JP2007131992A - Textile fiber treatment agent composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a textile fiber treatment agent composition subject to no demulsification even if diluted with a large excess of water, improving the adsorption of a silicone compound as a component onto the surface of an object such as a textile product, and good in storage stability. <P>SOLUTION: The textile fiber treatment agent composition comprises an oil-in-water type emulsified product that is obtained by emulsifying an aqueous mixed solution (A) containing (b) a water-soluble polyol, (c) a nonionic surfactant of the general formula (4) (wherein, R<SP>4</SP>is a 8-30C hydrocarbon group or cholesteryl group) and (d) a polyether-modified silicone with an HLB number of greater than 0 but not greater than 7 with (a) a macromolecular compound having one or more groups selected from hydroxy, carboxylic acid, quaternary ammonium, amino and amido groups and composed of monomer constituent units (a1) each with the number of carbon atoms totaling 2-20 and other monomer constituent units (a2) each having a 8-22C hydrocarbon group in the molar ratio a1/a2=(100:30) to (10,000:1). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fiber treatment composition containing an oil-in-water emulsion and a method for producing the same.

Silicone compounds are applied in various fields such as cleaning agents, finishing agents, fiber treatment agents, lubricants, etc., especially for the purpose of imparting effects such as improving the texture of objects to finishing agents for textile products such as clothing. It is widely used. Many techniques using a silicone compound and a polymer compound in combination are also disclosed. Patent Documents 1 to 13 disclose fiber treatment agent compositions containing a water-soluble polymer compound and a silicone compound that are generally known as paste bases. Patent Document 14 discloses a specific polysaccharide derivative, which describes that the polysaccharide derivative of the Patent Document can stabilize a hydrophobic compound.
JP 2000-129570 A JP 2000-129577 A JP 2000-129578 A JP 2000-239970 A JP 2003-89978 A JP-A-5-239774 JP-A-8-260356 Japanese Patent Laid-Open No. 9-13272 Japanese Patent Application Laid-Open No. 9-111162 Japanese Patent Laid-Open No. 11-229266 Japanese National Patent Publication No. 10-508911 Japanese National Patent Publication No. 10-508912 Japanese Patent Laid-Open No. 5-44169 International Publication No. 00/73351 Pamphlet

  Silicone compounds are insoluble in water, and when applied to an aqueous composition such as a finish used for washing clothes in general households, they are emulsified with a surfactant or the like. . In addition, such an aqueous composition is often added at the rinsing stage of the washing process, and a method is adopted in which it is diluted with a large excess of water and brought into contact with a textile product such as clothing. However, when the silicone compound emulsified with a surfactant or the like is diluted with a large excess of water, the emulsifying power of the surfactant is extremely reduced, the emulsification is broken, and the silicone compound cannot be present stably. For this reason, the silicone compound cannot be efficiently adsorbed to the fiber, and most of the silicone compound in the aqueous composition flows out into the waste water or adheres to the washing tub, and the effect of the silicone compound is sufficiently applied to the fiber product. It is difficult to grant.

  Patent Documents 1 to 13 disclose techniques in which a water-soluble polymer compound and a silicone compound are used in combination, but these use a water-soluble polymer compound as a paste base or a film-forming agent to emulsify the silicone compound. Water-soluble polymer compounds are not used for this purpose, and the silicone compounds described in these patent documents are emulsified with a surfactant, which can solve the problem when diluted in a large excess of water. is not.

  Patent Document 14 discloses a polysaccharide derivative modified with a long-chain alkyl group, and Examples of the Patent Document disclose a technique in which a polysaccharide derivative and a silicone compound are used in combination. However, this patent document aims to stabilize the solution of the silicone compound, and does not suggest any problem when the aqueous composition containing the silicone compound is diluted excessively. In addition, it improves the adsorptivity of the silicone compound. It does not remind me of the points to be made.

  Accordingly, the object of the present invention is to prevent the emulsification from being broken even when the aqueous composition containing the silicone compound is diluted in a large excess of water, and to improve the adsorption property of the silicone compound on the surface of the object such as a textile product and to preserve it. An object of the present invention is to provide a fiber treating agent composition having good stability.

〔式中、Ｒ⁴は炭素数８〜３０の直鎖若しくは分岐鎖の飽和あるいは不飽和の炭化水素基又はコレステリル基を示す。〕
（ｄ）成分：ＨＬＢが０を越え７以下であるポリエーテル変性シリコーン The present invention provides a fiber treating agent composition comprising an oil-in-water emulsion in which a mixed solution (A) containing the following component (b), component (c) and component (d) is emulsified with component (a) below: And a method for producing the same.
Component (a): a structural unit (a1) having at least one group selected from a hydroxy group, a carboxylic acid group, a quaternary ammonium group, an amino group, and an amide group and having a total carbon number of 2 to 20 (provided ( a2) and a structural unit (a2) having a hydrocarbon group having 8 to 22 carbon atoms in a molar ratio of (a1) / (a2) = 100/30 to 10000/1 Molecular compound (b) component: water-soluble polyol (c) component: nonionic surfactant represented by general formula (4)

[Wherein, R ⁴ represents a linear or branched saturated or unsaturated hydrocarbon group or cholesteryl group having 8 to 30 carbon atoms. ]
(D) Component: Polyether-modified silicone with HLB exceeding 0 and 7 or less

  The fiber treatment agent composition of the present invention has good storage stability and can maintain an emulsified state even when diluted with a large excess of water, and is adsorbed on an object such as a textile product to thereby form a silicone compound. Can be efficiently applied to the object.

[(A) component]
The component (a) of the present invention has at least one group selected from a hydroxy group, a carboxylic acid group, a quaternary ammonium group, an amino group, and an amide group, and has a total carbon number of 2 to 20 (a1). ) (Excluding the structural unit of (a2)) and the structural unit (a2) having a hydrocarbon group having 8 to 22 carbon atoms, a molar ratio of (a1) / (a2) = 100/30 to 10000/1 It is a polymer compound contained in

  In the structural unit (a1), the functional group selected from a hydroxy group, a carboxylic acid group, a quaternary ammonium group, an amino group and an amide group has an effect of imparting water solubility to the polymer compound and an effect of adsorbing to the textile product. It is a group having both of them, and the hydrocarbon group having 8 to 22 carbon atoms in the structural unit (a2) has the effect of adsorbing to the silicone compound droplet of the component (d) and stabilizing the oil agent in an aqueous solution. These have important functions in the present invention. The molar ratio of (a1) to (a2) is 100/30 to 150/150 / (a2-1) when the component (a) is the compound (i) below. 1 is preferable, 100/20 to 100/1 is more preferable, and 100/15 to 100/3 is particularly preferable. On the other hand, when the component (a) is a compound of the following (ii), the molar ratio of (a1-2) / (a2-2) is preferably 1000/100 to 10000/1, and 1000/80 to 5000/1. More preferred is 1000/50 to 1000/1. By adjusting to such a ratio, the silicone compound can be stably emulsified, and even if diluted with a large excess of water, the emulsification does not break, and the effect of promoting adsorption to the target surface such as textiles is obtained. Is possible.

The component (a) of the present invention includes at least one polymer compound selected from the following (i) or (ii).
(I) The monomer unit (a1-1) represented by the general formula (1) and the monomer unit (a2-1) represented by the general formula (2) are contained, and (a1-1) / (a2-1) ) Is a molar ratio of 100/30 to 150/1, and the ratio of the total monomer units of (a1-1) and (a2-1) to all monomer units in the molecule is 50 to 100 mol% .

Wherein R ^1a and R ^2a are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^1b and R ^2b are each independently a hydrogen atom or —COOM ¹ (M ¹ is a hydrogen atom Or an alkali metal atom or an alkaline earth metal atom), R ^1c and R ^2c are each independently a group selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxy group, R ^2d is a hydrocarbon group having 8 to 22 carbon atoms, and A is —COOM ² , —OH, —CON (R ^1d ) (R ^1e ), —COO—R ^1f —N ⁺ (R ^1g ) (R ^1h ) (R ¹ⁱ ) · X ⁻ , —COO—R ^1f —N (R ^1g ) (R ^1h ), —CON (R ^1d ) —R ^1f −N ⁺ (R ^1g ) (R ^1h ) (R ¹ⁱ ) · ^{X -, -CON (R 1d)} -R 1f -N (R 1g) (R 1h), or heterocyclic 5- or 6-membered ring structure having at least one amino or amide group in the ring It is. Here, M ² is a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, R ^1d , R ^1e , R ^1g , R ^1h and R ¹ⁱ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or A hydroxyalkyl group having 1 to 3 carbon atoms, R ^1f represents an alkylene group having 1 to 5 carbon atoms, and X ⁻ represents an organic or inorganic anionic group. B is a group selected from —O—, —COO—, —OCO— or —CONR ^2e — (R ^2e is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms). , D is a divalent hydrocarbon group having 2 to 6 carbon atoms which is bonded to R ^2d through a group selected from an ether group, an ester group, a cationic group or an amide group and connects B and R ^2d , oxyalkylene It is at least one group selected from a polyoxyalkylene group having an average added mole number of 1 to 300 and a polyglyceryl group having an average added mole number of 1 to 10 glyceryl groups. a represents a number of 0 or 1; ]
(Ii) Monosaccharide unit, or hydroxyalkyl (C1-3), carboxyalkyl (C1-3), or cationized monosaccharide unit (a1-2), and monosaccharide unit or hydroxy Part or all of the hydrogen atoms of the hydroxy group of the monosaccharide unit that is alkylated (carbon number 1 to 3), carboxyalkyl (carbon number 1 to 3), or cationized is represented by the general formula (3). A polysaccharide derivative having a monosaccharide unit (a2-2) substituted with a group and (a1-2) / (a2-2) in a molar ratio of 1000/100 to 10,000 / 1.

-R ^3a- (OR ^3b ) _b -E-R ^3c (3)
[Wherein, R ^3a represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hydroxy group or an oxo group, and R ^3b represents a hydroxy group or an oxo group. 1 represents a C1-C6 linear or branched divalent saturated hydrocarbon group which may be substituted, b represents a number of 1 to 300, and b R ^3b may be the same or different. Good. E represents a group selected from —O—, —COO— or —OCO—, and R ^3c represents a linear or branched hydrocarbon group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. ]

<Polymer compound (i)>
The polymer compound (i) is a synthetic polymer compound obtained by synthesizing a polymerizable unsaturated compound by an ordinary method such as radical polymerization.

In general formula (1), R ^1a and R ^1b are preferably hydrogen atoms, and R ^1c is preferably a hydrogen atom or a methyl group. R ^1d , R ^1e , R ^1g , R ^1h and R ¹ⁱ are preferably a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group. Particularly, R ^1e , R ^1g , R ^1h and R ¹ⁱ are most preferably a methyl group. ^1d is most preferably a hydrogen atom or a methyl group. R ^1f is preferably an ethylene group or a propylene group. In addition, examples of the heterocyclic group include a pyrrolidone group, a pyridine group, a piperidine group, a piperazine group, an imidazole group, and a caprolactam group, and a pyrrolidone group is preferable. As X ⁻ , 1 to 3 chloro ions, sulfate ions, alkyl sulfate ester ions having 1 to 3 carbon atoms, fatty acid ions having 1 to 12 carbon atoms, and alkyl groups having 1 to 3 carbon atoms may be substituted. Examples thereof include benzene sulfonate ion, and chloro ion or ethyl sulfate ion is preferable.

In the general formula (2), R ^2a and R ^2b are preferably hydrogen atoms, and R ^2c is preferably a hydrogen atom or a methyl group. R ^2d is preferably an alkyl group or alkenyl group having 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, and an alkyl group is particularly preferable. B is preferably —COO— or —CONR ^2e —, and R ^2e is preferably a hydrogen atom. D is a group linking the B and R ^2d, B and preferable examples of the specific structure, including _{^{R 2d, -B- [CH 2 CH}} (OH) CH 2 O] c - (C 2 H 4 O _{) d - (C 3 H 6} O) e -R 2d, -B-C n H 2n -N + (CH 3) 2 (R 2d) · X -, -B-C n H 2n -COO-R 2d , can be exemplified _{-B-C n H 2n -CONH-} R 2d. Here, c is a number from 0 to 10, preferably from 0 to 5. d is a number from 0 to 300, preferably a number from 0 to 100, more preferably a number from 0 to 75, particularly preferably a number from 0 to 50, and e is a number from 0 to 300, particularly preferably from 0 to 100. Is the number of When c is 0, d + e is a number of 1 to 300, preferably 1 to 100, particularly preferably 1 to 50, and c is 1 to 10, preferably 1 to 5, more preferably 1 or 2, particularly preferably. When is 1, d + e is a number from 0 to 300. n is a number of 2 to 6, preferably 2 or 3. X ⁻ is the same anionic group as described above.

In the polymer compound (i) of the present invention, the structural unit in which a is 1 in the general formula (2) is preferable for the purpose of obtaining the effects of the present invention, and the hydrophobicity having affinity for the main chain of the polymer compound and the silicone compound It is presumed that the stability of the emulsified particles is improved by providing a spacer between the groups R ^2d . In the present invention, in the general formula (2), a monomer unit in which D is — (C ₂ H ₄ O) _d — and d is 5 to 40 is most preferable.

The polymer compound (i) having the above monomer unit includes a monomer (a1 ′) derived from the monomer unit (a1-1) and a monomer (a2 ′) derived from the monomer unit (a2-1). Can be obtained by copolymerization by a known method such as radical polymerization. The monomer unit (a2-1) is a monomer unit (a2 ″) represented by C (R ^2a ) ((R ^2b ) = C (R ^2c ) (Y). It can also be obtained by reacting a polymer compound previously copolymerized with the derived monomer (a1 ′) with R ^2d -Z, where Y and Z react to react with —B— (D) _a. It is a reactive group forming ^-R2d .

  Specific examples of the monomer (a1 ′) derived from the monomer unit (a1-1) include (meth) acrylic acid (or its alkali metal salt, alkaline earth metal salt), (anhydrous) maleic acid (or its) Alkali metal salt, alkaline earth metal salt), α-hydroxyacrylic acid (or its alkali metal salt, alkaline earth metal salt), (meth) acrylic acid dialkyl (C 1-3) amide, (meth) acrylic acid Dialkanol (2 to 3 carbon atoms) amide, (meth) acrylic acid monoalkanol (2 to 3 carbon atoms) amide, vinyl acetate (vinyl acetate is converted to vinyl alcohol skeleton after polymerization), N- ( (Meth) acryloyloxyalkyl (C1-3) -N, N-dialkyl (C1-3) amine, N- (meth) acryloyloxyalkyl (C1-3)- , N-dialkanol (1 to 3 carbon atoms) amine, N- (meth) acryloyloxyalkyl (1 to 3 carbon atoms) -N, N, N-dialkyl (1 to 3 carbon atoms) ammonium salt (as a salt Chloro salt, methyl sulfate ester salt, ethyl sulfate ester salt are preferred), N- (meth) acryloylaminoalkyl (C1-3) -N, N-dialkyl (C1-3) amine, N- (meta ) Acryloylaminoalkyl (C1-3) -N, N-dialkanol (C1-3) amine, N- (meth) acryloylaminoalkyl (C1-3) -N, N, N-dialkyl (C1-C3) ammonium salt (as the salt, chlor salt, methyl sulfate ester salt, ethyl sulfate ester salt is preferable), N-vinyl pyrrolidone, 2-vinyl pyridine, 3-vinyl pyridi , 3-vinylpiperidine, N-vinylimidazole, N-vinyl-2-caprolactam and the like.

  Examples of the monomer (a2 ′) derived from the monomer unit (a2-1) include the following compounds.

_{CH 2 = CHCOO (C 2 H} 4 O) d -R 2d
_{CH 2 = C (CH 3)} COO (C 2 H 4 O) d -R 2d
CH ₂ = CHCOOC ₂ H ₄ N ⁺ (CH ₃ ) ₂ (R ^2d ) · X ⁻
CH ₂ = C (CH ₃ ) COOC ₂ H ₄ N ⁺ (CH ₃ ) ₂ (R ^2d ) · X ⁻
CH ₂ = CHCONHC ₃ H ₆ N ⁺ (CH ₃ ) ₂ (R ^2d ) · X ⁻
CH ₂ = C (CH ₃ ) CONHC ₃ H ₆ N ⁺ (CH ₃ ) ₂ (R ^2d ) · X ⁻
CH ₂ = CHCOOR ^2d
CH ₂ = C (CH ₃ ) COOR ^2d
(In the above series of formulas, R ^2d , d and X ⁻ have the above-mentioned meanings.)
Further, after copolymerizing the monomer (a1 ′) and vinyl acetate, OH of the vinyl alcohol unit obtained by saponification is converted to the formula (5)

(In the formula, R ^2d and d have the above-mentioned meanings.)
It is also possible to obtain a monomer unit (a2-1) by reacting the glycidyl ether compound represented by formula (1) with an average addition mole number of the monomer (a1 ′) and the oxyethylene group of 1 to 300, preferably 1. ~ 100, more preferably 1-50 after polyoxyethylene vinyl ether is copolymerized, then the formula (6)

(In the formula, R ^2d has the above-mentioned meaning.)
It is also possible to obtain a monomer unit (a2-1) by reacting a compound represented by the formula: Furthermore, the monomer (a1 ′), N- (meth) acryloyloxyethyl-N, N-dialkyl (C 1-3) amine and / or N- (meth) acryloylaminopropyl-N, N-dialkyl ( After copolymerization of an amine having 1 to 3 carbon atoms, a quaternization reaction is performed using an alkylating agent such as a compound represented by the formula R ^2d —Cl (R ^2d is as defined above), and monomer units It is also possible to obtain (a2-1).

  The polymer compound (i) is a total of the monomer units (a1-1) and (a2-1) in the molecule, preferably 50 to 100 mol%, more preferably 55 to 100 mol%, particularly preferably 60. Copolymerizing monomer (a1 ′) and monomer (a2 ′) or other monomer copolymerizable with monomer (a2 ″), which is a high molecular compound containing ˜100 mol% Other monomers that can be copolymerized include ethylene, propylene, N-butylene, isobutylene, N-pentene, isoprene, 2-methyl-1-butene, N-hexene, 2-methyl-1 Examples include compounds such as -pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, and α-methylstyrene.

The polymer compound (i) may be obtained by any polymerization method, but a radical polymerization method is particularly preferred, and this can be carried out in a lump, solution, or emulsion system. Radical polymerization may be initiated by heating, but as an initiator, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N-dimethyleneisobutylamidine) Azo initiators such as dihydrochloride, hydrogen peroxide and organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, perbenzoic acid, sodium persulfate, Existing radical initiators such as persulfates such as potassium persulfate and ammonium persulfate, and redox initiators such as hydrogen peroxide-Fe ³⁺ may be used, and in the presence or absence of a photosensitizer. The polymerization may be initiated by light irradiation or radiation irradiation.

  The weight average molecular weight of the polymer compound (i) is preferably 2000 to 200,000, more preferably 3000 to 150,000, and particularly preferably 4000 to 120,000. The weight average molecular weight can be obtained by gel permeation chromatography using polyethylene glycol as a standard.

<Polymer compound (ii)>
In the polymer compound (ii), examples of the monosaccharide unit constituting the monosaccharide unit (a1-2) include glucose, mannose, fructose, galactose, and xylose, and glucose is most preferable. Further, for the purpose of imparting water solubility to the polymer compound, it is converted to hydroxyalkyl (C1-3), preferably hydroxyethylated, carboxyalkyl (C1-3), preferably carboxymethylated, or cationized. The monosaccharide units made are preferred.

  In the polymer compound (ii), examples of the monosaccharide unit constituting the monosaccharide unit (a2-2) include glucose, mannose, fructose, galactose, and xylose, and glucose is most preferable. Further, for the purpose of imparting water solubility to the polymer compound, it is converted to hydroxyalkyl (C1-3), preferably hydroxyethylated, carboxyalkyl (C1-3), preferably carboxymethylated, or cationized. The monosaccharide units made are preferred.

  The monosaccharide unit (a2-2) is obtained by substituting a part or all of the hydrogen atoms of the hydroxy group of the monosaccharide unit (a1-2) with the group represented by the general formula (3).

In the general formula (3), R ^3a preferably represents an alkylene group having 2 or 3 carbon atoms which may be substituted with a hydroxy group, and R ^3b preferably represents an alkylene group having 2 or 3 carbon atoms, more preferably Represents an ethylene group, b is preferably 3 to 120, more preferably 5 to 60, and particularly preferably 8 to 60, and b R ^3b may be the same or different. E represents an ether bond (—O—) or an ester bond (—COO— or —OCO—), and an ether bond is preferred. R ^3c is preferably a linear or branched hydrocarbon group having 4 to 30 carbon atoms, more preferably 8 to 18 carbon atoms, particularly preferably 10 to 18 carbon atoms, and most preferably 12 to 18 carbon atoms. Is more preferable. Specifically, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isostearyl group, hexyldecyl group, octyldecyl group and the like are preferable.

In the present invention, the polymer compound (ii) has a molar ratio (a1-2) / (a2-2) of 1000/100 to 10,000 / 1, preferably 1000/80 to 5000/1, particularly preferably 1000/50. It is a polysaccharide derivative of ˜1000 / 1. Such a polysaccharide derivative is represented by the formula (7) on the polysaccharide or the hydroxy group of these polysaccharides, hydroxyalkylated product, carboxyalkylated product or cationized product.
G- (OR ^3b ) _b -E-R ^3c (7)
(In the formula, G represents a group that reacts with a hydroxy group to form an ether bond or an ester bond, and R ^3b , b, E, and R ^3c have the above-mentioned meanings.)
It is obtained by making it react so that it may enter into the range of the molar ratio of said (a1-2) / (a2-2).

  Examples of the polysaccharide used in the polymer compound (ii) include polysaccharides such as cellulose, guar gum, starch, bull run, dextran, fructan, mannan, agar, carrageenan, chitin, chitosan, pectin, alginic acid, hyaluronic acid: And derivatives substituted with a group, ethyl group, hydroxyethyl group, hydroxypropyl group, and the like. These substituents can be substituted singly or in combinations in the constituent monosaccharide residues, and examples of these polysaccharide derivatives include hydroxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose. , Methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methylcellulose, hydroxypropyl methyl guar gum, And hydroxypropylmethyl starch. Among these polysaccharides, cellulose, starch, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose are preferable, and hydroxyethyl cellulose is particularly preferable. Further, the substituent of the polysaccharide derivative is further substituted with a hydroxy group of hydroxyethyl group or hydroxypropyl group to form, for example, a polyoxyethylene chain or the like, so that the substitution exceeds 3.0 per constituent monosaccharide residue. The degree of substitution per constituent monosaccharide residue is preferably 0.1 to 10.0, and particularly preferably 0.5 to 5.0. Further, the weight average molecular weight of these polysaccharides is preferably 10,000 to 10,000,000, more preferably 100,000 to 5,000,000, and particularly preferably 100,000 to 750,000.

  As a compound represented by Formula (7), the following compounds are preferable.

(Wherein, b, R ^3c and n have the same meanings as defined above.)
When the polysaccharide is a carboxyalkylated sugar, R ^3c —O— (C ₂ H ₄ O) _b —H
R ^3c —OCOCH ₂ O— (C ₂ H ₄ O) _b —H
(In the formula, b and R ^3c have the above-mentioned meanings.)
Etc. can also be used.

  In the present invention, the compound represented by the formula (7-1) is most preferable as the compound represented by the formula (7).

(In the formula, b and R ^3c have the above-mentioned meanings.)
When the polysaccharide is a hydroxyalkylated product, the introduction rate of hydroxyalkyl groups (the number of hydroxyalkyl groups in the monosaccharide unit) is preferably 0.01 to 3.5, more preferably 0.01 to 3. When the polysaccharide is a carboxyalkylated product, the introduction rate of carboxyalkyl groups (the number of hydroxyalkyl groups in the monosaccharide unit) is preferably 0.01 to 3.0, more preferably 0.1 to 0.1. When the polysaccharide is a cationized product, the introduction rate of the cationic group is preferably 0.01 to 3.0, more preferably 0.1 to 2.5.

  As the polymer compound (ii) of the present invention, the compound represented by the above formula (7-1) is added to hydroxyethyl cellulose having a hydroxyethyl group introduction rate of 0.01 to 3.5. A compound reacted at a ratio falling within the range of the molar ratio of / (a2-2) is most preferable.

  The polymer compound (ii) of the present invention can be produced by the method described in International Publication No. 00/73351 pamphlet.

[Component (b)]
The water-soluble polyol as the component (b) of the present invention is a polyhydric alcohol having two or more hydroxyl groups in the molecule. Specifically, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4 -Alkylene glycols such as butylene glycol, polyalkylene glycols such as dipropylene glycol, glucose, maltose, maltose, sucrose, fructose, xylitol, sorbitol, maltotriose, threitol, etc. sugar alcohols, glycerin, polyglycerin, erythritol, and Starch decomposition reduced alcohol etc. are mentioned, and these 1 type or 2 types or more are used.

[Component (c)]
The component (c) of the present invention is a nonionic surfactant represented by the general formula (4).

R ⁴ in the nonionic surfactant represented by the general formula (4) is a linear or branched saturated or unsaturated hydrocarbon group or cholesteryl group having 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms. Specifically, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-ethylhexyl group, isodecyl group, isocetyl group, isostearyl group, hexyldecyl group, heptylundecyl group, octyldodecyl group, Examples include an oleyl group and a cholesteryl group.

[Component (d)]
The component (d) of the present invention is a polyether-modified silicone having an HLB of more than 0 and 7 or less, and the HLB of the polyether-modified silicone is preferably more than 0 and 5 or less, more preferably more than 0 and 3 or less.

  Examples of the component (d) include a compound represented by the following general formula (8) (hereinafter referred to as “component (d1)”) and a compound represented by the general formula (9) (hereinafter referred to as “component (d2)”).

[Wherein, R ^8a represents a hydrogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom or a methyl group. R ^8b represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably a divalent hydrocarbon group having 3 to 6 carbon atoms, and particularly preferably an alkylene group. R ^8c represents an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a hydroxy group, preferably a methyl group. EO is an oxyethylene group and PO is an oxypropylene group. f is an average addition mole number of oxyethylene groups, g is an average addition mole number of oxypropylene groups, h is an average number of 0 or more, i is an average number of 0 or more, and these values are at 25 ° C. The viscosity of the polyether-modified silicone is preferably 2 to 1,000,000 mm ² / s, more preferably 500 to 500,000 mm ² / s, particularly preferably 150 to 100,000 mm ² / s, As for f and g, the number of 0-60 is preferable respectively, and the number of 0-35 is still more preferable. h is preferably a number of 1 to 500 on average. i is preferably a number of 1 to 100 on average. The plurality of R ^8a , R ^8b , R ^8c , f, g and h may be the same or different.

[Wherein, R ^9a is selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a hydrogen atom, and a hydroxy group, and a methyl group is particularly preferable. R ^9b and R ^9c are each independently selected from an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, and a hydroxy group, and particularly preferably a methyl group. p and q are average degrees of polymerization, and these values indicate that the viscosity of the polyether-modified silicone at 25 ° C. is preferably 2 to 1 million mm ² / s, more preferably 500 to 500,000 mm ² / s, particularly preferably. Is selected to be 150 to 100,000 mm ² / s, p is 10 to 10000, preferably 10 to 1000, and q is 1 to 1000, preferably 3 to 100. R ^9d is an alkylene group having 1 to 3 carbon atoms, R ^{9e is-} (EO) _j- (PO) _k -L (L is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and EO is oxyethylene. Group, PO is an oxypropylene group, j and k each represent an average number of added moles, and the sum thereof is 1 to 100, preferably 2 to 100, particularly preferably 2 to 50). . ]

  The HLB value of the component (d1) is a value obtained by the following formula from the clouding number A measured as follows.

HLB = clouding number A × 0.89 + 1.11
<Measurement method of cloud number>
The cloud number A is measured as follows according to a known method [surfactant handbook, pages 324 to 325 (published on July 5, 1960, Sangyo Tosho Co., Ltd.)].
Weigh 2.5 g of anhydrous polyale-modified silicone, add 98% ethanol to a constant volume of 25 ml (use a 25 ml volumetric flask). Next, this is dispensed with a 5 ml whole pipette, put into a 50 ml beaker, and kept at a low temperature of 25 ° C. while stirring (using a magnetic stirrer), and measured with a 2% phenol aqueous solution using a 25 ml burette. The point at which the liquid becomes turbid is regarded as the end point, and the number of ml of 2% aqueous phenol solution required for the titration is defined as the cloud number A.

The HLB value of the component (d2) is a value obtained by the following formula.
HLB = [% by weight of (EO) +% by weight of (PO)] ÷ 5

  Specific examples of the component (d1) used in the present invention include FZ-2203, FZ-2206, FZ-2207, FZ-2222, F1-009-01, F1-009-05, manufactured by Nippon Unicar Co., Ltd. And F1-009-09, F1-009-11, and F1-009-13.

  Specific examples of the component (d2) used in the present invention include SH3772M and SH3775M manufactured by Toray Dow Corning Silicone Co., Ltd., KF6012, KF6016, KF6017 manufactured by Shin-Etsu Chemical Co., Ltd., and Toshiba Silicone Co., Ltd. TSF4445 and TSF4446.

[Oil-in-water emulsion and its production method]
The oil-in-water emulsion of the present invention can be produced by mixing (a) component, (b) component, (c) component, (d) component and water, and diluting the resulting mixture with water. (B) component 2 to 50 parts by weight, (c) component 0.1 to 10 parts by weight, (d) component 0.01 to 70 parts by weight, and water 5 A method of mixing -30 parts by weight to obtain a mixture (1) and diluting it with water is preferred. The weight ratio of the component (b) and the water in the mixture (1) is preferably (b) component / water = 10/90 to 99/1, more preferably 10/90 to 90/10. In obtaining the mixture (1), the component (b) and water may be mixed in advance to form a water-soluble polyol aqueous solution and then mixed with other components.

  In a further preferred embodiment of the present invention, first, the component (a), the component (b), the component (c) and water are mixed to obtain a mixture (1a), and the component (d) is further mixed to form the mixture (1 ). In that case, the content of the component (a) in the mixture (1a) is 1 to 10% by weight, the content of the component (b) is 10 to 90% by weight, and the content of the component (c) is 0.1 to 20%. It is preferable that the content of water is 10% to 90% by weight. Moreover, it is preferable that the weight ratio of (b) component and water is 10 / 90-90 / 10. Here, after preparing (b) component and water first and preparing water-soluble polyol aqueous solution, this aqueous solution is mixed with (a) component preferably, stirring, and also (c) component is added. More preferably, the mixture (1a) is produced. By such a production method, a stable oil-in-water emulsion having a small emulsion particle size can be prepared.

  The amount of the component (d) to be mixed with the mixture (1a) is 0.01 to 70 parts by weight, further 0.1 to 50 parts by weight with respect to 1 part by weight of the component (a) contained in the mixture (1a). In particular, the amount is preferably 1.0 to 45 parts by weight. The mixing method is not particularly limited, but the component (d) is added to the mixture (1a) at a time under appropriate mixing mechanical force, gradually added continuously, or a predetermined amount is added in several portions. May be. At this time, the dropping speed or the number of divided additions is not particularly limited, but it is preferable to adjust appropriately so as to obtain a good mixed state. A predetermined amount of component (d) is all mixed to obtain a mixture (1).

  In another preferred embodiment of the present invention, the mixture (1) can be prepared as follows. That is, the component (a) and the component (d) are mixed to prepare a mixture (1b). The amount of the component (d) in the mixture (1b) is 0.01 to 70 parts by weight, more preferably 0.1 to 50 parts by weight, particularly 1 part by weight of the component (a) contained in the mixture (1b). It is preferable that it is 1.0-45 weight part. Next, the mixture (1b), the component (b) and water are mixed with stirring, and the component (c) is further mixed to produce the mixture (1). In this case, the component (b) and water may be mixed first to prepare a water-soluble polyol aqueous solution, and then mixed with the mixture (1b) while stirring. The content of the component (b) in the mixture (1) is preferably 2 to 50 parts by weight, more preferably 2 to 40 parts by weight, particularly 4 to 35 parts by weight, based on 1 part by weight of the component (a). The mixing method is not particularly limited, but it is preferable to add the aqueous polyol solution to the mixture (1b) all at once or gradually continuously under a suitable mixing mechanical force, or to add a predetermined amount in several portions. . At this time, the dropping speed or the number of divided additions is not particularly limited, but it is preferable to adjust appropriately so as to obtain a good mixed state. After mixing a predetermined amount of the aqueous polyol solution, the component (c) is added to obtain a mixture (1).

  Next, the mixture (1) prepared as described above is diluted with water to obtain the oil-in-water emulsion of the present invention. The mixing method at the time of diluting with water is not specifically limited, It mixes under appropriate mechanical force according to the viscosity of mixture (1) and the quantity of the water to dilute. The amount of water to be mixed is such that the weight ratio of the mixture (1) / water is in the range of 1/99 to 99/1, more preferably 1/99 to 65/35, especially 1/99 to 50/50. preferable.

  The average emulsion particle diameter of the emulsion particles containing the component (d) present in the oil-in-water emulsion of the present invention is preferably 0.1 to 5.0 μm, and preferably 0.3 to 3 μm. Is more preferable, and it is especially preferable that it is 0.5-2 micrometers. The average emulsified particle diameter of the emulsified particles is a value obtained by measuring the particle size distribution by laser scattering, and is specifically a value measured using LA-910 (manufactured by Horiba Seisakusho). The measurement condition is that 0.5 g of the emulsion is diluted with 99.5 g of physiological saline and measured at room temperature.

[Fiber treatment agent composition]
In the present invention, the oil-in-water emulsion produced as described above can be used as a fiber treatment composition as it is, but in order to increase the added value of those products, these products are usually used. You may contain various additives, such as surfactant used, a dispersing agent, a solvent, a fragrance | flavor, dye, an inorganic salt, antiseptic | preservative, antioxidant, and a pH adjuster. In particular, the oil-in-water emulsion of the present invention exhibits good stability without causing changes in viscosity and separation of appearance due to aging even when a surfactant is contained.

  In the method of using the fiber treating agent composition of the present invention, the amount of the silicone compound as the component (d) is 0.05 to 5.0% by mass with respect to the clothing as the amount to be treated with respect to the target fiber clothing. The amount is preferably 0.07 to 4.0% by mass, more preferably 0.1 to 3.0% by mass. Specifically, the component (d) is efficiently added by adding and treating the fiber treatment agent composition of the present invention in washing water or rinsing water containing a textile product so as to be in the range of the above mass%. Can be adsorbed on the fiber. Further, the present invention is carried out so that the mass ratio of the textile product to be treated and water (bath ratio = mass of water / mass of textile product) is 5 to 30, preferably 8 to 20%. It is preferable to add the fiber treatment agent composition of the invention.

  In the fiber treatment agent composition of the present invention, it is preferable from the viewpoint of stability that the pH at 20 ° C. is adjusted to 2 to 8, preferably 4 to 7.5. As pH adjusters, acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, sodium hydroxide and potassium hydroxide, It is preferable to use alkali agents such as sodium carbonate and potassium carbonate alone or in combination, such as ammonia and derivatives thereof, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and particularly selected from hydrochloric acid, sulfuric acid, and citric acid. And an alkali agent selected from sodium hydroxide and potassium hydroxide are preferably used.

  In the present invention, it is possible to provide a fiber treatment composition containing an oil-in-water emulsion containing the component (d). According to the present invention, the emulsion is not broken by dilution, and (d) Components can be adsorbed efficiently.

  The compounding components used in the examples are summarized below. Further, “%” in the examples is “% by mass” unless otherwise specified.

<Compounding ingredients>
(A) Component (a-1): Vinylpyrrolidone, dimethylaminopropyl methacrylate, and a copolymer of quaternary ammonium salts with lauryl chloride of dimethylaminopropyl methacrylate (Styliese W-20, manufactured by IS Japan Co., Ltd., (A1-1) / (a2-1) = 90/10 (molar ratio))
(A-2): Polymer compound (a-2) produced in Synthesis Example 1
(A-3): polysaccharide derivative produced in Synthesis Example 2 (a-3)
(A-4): polysaccharide derivative produced in Synthesis Example 3 (a-4)
(A-5): polysaccharide derivative (a-5) produced in Synthesis Example 4
(A-6): Polysaccharide derivative produced in Synthesis Example 5 (a-6)
Comparative compound (a′-1): sodium polyacrylate (manufactured by Nippon Shokubai Co., Ltd., Aquaric DL-384, weight average molecular weight: 8000)
(B) Component (b-1): Glycerin (b-2): Ethylene glycol (b-3): 1,3-butylene glycol (b-4): Polyglycerin (degree of polymerization: 4)
(C) Component (c-1): Nonionic surfactant represented by formula (4-1) (c-2): Nonionic surfactant represented by formula (4-2) (c -3): nonionic surfactant represented by formula (4-3)

(D) Component (d-1): SM-3775M (Toray Dow Corning, polyether-modified silicone manufactured by Silicone Corp., HLB value 5)
(D-2): FZ-2109 (polyether-modified silicone manufactured by Toray Dow Corning Silicone Co., Ltd., HLB value 1)
(D-3): polyether-modified silicone represented by formula (9-1) (HLB value 1)

[Wherein, p ₁ is 450 to 550, q ₁ is 5 to 15, and j ₁ is 2 to 5. ]
(D-4): polyether-modified silicone represented by formula (9-2) (HLB value 1)

[Wherein, p ₂ is a number from 380 to 480, q ₂ is a number from 5 to 15, and j ₂ is a number from ₂ to 5. ]
(D-5): polyether-modified silicone represented by formula (9-3) (HLB value 1)

[Wherein, p ₃ is a number from 340 to 440, q ₃ is a number from 5 to 15, and j ₃ is a number from 2 to 5. ]
(D-6): FZ-2203 (polyether-modified silicone manufactured by Toray Dow Corning Silicone Co., Ltd., HLB value 1)
In the following synthesis examples, “degree of substitution” indicates the average number of substituents per constituent monosaccharide residue or constituent monomer unit.

Synthesis Example 1: Synthesis Example of Polymer Compound (a-2) 94.2 g of N, N-dimethylacrylamide, ALE-900 (Noroxy Polyethylene Glycol (EO = 18) monoacrylate) 51.7 g 200 g of ethanol was mixed. Nitrogen gas was blown into this solution (20 ml / min, 1 hour), the system was deaerated, and then the temperature was raised to 60 ° C. Then, 82.8 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd., polymerization initiator) ethanol solution (3%) was added dropwise while maintaining the temperature at 60 ° C. After completion of the dropping, aging was performed at 60 ° C. for 12 hours. After completion of the reaction, the obtained reaction product was dropped into 2 kg of diisopropyl ether. The resulting white solid was filtered off and further washed with diisopropyl ether (500 g × 2 times). After drying under reduced pressure, 115 g of the polymer compound (a-2) represented by the formula (10) was obtained. As a result of measuring the introduction rate [m2 / (m1 + m2)] of the obtained (a-2) lauroxypolyethylene glycol monoacrylate by NMR, it was 0.054. Moreover, the weight average molecular weight was 65000.

Synthesis Example 2: Synthesis Example of Polysaccharide Derivative (a-3) 160 g of hydroxyethyl cellulose (SE400, manufactured by Daicel Chemical Industries) having a weight average molecular weight of 200,000 and a substitution degree of hydroxyethyl group of 2.5, 850 g of water-containing 80% isopropyl alcohol, A slurry solution was prepared by mixing 9.8 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature for 30 minutes in a nitrogen atmosphere. In this solution, the following formula (11)

The compound represented by this was added, and it was made to react at 80 degreeC for 8 hours, and polyoxyalkylenation was performed. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 700 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 152 g of a polyoxyalkylenated hydroxyethyl cellulose derivative (polysaccharide derivative (a-3)).

  The degree of substitution of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-3) was 0.009.

Synthesis Example 3: Synthesis Example of Polysaccharide Derivative (a-4) 160 g of hydroxyethyl cellulose having a weight average molecular weight of 200,000 and a substitution degree of hydroxyethyl group of 2.5 (NATROZOL250G, manufactured by Hercules), 1280 g of water-containing 80% isopropyl alcohol, 48% A slurry solution was prepared by mixing 9.8 g of an aqueous sodium hydroxide solution and stirred at room temperature for 30 minutes under a nitrogen atmosphere. In this solution, the following formula (12)

31.8 g of the compound represented by the above formula was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 700 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 152 g of a polyoxyalkylenated hydroxyethyl cellulose derivative (polysaccharide derivative (a-4)).

  The substitution degree of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-4) was 0.015.

Synthesis Example 4: Synthesis Example of Polysaccharide Derivative (a-5) 80 g of hydroxyethyl cellulose having a weight average molecular weight of 500,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-QP4400H, manufactured by Union Carbide), 640 g of water-containing 80% isopropyl alcohol A 48% sodium hydroxide aqueous solution (5.34 g) was mixed to prepare a slurry solution, which was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this solution, 12.78 g of the compound represented by the formula (11) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol and then dried overnight at 60 ° C. under reduced pressure to obtain 73 g of a polyoxyalkylenated hydroxyethyl cellulose derivative (polysaccharide derivative (a-5)).

  The degree of substitution of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-5) was 0.004.

Synthesis Example 5: Synthesis Example of Polysaccharide Derivative (a-6) 80 g of hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of 1,500,000 and a hydroxyethyl group substitution degree of 1.8, 640 g of water-containing 80% isopropyl alcohol And 48% sodium hydroxide aqueous solution 5.34g was mixed, the slurry liquid was prepared, and it stirred for 30 minutes at room temperature in nitrogen atmosphere. To this solution, 12.78 g of the compound represented by the formula (11) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was dried twice with 500 g of isopropyl alcohol and dried for one day at 60 ° C. under reduced pressure to obtain 72.0 g of a polyoxyalkylenated hydroxyethyl cellulose derivative (polysaccharide derivative (a-6)).

  The degree of substitution of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-6) was 0.004.

Example 1
Using the compounding components shown in Table 1, fiber treatment agent compositions having the compositions shown in Table 1 were prepared by the method described below. The obtained composition was diluted 500 times with water, placed on a preparation, and the state of emulsified particles was observed with a digital microscope (KEYENCE VH-8500). Moreover, the fiber treatment agent composition was processed to clothing by the following method, and the adsorption amount of (d) component was measured. These results are shown in Table 1.

<Method for Preparing Fiber Treatment Agent Composition>
45% of the components (a), (b) and (b) in Table 1 are stirred at 80 ° C. for 1 hour and cooled to 30 ° C. Next, (c) component was added, and after stirring for 20 minutes, (d) component was dripped, stirring. After completion of dropping, the temperature is raised to 60 ° C., stirred for 1 hour, cooled to 40 ° C. over 1 hour, added with the remaining water, stirred for 30 minutes or more, and a fiber treating agent composition containing an oil-in-water emulsion. Got. The stirring speed is 500 rpm in all steps.

<Measurement method of adsorption amount>
Wash the cotton knives # 2003 (manufactured by Tanigami Shoten) with a two-tank washing machine (Toshiba Co., Ltd., two-tank washing machine VH-360S1) using a commercial detergent (Kao Co., Ltd. attack, detergent concentration 0. 0667% by mass, using tap water, water temperature 20 ° C., washed for 10 minutes, rinsed with running water for 15 minutes, dehydrated for 5 minutes), and allowed to dry naturally. This is cut to obtain about 16 g × 8 pieces (about 150 g in total) of test cloth. 2 g of each composition is added to 2250 ml of 4 ° hard water at 20 ° C., and stirred for 1 minute (using National Electric Fiber NA-35). Then, the test cloth is added and treated for 5 minutes.
After completion of the treatment, dehydration (3 minutes) is carried out and dried overnight (air drying). After drying, cut 1g from the treated cloth, put it in a screw tube vial, add 50g of chloroform, and leave it overnight. Then, ultrasonic irradiation is performed with a bath-type sonicator for 30 minutes. To this solution is added 1.0 ml of a standard solution (internal standard: dimethyl terephthalate, using a solution of about 500 mg dissolved in 100 ml) and vigorously stirred. Chloroform is distilled off from the resulting solution with an evaporator. The residue is dissolved in 1.5 ml of deuterated chloroform, ¹ H-NMR is measured, and the component (d) is calculated.
The adsorption rate (%) of the component (d) was calculated using the amount of dimethyl terephthalate in the standard solution, the peak area of the aromatic ring proton of dimethyl terephthalate, and the peak area of the methyl group of the silicone molecule.

*: Adjusted using pH at 20 ° C., 1/10 N aqueous sulfuric acid solution and 1/10 N aqueous sodium hydroxide solution.

Example 2
A fiber treatment composition having the composition shown in Table 2 was prepared in the same manner as in Example 1 using the blending components shown in Table 2. About the obtained fiber processing agent composition, the average emulsion particle diameter and stability were evaluated by the following method. The results are shown in Table 2.

<Average emulsified particle size>
The average particle size of the emulsified particles in the emulsion was measured using a LA-910 particle size distribution measuring device by laser scattering manufactured by HORIBA, Ltd. at room temperature after diluting the composition 500 times with water. .

<Stability>
The fiber treating agent composition was stored at room temperature and 40 ° C. for 1 month, and the presence or absence of separation was visually observed and evaluated according to the following criteria.
○: No separation observed ×: Separated

*: Adjusted using pH at 20 ° C., 1/10 N aqueous sulfuric acid solution and 1/10 N aqueous sodium hydroxide solution.

Claims (10)

A fiber treatment agent composition comprising an oil-in-water emulsion in which a mixed solution (A) containing the following component (b), component (c) and component (d) is emulsified with the component (a) below.
Component (a): a structural unit (a1) having at least one group selected from a hydroxy group, a carboxylic acid group, a quaternary ammonium group, an amino group, and an amide group and having a total carbon number of 2 to 20 (provided ( a2) and a structural unit (a2) having a hydrocarbon group having 8 to 22 carbon atoms in a molar ratio of (a1) / (a2) = 100/30 to 10000/1 Molecular compound (b) component: water-soluble polyol (c) component: nonionic surfactant represented by general formula (4)

[Wherein, R ⁴ represents a linear or branched saturated or unsaturated hydrocarbon group or cholesteryl group having 8 to 30 carbon atoms. ]
(D) Component: Polyether-modified silicone with HLB exceeding 0 and 7 or less The fiber treatment agent composition according to claim 1, wherein the component (a) is at least one polymer compound selected from the following (i) or (ii).
(I) The monomer unit (a1-1) represented by the general formula (1) and the monomer unit (a2-1) represented by the general formula (2) are contained, and (a1-1) / (a2-1) ) Is a molar ratio of 100/30 to 150/1, and the ratio of the total monomer units of (a1-1) and (a2-1) to all monomer units in the molecule is 50 to 100 mol% .

Wherein R ^1a and R ^2a are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^1b and R ^2b are each independently a hydrogen atom or —COOM ¹ (M ¹ is a hydrogen atom Or an alkali metal atom or an alkaline earth metal atom), R ^1c and R ^2c are each independently a group selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxy group, R ^2d is a hydrocarbon group having 8 to 22 carbon atoms, and A is —COOM ² , —OH, —CON (R ^1d ) (R ^1e ), —COO—R ^1f —N ⁺ (R ^1g ) (R ^1h ) (R ¹ⁱ ) · X ⁻ , —COO—R ^1f —N (R ^1g ) (R ^1h ), —CON (R ^1d ) —R ^1f −N ⁺ (R ^1g ) (R ^1h ) (R ¹ⁱ ) · ^{X -, -CON (R 1d)} -R 1f -N (R 1g) (R 1h), or heterocyclic 5- or 6-membered ring structure having at least one amino or amide group in the ring It is. Here, M ² is a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, R ^1d , R ^1e , R ^1g , R ^1h and R ¹ⁱ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or A hydroxyalkyl group having 1 to 3 carbon atoms, R ^1f represents an alkylene group having 1 to 5 carbon atoms, and X ⁻ represents an organic or inorganic anionic group. B is a group selected from —O—, —COO—, —OCO— or —CONR ^2e — (R ^2e is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms). , D is a divalent hydrocarbon group having 2 to 6 carbon atoms which is bonded to R ^2d through a group selected from an ether group, an ester group, a cationic group or an amide group and connects B and R ^2d , oxyalkylene It is at least one group selected from a polyoxyalkylene group having an average added mole number of 1 to 300 and a polyglyceryl group having an average added mole number of 1 to 10 glyceryl groups. a represents a number of 0 or 1; ]
(Ii) Monosaccharide unit, or hydroxyalkyl (C1-3), carboxyalkyl (C1-3), or cationized monosaccharide unit (a1-2), and monosaccharide unit or hydroxy Part or all of the hydrogen atoms of the hydroxy group of the monosaccharide unit that is alkylated (carbon number 1 to 3), carboxyalkyl (carbon number 1 to 3), or cationized is represented by the general formula (3). A polysaccharide derivative having a monosaccharide unit (a2-2) substituted with a group and (a1-2) / (a2-2) in a molar ratio of 1000/100 to 10,000 / 1.
-R ^3a- (OR ^3b ) _b -E-R ^3c (3)
[Wherein, R ^3a represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hydroxy group or an oxo group, and R ^3b represents a hydroxy group or an oxo group. 1 represents a C1-C6 linear or branched divalent saturated hydrocarbon group which may be substituted, b represents a number of 1 to 300, and b R ^3b may be the same or different. Good. E represents a group selected from —O—, —COO— or —OCO—, and R ^3c represents a linear or branched hydrocarbon group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. ] The component (a) is substituted in the formula (3) with a group in which R ^3b is an ethylene group, b is a number of 1 to 200, and R ^3c is a linear or branched alkyl group having 4 to 30 carbon atoms. The fiber treatment agent of Claim 2 which is a polysaccharide derivative which has the monosaccharide unit (a2-2) which is, and (a1-2) / (a2-2) is 1000 / 100-10000 / 1 by molar ratio. Composition.   The fiber treatment agent composition according to any one of claims 1 to 3, wherein an average emulsion particle size of the emulsion in the oil-in-water emulsion is 0.1 to 5.0 µm.   The oil-in-water emulsion obtained by mixing (a) component, (b) component, (c) component, (d) component, and water, and diluting this mixture with water is contained. The fiber treatment agent composition in any one.   The fiber treatment agent composition according to any one of claims 1 to 4, wherein (a) component, (b) component, (c) component, (d) component and water are mixed, and the resulting mixture is diluted with water. Manufacturing method.   (A) 2 parts by weight of component (b), 0.1 to 10 parts by weight of component (c), 0.01 to 70 parts by weight of component (d), and 5 to 30 parts by weight of water with respect to 1 part by weight of component The manufacturing method of the fiber treatment agent composition of Claim 6 which mixes a part and obtains a mixture (1) and dilutes this with water.   The manufacturing method of the fiber treatment agent composition of Claim 7 whose (b) component and water in mixture (1) are the weight ratio of 10 / 90-99 / 1.   The component (a), the component (b), the component (c) and water are mixed, and then the component (d) is added and mixed to obtain a mixture (1), which is diluted with water. A method for producing a fiber treating agent composition.   The mixture of the component (a) and the component (d) is added with and mixed with the component (b) and water and the component (c) to obtain a mixture (1), which is diluted with water. The manufacturing method of the fiber treatment agent composition of description.