amine or its acid salt or quaternized product (d1) and/or a cationic water-soluble polymer compound (d2). The method for treating the fabric product includes the step of adding the fabric product treating agent to a rinsing water in the rinsing step of cleaning and rinsing the fabric. In the formula (I), R is a 6-22C aliphatic hydrocarbon group; -(C<SB>3</SB>H<SB>6</SB>O<SB>2</SB>)- is a glycerol skeleton; and n is a number of 1-7. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a textile product treating agent and a textile product treating method.

  Since silicone compounds can impart a unique smoothness and feel to textile products, they are commonly used compounds for treating textile products. In recent years, as described in Patent Documents 1 to 3, a general household washing process is used. In the treatment agents used in the present invention, textile product treatment agents based on silicone compounds have been studied.

On the other hand, a polyester polymer compound having alkylene terephthalate or alkylene isophthalate as a structural unit is known as a soil release agent (stain release agent), and is applied to detergents and the like. Further, for the purpose of industrially imparting a soil release effect to a textile product, Patent Document 4 discloses a technique of using a polyester polymer compound and a polyether-modified silicone in combination.
JP 2001-279581 A JP 2000-110076 A JP-A-5-508889 JP-A-9-291383

  A textile treatment agent based on a silicone compound gives a favorable texture to the textile product, while deteriorating the water absorption, and particularly impairing the water absorption of the textile product containing cotton. Yes. Patent Documents 1 to 3 do not yet have satisfactory effects for such problems.

  On the other hand, Patent Document 4 discloses means for solving the problem in the process of imparting an antifouling effect to a fiber product, and describes that it can impart a softening effect, hydrophilicity, and antifouling property to a fiber product. In addition, it is difficult to say that a treatment agent that provides excellent flexibility and water absorption is also disclosed in a usage mode in which the treatment agent is used at a relatively low concentration, for example, in a usage mode such as a daily treatment in a general household. .

  Therefore, the problem to be solved by the present invention is to solve the problem of deteriorating the water absorption when treated with a textile product treating agent having a silicone compound as a main base, and to achieve both excellent flexibility and water absorption. An object of the present invention is to provide a fiber product treating agent that improves the texture derived from a silicone compound.

In the present invention, the following (a) component, (b) component, (c) component and (d) component-containing textile product treating agent, and this textile product treating agent are added to the rinsing water at the stage of the laundry rinsing step The present invention relates to a textile product processing method for treating textile products.
Component (a): at least one selected from glyceryl monoether and polyglyceryl monoether represented by formula (I) R—O— (C ₃ H ₆ O ₂ ) _n —H (I)
(In the formula, R is an aliphatic hydrocarbon group having 6 to 22 carbon atoms.-(C ₃ H ₆ O ₂ )-is a glycerol skeleton, and n is a number from 1 to 7 indicating the degree of condensation of glycerol. (The condensation position of glycerin may be any hydroxyl group of glycerin, including linear, branched, and random mixtures of linear and branched.)
(B) component: silicone compound (c) component: a polymer having a weight average molecular weight of 1,000 to 100,000, comprising at least one unit selected from an alkylene terephthalate unit and an alkylene isophthalate unit, and a polyoxyalkylene unit. Compound (d) component: Among 3 or 4 groups bonded to the nitrogen atom, 1 to 3 are hydrocarbon groups having 10 to 24 carbon atoms, and the rest are alkyl groups or hydroxyalkyl having 1 to 3 carbon atoms. At least one compound selected from a tertiary amine or a salt thereof or a quaternized product (d1) thereof and a cationic water-soluble polymer compound (d2)

  ADVANTAGE OF THE INVENTION According to this invention, the adsorption | suction property to the textiles of a silicone compound can be improved, and the textiles processing agent which has the softness | flexibility and the water absorption which have the silicone compound as the main base can be provided.

[(A) component]
The component (a) of the present invention is at least one selected from glyceryl monoether and polyglyceryl monoether represented by the general formula (I) (hereinafter collectively referred to as “(poly) glyceryl monoether”). It is.

  R in the general formula (I) represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms, which may be linear or branched, saturated or unsaturated, and an alkyl group or alkenyl having 6 to 22 carbon atoms. Group is preferred, and an alkyl group having 6 to 22 carbon atoms, more preferably 12 to 14 carbon atoms, and particularly 12 carbon atoms is preferred.

  In the component (a), the ratio of (poly) glyceryl monoether in which R in the general formula (I) is an alkyl group having 12 to 14 carbon atoms, particularly 12 and 14 carbon atoms, is 40% by mass or more in total. It is preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably 95% by mass or more.

In component (a), the glycerin moiety to be condensed in general formula (I) is labeled (C ₃ H ₆ O ₂ ), and the degree of condensation is n. However, this does not represent only the linear type as the condensed form of glycerin, but includes a branched type and a random mixture of the linear type and the branched type. It is expressed in this way for convenience of expression.

  The component (a) preferably has n in the general formula (I) of 3 to 5. In the case where the component (a) is composed of only a single n in the general formula (I), it is easy to crystallize, so that the solubility in water is particularly poor at low temperatures. Adsorption performance tends to decrease. On the other hand, when the component (a) contains a plurality of (poly) glyceryl monoethers having different n in the general formula (I), crystallization is suppressed, so that high solubility is exhibited even at a low temperature. Adsorption performance of compounds to textiles can be obtained. Accordingly, the component (a) is preferably composed of a plurality of (poly) glyceryl monoethers having different n in the general formula (I), particularly n is 3 to 5, n = 3 and 4, and n = 3. And those containing polyglyceryl monoethers with n = 4 and 5 or n = 3, 4 and 5 are preferred, and those containing polyglyceryl monoethers with n = 3, 4 and 5 are particularly preferred.

  From the viewpoint of storage stability, n in the general formula (I) is most preferably n = 4, and in the component (a), the ratio of the polyglyceryl monoether where n = 4 is preferably 10% by mass or more. 15 mass% or more is more preferable, 20 mass% or more is still more preferable, and 30 mass% or more is especially preferable.

  Moreover, the ratio of the (poly) glyceryl monoether in which n in the general formula (I) is 1 or 2 is preferably less than 50% by mass and more preferably 35% by mass or less. Furthermore, in the component (a), the content of glyceryl monoether where n is 1 is preferably less than 30% by mass, and more preferably 20% by mass or less.

  The component (a) preferably contains a polyglyceryl monoether in which R in the general formula (I) is an alkyl group having 12 and / or 14 carbon atoms and n is 3 to 5, The ratio is preferably 40% by mass or more from the viewpoint of low temperature solubility. The ratio is more preferably 50% by mass or more, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more. The upper limit is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and particularly preferably 85% by mass, from the viewpoint of the adsorption performance of a good silicone compound to a fiber product at a low temperature. % Or less.

  (A) Component is 99 mass% of the total ratio of the polyglyceryl monoether whose R in general formula (I) is a C12 and / or C14 alkyl group, and n is 3-5. In the case of the following, the solubility at a low temperature is remarkably improved, and as a result, the effect of greatly improving the adsorption performance of the silicone compound to the fiber product can be obtained. Generally, the lower the content, the better the solubility at a low temperature, but at the same time, the adsorption performance of the silicone compound to the fiber product at room temperature tends to be lowered. Therefore, the above lower limit and upper limit ranges are preferable.

  The component (a) is composed of polyglyceryl monoether (a-1) in which R in the general formula (I) is an alkyl group having 12 carbon atoms and n is 3 to 5, and R in the general formula (I) is carbon. It is preferable that both the polyglyceryl monoethers (a-2) whose n is 3-5 are contained in the number 14 alkyl group. Furthermore, the component (a-1) and the component (a-2) both contain a plurality of (poly) glyceryl monoethers having different n, particularly, three types of polyglyceryl monoethers with n = 3, 4, and 5. preferable. The total ratio of the component (a-1) and the component (a-2) in the component (a) is preferably 40% by mass or more.

  The mass ratio of the degree of condensation n of glycerin constituting the component (a) [mass ratio in the component (a)] can be determined from area% of the gas chromatography (GC) method.

  The component (a) of the present invention can be obtained, for example, by reacting a predetermined amount of 2,3-epoxy-1-propanol (glycidol) with an alcohol having 6 to 22 carbon atoms in the presence of an alkali catalyst. Moreover, it can also manufacture by the method as described in Paragraphs 0007-0011 of Unexamined-Japanese-Patent No. 2000-160190.

  In addition, in order to use what has polyglyceryl monoether of n = 3-5 in General formula (I) in a predetermined ratio, the condensation degree of a predetermined range is refine | purified by distillation etc. as needed. Can be obtained.

  For example, n = 1, 2 in the general formula (I) can be distilled off by distillation under reduced pressure. By reducing the components of n = 1, 2, the ratio of the components of n = 3-5 can be increased. Although there is no limitation in a distillation apparatus, these components can be isolate | separated efficiently by performing thin film distillation. The optimum distillation temperature varies greatly depending on the degree of vacuum. When the degree of vacuum is 0.13 kPa, it is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 170 ° C. or higher and 300 ° C. or lower, and further 200 ° C. or higher and 300 ° C. or lower. preferable. By distilling at a temperature of 300 ° C. or lower, quality deterioration such as coloring can be prevented.

  Further, for example, when removing n = 6 or more in the general formula (I), separation by a column can be performed. Separation by a column can be used to remove n = 1 and 2 components by devising conditions.

[Component (b)]
Examples of the silicone compound of component (b) of the present invention include dimethylpolysiloxane, quaternary ammonium-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, carboxy-modified dimethylpolysiloxane, poly Examples thereof include silicone compounds such as oxyalkylene-modified dimethylpolysiloxane and fluorine-modified dimethylpolysiloxane. Among these silicone compounds, dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, and polyoxyalkylene (eg, polyoxyethylene and / or polyoxypropylene, preferably polyoxyethylene) modified dimethylpolysiloxane In particular, amino-modified dimethylpolysiloxane and polyoxyalkylene (for example, polyoxyethylene and / or polyoxypropylene, preferably polyoxyethylene) -modified dimethylpolysiloxane are preferable from the viewpoint of softening effect. .

The dimethylpolysiloxane has a weight average molecular weight of 1,000 to 1,000,000, preferably 3,000 to 500,000, particularly preferably 5,000 to 250,000, and a viscosity at 25 ° C. of 100,000 to 100,000 mm ² / s, preferably 500 to 50,000. Examples of the compound include mm ² / s, particularly preferably 1,000 to 40,000 mm ² / s.

The amino-modified dimethylpolysiloxane has an amino equivalent (amino equivalent is a molecular weight per nitrogen atom) of 1,500 to 40,000 g / mol, preferably 2,500 to 20,000 g / mol, more preferably , 3,000 to 10,000 g / mol of the compound. The viscosity is 100~20000mm ² / s at 25 ° C., preferably 200~10000mm ² / s, particularly preferably include compounds of 500~5000mm ² / s.

The polyoxyalkylene-modified dimethylpolysiloxane is preferably a compound having a clouding point of 1% aqueous solution of 80 ° C. or lower, more preferably 70 ° C. or lower. A compound having a cloud point in such a range is considered to be highly hydrophobic and easily adsorbed to a fiber product. Further, compounds having a viscosity at 25 ° C. of 100 to 6500 mm ² / s, preferably 200 to 6000 mm ² / s, particularly preferably 500 to 5500 mm ² / s can be mentioned.

  In the present invention, amino-modified dimethylpolysiloxane and polyoxyalkylene-modified dimethylpolysiloxane are preferably used in combination from the viewpoint of the effect of improving water absorption particularly in repeated use. The mass of amino-modified dimethylpolysiloxane / polyoxyalkylene-modified dimethylpolysiloxane is preferred. The ratio is preferably 100/0 to 10/90, more preferably 95/5 to 20/80, and particularly preferably 90/10 to 30/70.

  It is also possible to use a commercially available silicone compound, and preferable ones are Shin-Etsu Chemical Co., Ltd., Polon MF-14, Polon MF-14D, Polon MF-14EC, Polon MF-29, Polon MF-39, Polon MF-44, Polon MF. -52, KF-615A, KF-618, KF-864, KF-945A, KF-6008, Y-7006, Toray Dow Corning Co., Ltd., FZ-2203, FZ-2207, FZ-2120, FZ-2161 , FZ-2163, FZ-2165, SM8702, SM8704, SM8702C, SM8704C, BY22-812, BY22-816, BY22-819, BY22-823, BY16-850, BY16-906, SF8471, BY22-01 , Mention may be made of SH-3746, SH-3771, SH3775M, SH-8400, SF-8410, SF8457C, the SH-8700 and the like.

[Component (c)]
The component (c) of the present invention is a polymer compound containing at least one unit selected from an alkylene terephthalate unit and an alkylene isophthalate unit and a polyoxyalkylene unit, and is selected from an alkylene terephthalate unit and an alkylene isophthalate unit. The polymer compound is polymerized in a random or block manner using at least one kind of unit and a polyoxyalkylene unit as a basic unit. In addition, in order to improve the dispersibility in water, a polymer compound into which a sulfo group is partially introduced can be used.

  Examples of the alkylene terephthalate unit include at least one selected from an ethylene terephthalate unit, a propylene terephthalate unit, a butylene terephthalate unit, and the like. Among these, an ethylene terephthalate unit is preferable.

  Examples of the alkylene isophthalate unit include at least one selected from an ethylene isophthalate unit, a propylene isophthalate unit, a butylene isophthalate unit, and the like. Among these, an ethylene isophthalate unit is preferable.

  Examples of the polyoxyalkylene unit include at least one selected from a polyoxyethylene unit, a polyoxypropylene unit, a polyoxyethylene polyoxypropylene unit, and the like.

  The molar ratio of at least one unit selected from alkylene terephthalate units and alkylene isophthalate units to polyoxyalkylene units is preferably 90/10 to 40/60, more preferably 80/20 to 45/55, and 70/30. More preferred is ˜50 / 50. Moreover, the weight average molecular weight of (c) component is 1,000-100,000, and 6000-85000 are preferable.

  The weight average molecular weight of component (c) can be measured by gel permeation chromatography using a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance.

  In addition, in the component (c), the proportion of at least one unit selected from alkylene terephthalate units and alkylene isophthalate units and the polyoxyalkylene units is 90 mol% or more, further 95 mol% or more in all the structural units. It is preferable.

  As the component (c) of the present invention, in particular, a monomer structural unit represented by the following general formula (II-1) and a monomer structural unit represented by the following general formula (II-2) are represented by (II-1) : (II-2) = A polymer compound containing a molar ratio of 10:90 to 90:10 and having a weight average molecular weight of 1,000 to 100,000 is preferable. The arrangement of the monomer structural unit (II-1) and the monomer structural unit (II-2) may be random or block.

[Wherein, R ¹ and R ² are alkylene groups having 2 or 3 carbon atoms, and these may be the same or different. m is a number average of 1 to 150, preferably 10 to 100. ]
The method for producing the polymer compound (c) of the present invention is not particularly limited. For example, the dicarboxylic acid component and the glycol component are heated to 160 to 270 ° C. in the presence of a catalyst in an inert gas to form an ester. Then, a glycol ester is prepared by an esterification reaction or a transesterification reaction, and then a polyalkylene glycol is added and mixed at an appropriate time and polymerized under normal pressure or reduced pressure. As the catalyst, metal oxides such as barium oxide or antimony oxide, zinc acetate, manganese acetate, cobalt acetate, zinc succinate, tetrabutyl titanate, magnesium methoxide, sodium methoxide, and organic metal compounds can be used.

[Component (d)]
In the component (d) of the present invention, among the three or four groups bonded to the nitrogen atom, 1 to 3 are hydrocarbon groups having 10 to 24 carbon atoms, and the rest are alkyl groups having 1 to 3 carbon atoms. Or at least 1 sort (s) chosen from the tertiary amine which is a hydroxyalkyl group, its acid salt, or its quaternization thing (henceforth (d1) component), and a cationic water-soluble polymer compound (henceforth (d2) component). A compound.

  (D) component of this invention can improve the softness | flexibility provision effect by improving the adsorptivity of (b) component.

  Specifically, the component (d1) is dialkyl (10 to 16 carbon atoms) dimethylammonium salt, N, N-dialkyloyl (or alkenoyl) (12 to 20 carbon atoms) oxyethyl-N-hydroxyethyl-N-methyl ( Or, ethyl) ammonium salts are preferred.

  In the cationic water-soluble polymer compound (d2), water-soluble means that the polymer compound is dissolved and / or dispersed in water at 20 ° C. and the pH is adjusted to 5.0. It is defined that the compound is dissolved by 1% by mass or more. The term “cationic” means that the molecule contains an acid salt of a quaternary ammonium group or a tertiary amino group, and preferably a simple substance having an acid salt of a quaternary ammonium group or a tertiary amino group in the molecule. It is a polymer compound containing 5 to 100 mol%, preferably 10 to 95 mol%, more preferably 15 to 90 mol% of a monomer unit. In addition, when the anionic group (X) selected from a carboxylic acid group and a sulfonic acid group is present in the polymer compound, [the total number of moles of quaternary ammonium group and tertiary amino group acid salt in the molecule ] / [Number of moles of anionic group (X) in the molecule] is preferably 1.1 or more, more preferably 2 or more.

  Specifically, the component (d2) is a polymer obtained by polymerizing a compound represented by the following general formula (III), or an acid salt thereof, or a quaternized product thereof (hereinafter referred to as (d2 · m1)). Compounds are preferred.

[Wherein R ³ is a hydrogen atom or a methyl group, Y is selected from —COOR ⁶ —, —CON (R ⁷ ) R ⁸ —, —OCOR ⁹ —, —CH ₂ —, and Y is —CH ₂ In the case of —, R ⁴ is CH ₂ ═C (R ³ ) —CH ₂ —, and in the case where Y is otherwise, R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. R ⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, R ⁶ , R ⁸ and R ⁹ are each independently an ethylene group or a propylene group, and R ⁷ is a hydrogen atom or a methyl group. ]
Specific examples of (d2 · m1) include N- (meth) acryloyloxyethyl-N, N-dialkylamine or an acid salt thereof, or a quaternary ammonium salt thereof (the alkyl group has 1 to 3 carbon atoms), N -(Meth) acryloylaminopropyl-N, N-dialkylamine or an acid salt thereof, or a quaternary ammonium salt thereof (the alkyl group has 1 to 3 carbon atoms), N-vinyloxycarbonylethyl-N, N-dialkylamine Or an acid salt thereof, or a quaternary ammonium salt thereof (the carbon number of the alkyl group is 1 to 3), N, N-diallyl-N-alkylamine or an acid salt thereof, or a quaternary ammonium salt thereof (the carbon number of the alkyl group) Is preferably at least one selected from 1 to 3), particularly N- (meth) acryloyloxyethyl-N, N-dialkylamine, N- Meth) acryloyl aminopropyl -N, number of carbon atoms of N- dialkylamine or their salts or their quaternary ammonium salts (alkyl groups, 1 to 3) is preferable.

  When (d2 · m1) is in the form of an acid salt, an inorganic acid salt selected from hydrochloride, sulfate, and phosphate, a fatty acid salt having 1 to 12 carbon atoms, and an alkyl group having 1 to 3 carbon atoms are 1 In addition to an inorganic acid salt or an organic acid salt selected from aryl sulfonates which may be substituted by 3 groups, an alkylbenzene sulfonate having 10 to 24 carbon atoms in an alkyl group, an alkyl having 10 to 24 carbon atoms in an alkyl group A salt of an anionic surfactant selected from a sulfate ester salt and a polyoxyethylene alkyl ether sulfate ester salt having an alkyl group having 10 to 24 carbon atoms and an average addition mole number of oxyethylene groups of 1 to 4 can also be used. .

  When (d2 · m1) is in the form of a quaternary ammonium salt, the compound represented by the general formula (III) is an alkylating agent selected from methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, and propylene oxide. A quaternized product can be used.

  When (d2 · m1) is in the form of an amine, (d2 · m1) may be neutralized with a normal acid after polymerization, or quaternized with a normal alkylating agent to be cationic. it can. The neutralizing agent is selected from an inorganic acid selected from hydrochloric acid, sulfuric acid, and phosphoric acid, a fatty acid having 1 to 12 carbon atoms, and an aryl sulfonic acid optionally substituted by 1 to 3 alkyl groups having 1 to 3 carbon atoms. Commonly known inorganic or organic acids, alkylbenzene sulfonic acids having 10 to 24 carbon atoms in the alkyl group, alkylsulfuric acid monoesters having 10 to 24 carbon atoms in the alkyl group, oxyethylene groups having 10 to 24 carbon atoms in the alkyl group An acid type compound such as an anionic surfactant selected from polyoxyethylene alkyl ether sulfate monoesters having an average addition mole number of 1 to 4 can also be used. Examples of the alkylating agent include methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, and propylene oxide.

  The component (d2) of the present invention may be a copolymer with a compound copolymerizable with (d2 · m1) [hereinafter referred to as (d2 · m2)]. When a compound having a carboxylic acid (salt) group and a sulfonic acid (salt) group (hereinafter referred to as (d2 · m2a)) is copolymerized in (d2 · m2), (d2 · m1) / (d2 · m2a ) Is preferably copolymerized at a molar ratio of 1.1 or more, preferably 2 or more. Specific examples of (d2 · m2a) include (meth) acrylic acid (salt), maleic acid (salt), styrene sulfonic acid (salt), 2- (meth) acrylamido-2-methylpropane sulfonic acid (salt), and the like. Can be mentioned.

  As (d2 · m2) other than (d2 · m2a), (meth) acrylic acid ester having a hydroxyalkyl group having 1 to 22 carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylamide or the like (meta ) Acrylamide; polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate (ethylene glycol polymerization degree 1 to 100), polypropylene glycol (meth) acrylate (propylene glycol polymerization degree) 1-50), polybutylene glycol (meth) acrylate (the degree of polymerization of butylene glycol is 1-50), etc., polyalkylene (alkylene having 1 to 8 carbon atoms; linear or branched) oxide chain (Meth) acrylic acid ester; (meth) acrylic acid ester of polyhydric alcohol such as glycerin (meth) acrylate; acrylamide; diacetone (meth) acrylamide; N-vinyl cyclic amide such as N-vinylpyrrolidone; N- (meta ) Acrylyl morpholine; vinyl chloride; acrylonitrile and the like.

  In the present invention, the component (d) obtained by copolymerizing a compound represented by the following general formula (IV) as (d2 · m2) (hereinafter referred to as (d2 · m2e)) is preferable from the viewpoint of improving the effect of the silicone compound. It is.

[Wherein R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a monovalent hydrocarbon group having 3 to 22 carbon atoms, and Z is a linking group of CH ₂ ═C (R ¹⁰ ) — and R ^11. (However, a tertiary amino group or an acid salt thereof, or a quaternized product thereof is excluded). ]
In the general formula (IV), R ¹¹ is preferably an alkyl group or alkenyl group having 4 to 22 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 10 to 18 carbon atoms, and Z is —COO— or —CONH. A divalent group selected from-and -OCO- is preferable, and -COO- is particularly preferable.

  More specific examples of (d2 · m2e) include alkyl (meth) acrylate (the alkyl group has 4 to 22, preferably 4 to 20, more preferably 10 to 18 carbon atoms), (meth) Acryloylaminoalkyl [the carbon number of the alkyl group is 4-22, preferably 4-20, more preferably 10-18], vinyl carboxylate [the carbon number of the carboxylic acid is 4-22, preferably 4-20, More preferably, it is 10-18].

  A suitable compound of the component (d2) of the present invention is a polymer compound obtained by polymerizing monomers having the following constitution. The proportion of (d2 · m1) in the constituent monomers is 50 to 100 mol%, preferably 60 to 95 mol%. The ratio of (d2 · m2e) is 0 to 50 mol%, preferably 5 to 40 mol%. The ratio of (d2 · m2a) is 45 mol% or less, preferably 25 mol% or less. The ratio of (d2 · m2) other than (d2 · m2e) and (d2 · m2a) is 45 mol% or less, preferably 25 mol% or less. The ratio of each constituent monomer is preferably a molar ratio of (d2 · m1) / (d2 · m2a) of 1 / 0.9 or more, more preferably 1 / 0.5 or more.

  The component (d2) of the present invention is obtained by polymerizing the above-mentioned monomers (d2 · m1) and (d2 · m2) by an ordinary method, and is not particularly limited, but a radical polymerization method is particularly preferable. This can be done in bulk, solution, or emulsion systems.

  The weight average molecular weight of the component (d2) of the present invention is preferably 3,000 to 100,000, more preferably 4,000 to 80,000, and still more preferably 5,000 to 60,000. The weight average molecular weight was determined by gel permeation chromatography using a mixed solution of acetonitrile and water (phosphate buffer) or a mixed solution of ethanol and water (with LiBr / acetic acid added) as the eluent and polyethylene glycol as the standard substance. Can be measured.

[Textile treatment agent]
The textile product treating agent of the present invention contains the component (a), the component (b), the component (c), and the component (d). The content of the component (a) in the fiber product treating agent of the present invention is preferably 0.1 to 12% by mass, and 0.3 to 10% by mass from the viewpoints of solubility and adsorption performance of the silicone compound to the fiber product. % Is more preferable, 0.5-8 mass% is still more preferable, and 1-6 mass% is especially preferable. Further, the mass ratio of the component (a) / component (b) is preferably 1/100 to 1/1, more preferably 1/20 to 3/4, and still more preferably 1/10 to 1/2.

  1-30 mass% is preferable, as for content of the (b) component in the textile processing agent of this invention, 1.5-20 mass% is more preferable, and 2-15 mass% is still more preferable. Moreover, 0.01-10 mass% is preferable, as for content of (c) component, 0.03-5 mass% is more preferable, and 0.05-2 mass% is still more preferable. The mass ratio of the component (b) to the component (c) is preferably (b) component / (c) component = 80/20 to 99.9 / 0.1, more preferably 90/10 to 99/1. .

  0.2-20 mass% is preferable, as for content of the (d) component in the textile processing agent of this invention, 0.5-15 mass% is more preferable, and 1-10 mass% is still more preferable. The mass ratio of the component (b) to the component (d) is preferably (b) component / (d) component = 5/95 to 99/1, more preferably 10/90 to 90/10. The mass ratio of the component (c) to the component (d) is preferably (c) component / (d) component = 1/999 to 90/10, more preferably 1/99 to 80/20.

  Since the component (b) and the component (c) of the present invention are basically insoluble or slightly soluble compounds in water, they are not particularly required when a stable dispersion is obtained by self-dispersion or the like, but a uniform composition For the purpose of preparing a product such as an aqueous solution, it is preferable to use a nonionic surfactant other than the component (a) [hereinafter referred to as the component (e)] in combination. As the component (e), a compound represented by the following general formula (V) is preferable.

^{R 12 -E - [(R 13} O) p -H] q (V)
[Wherein R ¹² is an alkyl group or alkenyl group having 7 to 22 carbon atoms, and R ¹³ is an alkylene group having 2 or 3 carbon atoms. p shows the number of 2-150. E is -O-, -CON- or -N-, q is 1 when E is -O-, and q is 2 when E is -CON- or -N-. ]
Specific examples of the compound represented by the general formula (V) include compounds represented by the following general formulas (VI) to (IX).

^{_{R 12 -O- (C 2 H 4}} O) r -H (VI)
[Wherein R ¹² represents the above-mentioned meaning. r is a number from 2 to 150. ]
_{^{R 12 -O - [(C 2}} H 4 O) s / (C 3 H 6 O) t] -H (VII)
[Wherein R ¹² represents the above-mentioned meaning. s and t are each independently a number of 2 to 70, and ethylene oxide (C ₂ H ₄ O) and propylene oxide (C ₃ H ₆ O) may be random or block adducts. ]

[Wherein R ¹² represents the above-mentioned meaning. u and v are each independently a number from 2 to 70. ]
1-30 mass% is preferable, as for content of the (e) component in the textile processing agent of this invention, 2-25 mass% is more preferable, and 3-20 mass% is still more preferable. The mass ratio of the component (b) to the component (e) is preferably (b) component / (e) component = 95/5 to 5/95, more preferably 90/10 to 10/90, 85/15 to 15/85 is more preferable.

  The textile product treating agent of the present invention can further contain a water-soluble solvent for the purpose of optimizing storage stability and appearance of the product. As a suitable water-soluble solvent, C1-C3 monohydric alcohol, C2-C4 dihydric alcohol, glycerol, and the glycol ether compound represented by the following general formula (X) are suitable.

R ¹⁴ —O— (R ¹⁵ —O) _w —R ¹⁶ (X)
[In the formula, R ¹⁴ is selected from an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group; R ¹⁵ is selected from an ethylene group, a propylene group, —CH ₂ —CH (OH) —CH ₂ —; R ¹⁶ is selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. w shows the number of 1-5. ]
The content of the water-soluble solvent in the fiber product treating agent of the present invention is not particularly limited, but is preferably 0.5 to 40% by mass, and preferably 1 to 30% by mass because of flash point and odor problems. % Is more preferable, and 2 to 20% by mass is still more preferable.

  In the fiber product treating agent of the present invention, components usually used in a fiber treating agent can be optionally used, and examples thereof include fragrances, dyes, pigments, preservatives and chelating agents.

  The textile product treating agent of the present invention is preferably a liquid composition in which the above components are dissolved, dispersed and emulsified in water, particularly in the form of an aqueous solution, and the water content is preferably 20 to 90% by mass in the treating agent. Preferably it is 30-80 mass%, Most preferably, it is 40-70 mass%. Moreover, 2-8 are preferable and, as for pH at 20 degreeC of the processing agent of this invention, 3-7 are more preferable. For such pH adjustment, acids and bases usually used, for example, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, lactic acid, acetic acid and the like as acids, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate as bases, Alkanolamine and the like can be used.

[Textile processing method]
The textile product treating agent of the present invention is preferably added to the rinsing water at the stage of the washing rinsing step to treat the textile product, preferably 1.5 to 75 g, more preferably with respect to 30 L of rinsing water. It is added in a proportion of 3 to 60 g, more preferably 4.5 to 45 g. In addition, it is preferable to use 1 to 50 g, more preferably 2 to 40 g, and still more preferably 3 to 30 g of the treatment agent of the present invention with respect to 1 kg of the textile product. After the treatment, usual steps such as dehydration and drying can be performed. As an example, it is preferable that the fiber product treating agent of the present invention is used in an amount of 1 to 50 g per 1 kg of the fiber product.

  The compounding components used in the examples are summarized below. In the following components, EO is an abbreviation for ethylene oxide, PO is an abbreviation for propylene oxide, DMAEMA is an abbreviation for N- (meth) acryloyloxyethyl-N, N-dimethylamine, and LMA is an abbreviation for lauryl methacrylate.

<(A) component>
(A) -1: R in general formula (I) is a mixed alkyl group of 12 and 14, and n is 3 to 5 (poly) glyceryl monoether (a) -2: general (Poly) glyceryl monoether (a) in which R in formula (I) is a mixed alkyl group of 12 and 14, n is 3 to 5 and n is 55% by mass, and n is 1 to 2%. ) -3: R in general formula (I) is a mixed alkyl group of 12 and 14, n is 3 to 5 (42% by mass), n is 1 to 2 (38% by mass) (poly) Glyceryl monoether <component (b)>
(B) -1: KF-864 (Shin-Etsu Chemical Co., Ltd .: amino-modified dimethylpolysiloxane)
(B) -2: SF8457C (Toray Dow Corning Co., Ltd .: amino-modified dimethylpolysiloxane)
(B) -3: SH3775M (Toray Dow Corning Co., Ltd .: polyoxyalkylene-modified dimethylpolysiloxane)
(B) -4: FZ-2203 (Toray Dow Corning Co., Ltd .: polyoxyalkylene-modified dimethylpolysiloxane)
(B) -5: BY16-906 (Toray Dow Corning Co., Ltd .: Amide-modified dimethylpolysiloxane)
<(C) component>
(C) -1: SOREZ 100 (ISP: weight average molecular weight 7100, average EO addition mole number 88.9)
(C) -2: Texcare SRN-170 (Clariant: weight average molecular weight 2700, average EO addition mole number 33.7)
(C) -3: Texcare SRN-240 (Clariant: weight average molecular weight 6200, average EO addition mole number 80.5)
(C) -4: Texcare SRN-325 (Clariant: weight average molecular weight 12000, average EO addition mole number 35.6)
In addition, (c) -1 to (c) -4 are all the monomer constituent units of the general formula (II-1) and the monomer constituent units of the general formula (II-2) (II-1) :( II-2) = corresponds to a polymer compound comprising a molar ratio in the range of 10:90 to 90:10.

<(D) component>
(D1) -1: Dialkyl (C12-14) dimethylammonium chloride (d1) -2: Alkyl (C16-18) trimethylammonium chloride (d2) -1: DMAEMA / LMA copolymer (DMAEMA / LMA) = 80/20 raw material molar ratio, weight average molecular weight (PEG conversion) 11,000)
(D2) -2: MERQUAT 280 (manufactured by NALCO COMPANY: dimethyldiallylammonium chloride / acrylic acid copolymer, dimethyldiallylammonium chloride / acrylic acid = 65/35 raw material molar ratio, average molecular weight 450,000 (catalog value))
<(E) component>
(E) -1: nonionic surfactant obtained by adding an average of 40 mol of EO to a linear primary alcohol having 12 to 14 carbon atoms (e) -2: non-ionic surfactant obtained by adding an average of 20 mol of EO to stearyl alcohol Ionic surfactant (e) -3: Nonionic surfactant obtained by adding 50 mol of EO to stearyl alcohol on average (e) -4: Nonionic surfactant obtained by adding 140 mol of EO on average to stearyl alcohol <Others Ingredients>
PhG-30: glycol ether compound antibacterial agent obtained by adding 3 mol of EO on average to phenol: Proxel IB
Chelating agent: ethylenediaminetetraacetic acid.

Synthesis Example 1: Synthesis example of (a) -1 C3.2 / C14 mixed alcohol 93.2 g (0.50 mol) and lanthanum triflate 2.94 g (0.0050 mol) were placed in a 300 mL four-necked flask and stirred under a nitrogen stream. The temperature was raised to 90 ° C. Next, 148.16 g (2.0 mol) of glycidol was added dropwise over 24 hours while maintaining the temperature, and stirring was continued for 2 hours to obtain 251.5 g of a reaction product. As a result of analyzing the obtained reaction product by gas chromatography, the glycidol conversion rate was 99.9% or more, the C12 / C14 alcohol was 6.0% by mass, and the polyglycerol content was 2.2% by mass. In the obtained (poly) glyceryl mono C12 / C14 alkyl ether, the proportion of glycerin having a condensation degree n of 3 to 5 was 45% by mass relative to the total of n being 1 to 7. This reaction-finished product was distilled to obtain (a) -1. The ratio of the compound having a glycerin condensation degree n of 3 to 5 was 83% by mass.

Synthetic Examples 2 and 3: Synthetic Examples of (a) -2 and (a) -3 Using the same reaction finished product as in Synthetic Example 1, the distillation conditions were changed, and (a) -2 and (a) -3 were Obtained. (A) -2 is 55% by mass of the compound having a glycerin condensation degree n of 3-5, n is 22% by mass, and (a) -3 is glycerin. The ratio of the compound having a condensation degree n of 3 to 5 was 42% by mass, and the ratio of the compound having n of 1 to 2 was 38% by mass.

Examples 1-5, Comparative Examples 1-5
A textile product treating agent having the composition shown in Table 1 was prepared, and the adsorptivity of the silicone compound, the water absorption and flexibility of the textile product were evaluated by the following methods. The results are shown in Table 1.

<Adsorption evaluation method of silicone compound>
Cotton knitted fabric (manufactured by Tanigami Shoten) was washed five times in a two-tank washing machine (VH-360S1) using a commercially available detergent (attack made by Kao Corporation) (detergent concentration 0.067% by mass, using tap water) After washing at a water temperature of 20 ° C. for 10 minutes, rinsing with running water for 15 minutes, and then dehydrating for 5 minutes), it was naturally dried. This cotton knitted fabric was cut into 15 cm × 25 cm to prepare a test fabric. Ten test cloths (60 g) are obtained by adding 0.060% by mass of each fiber product treating agent to 85 r / min, 20 ° C. tap water using a Terg-O-Tometer (manufactured by Ueshima Seisakusho). Then, 1000 ml of the treating agent aqueous solution was used for 5 minutes, and rinsed. Furthermore, after dehydrating for 2 minutes, humidity was adjusted in a standard test room (20 ° C., 65% RH) by flat drying. 1 g of alkali (sodium carbonate / boric acid = 5/2) was added to the ash obtained by ashing 1 g of the treated cloth with a crucible and melted. After neutralizing with 4 mL of 6N hydrochloric acid, the amount of the silicone compound adsorbed was quantified by measuring the sample made up with pure water using an ICP emission analyzer (atomic absorption). About each Example of this invention, (a) Except not containing a component, compared with the comparative example of the same composition, and adsorption amount, it evaluated on the following reference | standard.

-Evaluation standard (circle): Compared with a comparative example, there are many silicone adsorption amounts and the feeling of texture derived from a silicone compound is expressing.
X: The amount of silicone adsorbed is equal to or less than that of the comparative example, and the feeling of texture derived from the silicone compound cannot be confirmed.

<Water absorption evaluation method>
A 1m x 1m gold cloth 2003 cloth (100% cotton) 1.5kg was washed in a two-tank washing machine (Toshiba Co., Ltd. Galaxy VH-360S1) using a commercially available laundry detergent (Kao Corporation Attack) [Detergent Concentration: 0.0667% by mass, 30L of tap water (20 ° C) used, 10 minutes for washing-3 minutes for dehydration-8 minutes for rinsing (rinsing with running water, 15 L / min.) When 5 minutes passed from the start of rinsing, running water was stopped and drained for 3 minutes. Next, 30 L of tap water (20 ° C.) was injected, 15 mL of each treatment agent shown in Table 1 was added, and the mixture was stirred for 3 minutes. After stopping the stirring, the mixture was dehydrated for 3 minutes, and the gold cloth 2003 was taken out and allowed to dry naturally at room temperature. These series of washing operations were repeated 20 times, and then naturally dried at room temperature for 4 hours, and then allowed to stand for 24 hours in a standard test room (25 ° C.-65% RH) for humidity conditioning.

  The gold cloth 2003 cloth subjected to humidity control was cut into a length of 2.5 cm × 25 cm, and dipped in ion exchange water at 20 ° C. to a depth of 1 cm with the short side down. Ten minutes after immersion, the height of water absorbed from the water surface by capillary action was measured (JIS L1907 (water absorption test method for textile products)) and evaluated according to the following criteria. In addition, the water absorption height of the gold width 2003 cloth which is not subjected to the softening treatment was 10 cm.

Evaluation criteria ◎: Water absorption height of 8 cm or more ○: Water absorption height of 6 cm or more and less than 8 cm Δ: Water absorption height of 4 cm or more and less than 6 cm ×: Water absorption height of less than 4 cm <Flexibility evaluation method>
Prepare 5 cotton towels (white, 100% cotton) and add 0.8kg of underwear (100% cotton) and 0.4kg shirt (white, cotton / polyester = 60/40%) Laundry was repeated 10 times using a commercially available laundry detergent (Kao Corporation Attack) in a two-tank washing machine (Toshiba Corporation Galaxy VH-360S1) [detergent concentration 0.0667 mass%, tap water (20 ° C) 30 L Use, washing 10 minutes-dehydration 3 minutes-rinsing 8 minutes (rinsing with running water, water volume 15 L / min.)]. When 5 minutes had passed since the last treatment (10th) rinse started, the running water was stopped and drained for 3 minutes. Next, 30 L of tap water (20 ° C.) was injected, 15 mL of each treatment agent shown in Table 1 was added, and the mixture was stirred for 3 minutes. After stopping the stirring, it was dehydrated for 3 minutes, and a towel was taken out as a textile product for evaluation and allowed to dry naturally at room temperature for 4 hours.

Thereafter, towels that were allowed to stand for 24 hours in a standard test room (25 ° C.-65% RH) and were conditioned were treated with the treating agent of Comparative Example 1 shown in Table 1 and similarly treated in the standard test room (25 ° C.-65 % RH), using a towel with a humidity control treatment as a reference product, 10 judges (5 men in their 30s and 5 women in their 30s) scored on the following criteria to determine the average score. . The average score exceeded 0.5 and 1.0 or less was evaluated as ◯, 0 or more and 0.5 or less as Δ, and less than 0 as ×.
・ Softer than the score reference control product: Equivalent to the +1 point control product: 0 point control product is softer: -1 point

Claims (6)

The textile product processing agent containing the following (a) component, (b) component, (c) component, and (d) component.
Component (a): at least one selected from glyceryl monoether and polyglyceryl monoether represented by formula (I) R—O— (C ₃ H ₆ O ₂ ) _n —H (I)
(In the formula, R is an aliphatic hydrocarbon group having 6 to 22 carbon atoms.-(C ₃ H ₆ O ₂ )-is a glycerol skeleton, and n is a number from 1 to 7 indicating the degree of condensation of glycerol. (The condensation position of glycerin may be any hydroxyl group of glycerin, including linear, branched, and random mixtures of linear and branched.)
(B) component: silicone compound (c) component: a polymer having a weight average molecular weight of 1,000 to 100,000, comprising at least one unit selected from an alkylene terephthalate unit and an alkylene isophthalate unit, and a polyoxyalkylene unit. Compound (d) component: Among 3 or 4 groups bonded to the nitrogen atom, 1 to 3 are hydrocarbon groups having 10 to 24 carbon atoms, and the rest are alkyl groups or hydroxyalkyl having 1 to 3 carbon atoms. At least one compound selected from a tertiary amine or a salt thereof or a quaternized product (d1) thereof and a cationic water-soluble polymer compound (d2)   (A) The ratio of the compound in which R in the general formula (I) is an alkyl group having 12 and / or 14 carbon atoms and the condensation degree n of glycerin is 3 to 5 is 40% by mass or more. The textile product treating agent according to claim 1, which is a product.   The fiber product treating agent according to claim 1 or 2, wherein the component (b) is at least one selected from dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, and polyoxyalkylene-modified dimethylpolysiloxane. The component (c) comprises a monomer structural unit represented by the following general formula (II-1) and a monomer structural unit represented by the following general formula (II-2): (II-1): (II-2) The fiber product treating agent according to any one of claims 1 to 3, which is a polymer compound having a weight average molecular weight of 1,000 to 100,000, which is contained in a molar ratio of 10:90 to 90:10.

[Wherein, R ¹ and R ² are alkylene groups having 2 or 3 carbon atoms, and these may be the same or different. m is a number of 1 to 150 on the number average. ]   Furthermore, the textiles processing agent in any one of Claims 1-4 which contains nonionic surfactant other than (a) component as (e) component.   A textile product processing method for treating a textile product by adding the textile product treating agent according to any one of claims 1 to 5 to rinsing water in a step of washing.