JP2007119964A - Fiber-treating agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-treating agent composition hardly damaging the emulsion even if being diluted with large excess of water, imparting good flexibility by improving the adsorptivity of a silicone compound on the surface of an object, and also capable of imparting perfume-remaining properties. <P>SOLUTION: The fiber-treating agent composition contains an oil-in-water type emulsion obtained by emulsifying a mixed solution (A) containing a silicone compound (b) and ≥20 mass% perfume component (c) having ≥2.0 logPow with the following component (a), wherein the proportions of the components (a), (b) and (c) are 1 pts.mass, 1-100 pts.mass and 0.005-30 pts.mass respectively. The component (a) is a macromolecular compound having a constituent unit (a1) having one or more groups selected from a hydroxy group, a carboxylic acid group, a quaternary ammonium group, an amino group and an amide group, and 2-20 total number of carbons (with the proviso that a constituent unit of (a2) is excluded), and the constituent unit (a2) having an 8-22C hydrocarbon group, regulated so that the molar ratio of the components (a1)/(a2) may be (100/30)-(1,000/1). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fiber treatment composition containing an oil-in-water emulsion.

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 problem of the present invention is that the emulsion does not break even when the aqueous composition containing the silicone compound is diluted in a large excess of water, and the adsorbability of the silicone compound to the surface of the object such as textiles is improved. It is providing the fiber processing agent composition which can provide a softness | flexibility and can also give a residual fragrance property.

In the present invention, the mixed solution (A) containing the following component (b) and component (c) contains an oil-in-water emulsion emulsified with the following component (a), and the oil-in-water emulsion is: (A) The fiber processing agent composition which is a ratio of 1-100 mass parts of (b) component and 0.005-30 mass parts of (c) component is provided with respect to 1 mass part of component.
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 1000/1 Molecular compound (b) component: silicone compound (c) component: a fragrance containing 20% by mass or more of a fragrance component having a log Pow of 2.0 or more

  The fiber treatment agent composition of the present invention can maintain an emulsified state even when diluted with a large excess of water by emulsifying a silicone compound and a fragrance with a polymer compound, and further to the target surface such as a textile product. It is possible to improve the adsorptivity of the silicone compound to impart good flexibility, and also to impart high residual fragrance to the textile product together with good flexibility.

[(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 1000/1 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 an effect of adsorbing to the droplet of the silicone compound of the component (b) 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 1000/1, and 1000/80 to 750/1. More preferred is 1000/50 to 1000/4. 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 1000/1.

-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 8 to 22 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- ( (Meth) acryloylaminoalkyl (C1-3) -N, N-dialkanol (C1-3) amine, N- (meth) acryloylaminoalkyl (C1-3) -N, N, N- Dialkyl (1 to 3 carbon atoms) ammonium salt (chlorine salt, methyl sulfate ester salt, ethyl sulfate ester salt is preferable as the salt), N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine Down, 3-vinyl piperidine, N- vinylimidazoline - can be exemplified Le, a N- vinyl-2-caprolactam.

  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.)
Moreover, after copolymerizing the monomer (a1 ′) and vinyl acetate, the OH of the vinyl alcohol unit obtained by saponification is converted to the formula (4)

(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 polyoxyethylene vinyl ether is copolymerized and then the formula (5)

(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 8 to 20 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) is (a1-2) / (a2-2) in a molar ratio of 1000/100 to 1000/1, preferably 1000/80 to 750/1, particularly preferably 1000/50. A polysaccharide derivative of ˜1000 / 4. Such a polysaccharide derivative is represented by the formula (6) on the hydroxy group of a polysaccharide or a hydroxyalkylated product, carboxyalkylated product or cationized product of these polysaccharides.
G- (OR ^<3b> ) _b- E-R ^<3c> (6)
(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 (6), 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 (6-1) is most preferable as the compound represented by the formula (6).

(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, a compound represented by the above formula (6-1) is added to hydroxyethyl cellulose having a hydroxyethyl group introduction rate of 0.01 to 3.5, and the above-mentioned (a1-2). 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 component (b) of the present invention is a silicone compound, and a water-insoluble silicone compound is preferable. Here, the water-insoluble compound is a compound having an amount of 1 g or less dissolved in 1 L of ion-exchanged water at 20 ° C. Specifically, dimethylpolysiloxane, quaternary ammonium modified dimethylpolysiloxane, amino modified dimethylpolysiloxane, amide modified dimethylpolysiloxane, epoxy modified dimethylpolysiloxane, carboxy modified dimethylpolysiloxane, polyoxyalkylene modified dimethylpolysiloxane, fluorine modified Examples include silicone compounds such as dimethylpolysiloxane.

In the present invention, the molecular weight is 1,000 to 1,000,000, preferably 3,000 to 1,000,000, particularly preferably 5,000 to 1,000,000, and the viscosity at 25 ° C. is 2 to 1,000,000 mm ² / s, preferably 500 to 1,000,000 mm ² /. s, particularly preferably 1,000 to 1,000,000 mm ² / s dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, polyoxyalkylene (polyoxyethylene and / or polyoxypropylene, preferably polyoxyethylene 1) One or more selected from modified dimethylpolysiloxane is preferred. 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. As polyoxyalkylene-modified dimethylpolysiloxane, surfactant manual (published by Sangyo Tosho Co., Ltd. issued on July 5, 1960), the cloud number A described on pages 324 to 325 is 0 to 18, preferably 0 to 10, more preferably 0 to 5.

Particularly in the present invention, dimethylpolysiloxane has a viscosity at 25 ° C. of 10,000 to 1,000,000 mm ² / s, and polyoxyalkylene-modified dimethylpolysiloxane has a cloud number A of 0 to 5. As the amino-modified dimethylpolysiloxane, those having a viscosity at 25 ° C. of 100 to 20,000 mm ² / s are preferable.

  Examples of the polyoxyalkylene-modified dimethylpolysiloxane include a compound represented by the following general formula (7) and a compound represented by the general formula (8).

[Wherein, R ^7a represents a hydrogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom or a methyl group. R ^7b represents a C 1-20 divalent hydrocarbon group, preferably a C 3-6 divalent hydrocarbon group, particularly preferably an alkylene group. R ^7c 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 number of moles of oxyethylene groups added, g is an average number of moles of oxypropylene groups added, h is an average number of 0 or more, i is an average number of 0 or more, and these values indicate a desired viscosity. The number of f and g is preferably from 0 to 60, and more preferably from 0 to 35. 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 ^7a , R ^7b , R ^7c , f, g and h may be the same or different.

[Wherein, R ^8a is selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a hydrogen atom, and a hydroxy group, and particularly preferably a methyl group. R ^8b and R ^8c are each independently selected from an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, and a hydroxy group, with a methyl group being particularly preferred. p and q are average polymerization degrees, and these values are selected so as to have a desired viscosity. However, p is 10 to 10000, preferably 10 to 1000, and q is 1 to 1000, preferably 3 to 3. 100. R ^8d is an alkylene group having 1 to 3 carbon atoms, R ^{8e 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). . ]

  Among these polyoxyalkylene-modified dimethylpolysiloxanes, those having an HLB of more than 0 and 10 or less are preferable, and those having an HLB of more than 0 and 7 or less are more preferable.

  In addition, HLB of the compound represented by the general formula (7) is a value obtained from the haze number A by the following formula.

    HLB = clouding number A × 0.89 + 1.11

Moreover, HLB of the compound represented by General formula (8) is a value calculated | required by a following formula.
HLB = [% by weight of (EO) +% by weight of (PO)] ÷ 5

  The above silicone compounds having low fluidity at 40 ° C. can be mixed with liquid paraffin, liquid isoparaffin, lower alcohol, lower fatty acid and low molecular weight ester compound.

[Component (c)]
The component (c) of the present invention has a log Pow of 2.0 or more, preferably 2.0 or more and 7.0 or less, more preferably 3.0 or more and 7.0 or less, hereinafter referred to as a fragrance component (c1). ) In an amount of 20% by mass or more. The content of the fragrance component (c1) in the component (c) is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more. On the other hand, it is preferable to contain a fragrance component having a higher log Pow, that is, a more hydrophobic fragrance component. It is preferable that a fragrance component having a log Pow of 3.0 or more is contained in the component (c) by 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more. Is particularly preferred. Here, logPow is a 1-octanol / water partition coefficient of a chemical substance, which is a value obtained by calculation by the f-value method (hydrophobic fragment constant method). Specifically, the chemical structure of a compound can be determined by decomposing the chemical structure into its constituent components and integrating the hydrophobic fragment constants (f values) of each fragment. CLOGP3 Reference Manual Daylight Software 4.34, Albert Leo, David You can refer to Weininger, Version1, March 1994. Such component (c) is a water-insoluble compound and exists in an aqueous composition containing a surfactant solubilized in the surfactant. However, the component (c) is stable in order to hydrophobically change the composition. And has the property of affecting the appearance of the composition.

  As the fragrance component (c1), (i) hydrocarbon fragrance, (ii) alcohol fragrance, (iii) aldehyde, ketone fragrance, (iv) ester fragrance, (v) phenol fragrance, (vi) ether A compound selected from perfume flavors can be selected.

  (I) Examples of the hydrocarbon-based fragrance include α-pinene, β-pinene, camphene, limonene, diterpene, terpinolene, myrcene, p-cymene, and β-caryophyllene, and limonene is particularly preferable.

  (Ii) Examples of alcohol-based fragrances include sandal mysole core, santalol, terpineol, l-menthol, citronellol, dihydromyrcenol, ethyl linalool, geraniol, linalool, mugor, myrsenol, nerol, and nerolidol. In particular, geraniol, dihydromyrcenol, linalool, and sandalmysol core are suitable.

  (Iii) Aldehydes and ketone-based fragrances include aldehyde C-111, greenal, mandarin aldehyde, trimethylundecenal, citral, citronellal, amyl cinnamic aldehyde, hexyl cinnamic aldehyde, lyial, dihydrojasmon, cis-jasmon, l -Carvone, ionone α, methyl ionone α, methyl ionone G. Particularly preferred are aldehyde C-111, citral, citronellal, hexylcinnamic aldehyde, methylionone G, and lyial.

  (Iv) As ester flavors, phenylethyl acetate, allyl amyl glycolate, rifarom, cis-3-hexyl acetate, styryl acetate, heptyl acetate, ot-butylcyclohexanone, pt-butylcyclohexanone, citronellyl Examples include acetate, geranyl acetate, linalyl acetate, acetyl eugenol, cinnamyl acetate, ethyl cinnamate, hexyl salicylate, and isobutyl salicylate. In particular, phenylethyl acetate, allyl amyl glycolate, styryl acetate, ot-butylcyclohexanone, citronellyl acetate, geranyl acetate, linalyl acetate, acetyleugenol, and cinnamyl acetate are preferable.

  (V) Examples of phenolic fragrances include eugenol, isoeugenol, mussins, thymol, and banitrope. In particular, eugenol and mussins are preferred.

  (Vi) Examples of ether-based fragrances include anisole, ambroxan, cedroxide, citronellyl ethyl ether, anethole, methyl eugenol, methyl isoeugenol, and nerolin yarayara. In particular, ambroxan, anethole, and nerorinarayara are suitable.

  The component (c) of the present invention is particularly preferably a fragrance containing 30% by mass or more of the fragrance component selected from the above (i) to (iv), more preferably 50% by mass or more, and further preferably 70% by mass. As described above, the fragrance is particularly preferably 80% by mass or more, most preferably 90% by mass or more.

  From the viewpoint of stability in the composition, the total content of the fragrance component (ii) + the fragrance component (iii) + the fragrance component (iv) is 20 to 90 mass% in the component (c). It is preferably 50 to 80% by mass. The mass ratio of the fragrance component (ii) / the fragrance component (iii) in the component (c) is preferably 2/8 to 8/2, and preferably 7/3 to 3/7. Further preferred.

  In addition to the above fragrance components, the component (c) of the present invention can contain a fragrance component, a diluent and a retention agent having a log Pow of −0.5 or more and less than 2.0. Preferable examples of the fragrance component having a log Pow of −0.5 or more and less than 2.0 include phenylethyl alcohol, cis-3-hexenol, helional, benzaldehyde, dimethylbenzylcarbinyl acetate, maltol, coumarin, anisaldehyde and the like. be able to. In addition, preferable examples of the diluent and the retention agent include dipropylene glycol, palmitic acid isopropyl ester, diethyl phthalate, pendyl benzoate, liquid paraffin, isoparaffin, and oil. The mass ratio of the fragrance component and the preservative is preferably 1/0 to 2/8.

[Component (d)]
The component (d) of the present invention is water, and ion-exchanged water or distilled water from which a heavy metal present in a trace amount is removed can be used. It is also possible to use sterilized water sterilized with chlorine or the like.

[Other ingredients]
The oil-in-water emulsion of the present invention comprises the components (a) to (d) as essential components, but from the viewpoint of controlling the rheology of the composition and the stability of the emulsion, the water-soluble solvent (e) It is preferable to use together. Specific examples of preferable water-soluble solvents include ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, glycerin, and 1,3-butanediol, and particularly glycerin, ethylene glycol, propylene glycol, and 1,3- Butanediol is preferred.

  In the composition of the present invention, a surfactant can be used as the component (f) for the purpose of improving the stability of the emulsion and promoting the adsorption of the oil to the target surface. Examples of surfactants that can be used include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. From the viewpoint of emulsion stability, nonionic surfactants can be used. The agent (f1) is preferable, and the cationic surfactant (f2) is preferably used in combination from the viewpoint of promoting adsorption onto the target surface.

  As the nonionic surfactant (f1), a compound represented by the general formula (9) is preferable from the viewpoint of the stability of the emulsion.

R ^9a -J-[(R ^9b -O) _r -R ^9c ] _s (9)
[Wherein R ^9a is an alkyl group or alkenyl group having 8 to 32 carbon atoms, preferably 10 to 28, more preferably 10 to 24, particularly preferably 10 to 18 carbon atoms, and R ^9b is an alkylene group having 2 or 3 carbon atoms. It is. R ^9c is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, J is a linking group selected from —O—, —COO—, —CON <or —N <, and J is —O— or —COO—. In this case, s is 1. When J is -CON <or -N <, s is 2. r is a number average of 1 to 150, preferably 2 to 80, particularly preferably 4 to 50. Here, the plurality of R ^9b and R ^9c may be the same or different. ]
In the general formula (9), R ^9a is most preferably an alkyl group having 10 to 18 carbon atoms, R ^9b is most preferably an ethylene group, and R ^9c is most preferably a hydrogen atom. J is preferably -O- or -COO-, particularly -O-.

  As the nonionic surfactant (f1), a compound represented by the general formula (9-1) is most preferable.

R ^9a —O— (C ₂ H ₄ O) _r —H (9-1)
[Wherein R ^9a and r are as defined above. ]
As the cationic surfactant (f2), a compound represented by the general formula (10) is preferable from the viewpoint of promoting the adsorption of the oil agent to the target surface.

[Wherein, R ^10a is a hydrocarbon group having 11 to 24 carbon atoms, W is a group selected from —COO— or —CONH—, and R ^10b is an alkylene group having 2 or 3 carbon atoms. t is a number of 0 or 1. R ^10c is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 2 or 3 carbon atoms, or R ^10a — [W—R ^10b ] _t —. R ^10d is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 2 or 3 carbon atoms, and R ^10e is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 2 or 3 carbon atoms, or a hydrogen atom. is there. T ⁻ is an organic or inorganic anion. ]
In the compound represented by the general formula (10), R ^10a is preferably an alkyl group having 14 to 18 carbon atoms or an alkenyl group, and t is preferably a number of 1. As the cationic surfactant (f2), a compound (f2-2) in which R ^10c is R ^10a — [W—R ^10b ] _t —, and a compound (f 2− in which R ^10c is a methyl group or a hydroxyethyl group) The mixture of 1) is preferable, and the mixture having a mass ratio of (f2-2) / (f2-1) of 100/1 to 100/10, preferably 100/2 to 100/6, promotes the adsorptivity of the oil agent. Suitable for the purpose. R ^10d is preferably a methyl group or a hydroxyethyl group, and R ^10e is preferably a hydrogen atom or a methyl group. T ^- is a halogen ion (preferably a chloro ion), an alkyl sulfate ester ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, or a benzenesulfonic acid optionally substituted with an alkyl group having 1 to 3 carbon atoms. Ions are preferred.

  In this invention, components, such as a normal additive used for a fiber processing agent, for example, antiseptic | preservative, dye, a pigment, a viscosity modifier, an inorganic salt, a hydrotrope agent, can be used as needed.

[Fiber treatment agent composition]
The content of the component (a) in the fiber treatment agent composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.05 to 8.0% by mass, and 0.1 to 5.0. Mass% is particularly preferred. (B) As for content of a component, 3-50 mass% is preferable, 4-45 mass% is more preferable, 5-40 mass% is especially preferable. Moreover, although the compounding ratio of (a) component and (b) component is 1-100 mass parts of (b) component with respect to 1 mass part of (a) component, when (a) component is a compound of (i), (A) 2-80 mass parts of (b) component is preferable with respect to 1 mass part of component, and 3-60 mass parts is more preferable. On the other hand, when (a) component is a compound of (ii), 2-80 mass parts of (b) component is preferable with respect to 1 mass part of (a) component, and 3-70 mass parts is more preferable. The content of the component (c) in the fiber treatment agent composition of the present invention is preferably 0.0001 to 15% by mass, more preferably 0.001 to 12% by mass, and particularly preferably 0.01 to 10% by mass. . Moreover, although the compounding ratio of (a) component and (c) component is 0.005-30 mass parts of (c) component with respect to 1 mass part of (a) component, 0.01-15 mass parts is preferable. 0.02 to 10 parts by mass is more preferable. 40-95 mass% is preferable, as for content of the water which is (d) component in the fiber treatment agent composition of this invention, 50-90 mass% is more preferable, and 60-90 mass% is especially preferable.

  In the method of using the fiber treatment agent composition of the present invention, as the amount of treatment for the target fiber garment, the silicone compound of component (b) is 0.01 to 5.0% by mass with respect to the garment. The amount is preferably 0.03 to 4.0% by mass, more preferably 0.05 to 3.0% by mass. Specifically, the component (b) can be 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.

  The content of the component (e) in the fiber treatment agent composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, and 4 to 20% by mass from the viewpoint of storage stability. Particularly preferred.

  Although it is an optional component, it is preferable to use the component (f1) in the fiber treatment composition of the present invention for the purpose of improving its stability, but a large amount may adversely affect the effect of the present invention. Therefore, be careful. 0.1-20 mass% is preferable, as for content of the (f1) component in the composition of this invention, 0.5-15 mass% is more preferable, and 1-10 mass% is especially preferable. The [(b) component + (a) component] / (f1) component (mass ratio) is preferably 1/1 to 50/1, more preferably 3/1 to 30/1, and 5/1 to 20 / 1 is particularly preferred. The component (f2) is preferably used in combination for the purpose of improving the adsorption of the component (b) to the target surface. However, in the same manner as the component (f1), a large amount may impair the effects of the present invention. 0-20 mass% is preferable, as for content of the (f2) component in the fiber treatment agent composition of this invention, 1-15 mass% is more preferable, and 2-10 mass% is especially preferable. In addition, the [(b) component + (a) component] / (f2) component (mass ratio) is preferably 1/5 to 80/1, more preferably 1/1 to 60/1, and 5/1 to 40. / 1 is particularly preferred.

  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.

  The viscosity at 20 ° C. of the fiber treatment agent composition of the present invention is preferably 2 to 300 mPa · s, more preferably 5 to 200 mPa · s, and more preferably 10 to 150 mPa · s from the viewpoint of ease of handling and stability of the emulsion. s is particularly preferred. Such viscosity adjustment is performed using the component (e), a normal viscosity modifier, or the like.

[Method for producing fiber treatment composition]
In the composition of the present invention, an O / W type emulsified form is preferable in that the adsorption of the component (b) to the target surface can be promoted. Further, an O / W type emulsion composition in which (a) component is used as an outer shell and capsule-like particles containing (b) component and (c) component are dispersed is more preferable. This is because the hydroxyl group in component (a) interacts with the object to be treated, or the alkyl group in component (a) interacts with component (b) and efficiently emulsifies. It is done.

  Although it does not specifically limit as a manufacturing method of the composition of this invention, It can manufacture with the following manufacturing method.

  Add component (a), optionally component (e), component (f1) and component (f2) to component (d) equivalent to 15% of the required amount at room temperature, After stirring at 0 ° C., it is cooled to 25 ° C. (this solution is referred to as (F)). Next, if necessary, the components (f1) and (f2) are added with stirring, and the mixture is left to stir. Thereafter, component (b) and component (c) are slowly added. When the component (b) is solid at normal temperature or does not flow, it is desirable to add it after heating it to the melting point or pour point. In that case, the solution (F) is also preferably heated to a temperature equal to or higher than the melting point or pour point of the component (b). After the addition, the mixture is further stirred, and then the temperature of the formulation is raised to 60 ° C. or higher than the melting point or pour point of the component (b) and further stirred to obtain a composition. Cool to the temperature as it is or to about 40 ° C. if necessary, and slowly add the remaining component (d) to the composition obtained by the above method and stir. Moreover, after adjusting pH as needed, the temperature of a formulation is slowly lowered to normal temperature and the oil-in-water emulsion of this invention is obtained. In the above production method, a part of the component (b) may be added together with the component (a).

  In this invention, it is suitable to adjust the solution of (F) to 20-75 degreeC, Preferably it is 30-60 degreeC, and mixes the water of (d) at 20-90 degreeC, Preferably it is 30-70 degreeC. The component (f1) and the component (f2) may be added in advance to the solution (F), may be previously dissolved in the component (e), and further after the solution (F) and the component (d) are mixed. It can be added.

  According to such a method, an oil-in-water emulsion containing capsule-shaped particles having a particle size of 0.1 to 50 μm in which the component (a) is an outer shell and the component (b) and the component (c) are included is obtained.

  In the present invention, a fiber treatment agent composition comprising an oil-in-water emulsion containing a silicone compound and a fragrance can be provided. According to the present invention, the emulsion does not break by dilution, and the silicone compound and the fragrance on the target surface. Can be efficiently adsorbed, and flexibility and residual fragrance can be efficiently imparted to the fiber.

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

（ｃ’−３）：ベンジルベンゾエート（香料の希釈剤として使用）
・（ｄ）成分：水
・（ｅ）成分
（ｅ−１）：グリセリン
・（ｆ）成分
（ｆ１−１−１）：ポリオキシエチレン（ＥＯ＝２１）ラウリルエーテル
（ｆ１−１−２）：２−エチルヘキシルグリセリルエーエル
（ｆ２−２−１）：Ｎ−ステアロイルアミノプロピル−Ｎ−ステアロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウムクロリド
（ｆ２−１−１）：Ｎ−ステアロイルアミノプロピル−Ｎ−２−ヒドロキシエチル−Ｎ，Ｎ−ジメチルアンモニウムクロリド
合成例１：高分子化合物（ａ−２）の合成例
Ｎ，Ｎ−ジメチルアクリルアミド９４．２ｇ，ＡＬＥ−９００（日本油脂（株）製 ラウロキシポリエチレングリコール（ＥＯ＝１８）モノアクリレート）５１．７ｇ、エタノール２００ｇを混合した。この溶液中に窒素ガスを吹き込み（２０ｍｌ／ｍｉｎ，１時間）、系内を脱気した後、６０℃に昇温した。その後Ｖ−６５（和光純薬工業（株）製、重合開始剤）エタノール溶液（３％）８２．８ｇを６０℃に保ちながら滴下した。滴下終了後６０℃で１２時間熟成を行った。反応終了後、得られた反応終了物をジイソプロピルエーテル２ｋｇ中に滴下した。得られた白色固体を濾別し、更にジイソプロピルエーテルで洗浄した（５００ｇ×２回）。減圧乾燥の後、式（１１）で表される高分子化合物（ａ−２）を１１５ｇ得た。得られた（ａ−２）のラウロキシポリエチレングリコールモノアクリレートの導入率［ｍ２／（ｍ１＋ｍ２）］をＮＭＲより測定した結果、０．０５４であった。また、重量平均分子量は６５０００であった。 <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): Nonionic surfactant obtained by adding 12 moles of ethylene oxide to lauryl alcohol on average per mole of alcohol. (B) Component (b-1): Shin-Etsu Chemical Co., Ltd. KF-96A (dimethylpolysiloxane, viscosity 5000 mm ² / s)
(B-2): KF-96A (dimethylpolysiloxane, viscosity 200,000 mm ² / s) manufactured by Shin-Etsu Chemical Co., Ltd.
(B-3): SH-200 (dimethylpolysiloxane, viscosity 1 million mm ² / s) manufactured by Toray Dow Corning Silicone Co., Ltd.
(B-4): Nippon Unicar Co., Ltd. FZ-2203 (polyoxyalkylene-modified dimethylpolysiloxane, viscosity 5000 mm ² / s, HLB: 1)
(B-5): Nihon Unicar Co., Ltd. FZ-2207 (polyoxyalkylene-modified dimethylpolysiloxane, viscosity 2500 mm ² / s, HLB: 3)
(B-6): Shin-Etsu Chemical Co., Ltd. KF-6013 (polyoxyalkylene-modified dimethylpolysiloxane, viscosity 400 mm ² / s, HLB: 10)
(B-7): KF-864 (amino-modified silicone, viscosity 1700 mm ² / s, amino equivalent 4300) manufactured by Shin-Etsu Chemical Co., Ltd.
(B-8): DC2-8630 manufactured by Toray Dow Corning Silicone Co., Ltd. (amino-modified silicone, viscosity 1500 mm ² / s, amino equivalent 4300)
-(C) component, comparative fragrance, etc. (c-1) to (c-4) and comparative fragrances (c'-1) to (c ') which are (c) components of the present invention described in Table 1 as fragrances -2) was used.

(C′-3): benzyl benzoate (used as a perfuming diluent)
(D) component: water (e) component (e-1): glycerin (f) component (f1-1-1): polyoxyethylene (EO = 21) lauryl ether (f1-1-2): 2-ethylhexyl glyceryl ether (f2-2-1): N-stearoylaminopropyl-N-stearoyloxyethyl-N, N-dimethylammonium chloride (f2-1-1): N-stearoylaminopropyl-N-2- Hydroxyethyl-N, N-dimethylammonium chloride Synthesis example 1: Synthesis example of polymer compound (a-2) N, N-dimethylacrylamide 94.2 g, ALE-900 (Noroxy polyethylene glycol Lauroxy polyethylene glycol ( EO = 18) Monoacrylate) 51.7 g and ethanol 200 g were 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 (11) 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 having a weight average molecular weight of 200,000 and a hydroxyethyl group substitution degree 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-3)).

  The substitution degree of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-3) was 0.014.

Synthesis Example 3: Synthesis Example of Polysaccharide Derivative (a-4) 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 (12) 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-4)).

  The degree of substitution of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-4) was 0.004.

Synthesis Example 4: Synthesis Example of Polysaccharide Derivative (a-5) 80 g of hydroxyethyl cellulose having a weight average molecular weight of 1,500,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-QP100MH, manufactured by Union Carbide), 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 (12) 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-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) 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 (13)

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 then dried overnight at 60 ° C. under reduced pressure to obtain 152 g of a polyoxyalkylenated hydroxyethyl cellulose derivative (polysaccharide derivative (a-6)).

  The substitution degree of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (a-6) was 0.015.

Example 1
Using the compounding components shown in Table 2, fiber treatment agent compositions having the compositions shown in Table 2 were prepared by the method described below. About the obtained fiber processing agent composition, the intensity | strength of a fragrance and the softness | flexibility were evaluated by the following method. These results are shown in Table 2.

<Method for producing fiber treatment composition>
Component (a), 1/5 (mass ratio) of component (b) and component (e) are added to 15% (25 ° C.) of component (d) necessary to obtain the composition shown in Table 2, and 25 After stirring at ° C. for 1 hour, the component (f) is added, and further stirred for 20 minutes, and then the remaining components (b) and (c) are added. Next, after stirring at 25 ° C. for 1 hour, the temperature of the formulation is raised to 60 ° C. and stirred for 1 hour to obtain a composition. After cooling the composition obtained by the above method to 40 ° C. over 1 hour, the remaining component (d) (40 ° C.) was added, stirred for 30 minutes, adjusted pH, and over 1 hour. The temperature of the formulation was lowered to 25 ° C. to obtain a fiber treatment agent composition containing an oil-in-water emulsion. The stirring speed is 400 rpm in all steps.

<Evaluation method of fragrance strength>
(1) Treatment of cotton cloth with fiber treatment composition Commercially available cotton underwear (Gunze Co., Ltd., 100% cotton) is marketed in a 2-tank washing machine (Toshiba Co., Ltd. 2-tank washing machine VH-360S1). Wash with detergent (Kao Corporation Attack, detergent concentration 0.0667% by weight, tap water use, bath ratio 17, water temperature 20 ° C., wash for 10 minutes, rinse for 15 minutes and then dehydrate for 5 minutes) Let dry naturally. The underwear is washed again with a commercially available detergent using a fully automatic washing machine (NA-F50K1 manufactured by Matsushita Electric Industrial Co., Ltd.) (Kao Co., Ltd. attack, detergent concentration 0.0667% by mass, using tap water, bath ratio 17, Water volume 30L, water temperature 20 ° C., washing 10 minutes, rinse twice, dehydration 40 seconds). At the last rinsing stage, the fiber treatment composition described in Table 2 or the control fiber treatment composition (instead of the component (a) in Table 2, (a′-1) corresponds to 5% by mass, respectively) 1 mL was added, stirred for 5 minutes, dehydrated, then spread each test cloth, laid flat and left to stand at 20 ° C. and 45% RH for 12 hours and air dried. Let

(2) Evaluation of fragrance strength The fragrance strength was evaluated according to the following criteria.
○: Stronger scent than the cotton treated with the control fiber treatment composition Δ: The same scent as the scent from the cotton treated with the control fiber treatment composition ×: Cotton treated with the control fiber treatment composition Fragrance weaker than cloth

<Flexibility evaluation method>
(1) Adjustment method of soft towel A Washing machine using 24 commercially available cotton towels (white, 34cm x 86cm, 68g / 1 sheet, 100% cotton) using a commercially available laundry detergent (Kao Corporation Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0677 mass%, using 30 L of tap water (water temperature 20 ° C.), water temperature 20 ° C., 10 minutes). Thereafter, the washing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. After stirring for 5 minutes, the rinsing water was discharged and dehydrated for 3 minutes. Next, 30 L of tap water (water temperature 20 ° C.) was poured, and after stirring for 5 minutes, the rinsing water was discharged and dehydrated for 3 minutes. This cycle was repeated 5 times and then air dried at room temperature. The mass of this air-dried cotton towel was measured.

  Next, this cotton towel was washed with a washing machine using a laundry detergent (Kao Corporation Attack) [Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0677% by mass, air-dried cotton towel 17 times the mass of water (water temperature 20 ° C.), water temperature 20 ° C., 5 minutes]. Thereafter, the washing liquid was discharged, and after dehydrating for 3 minutes, tap water (water temperature 20 ° C.) having a mass 17 times the mass of an air-dried cotton towel was poured. After stirring for 5 minutes, the rinse solution was drained and dehydrated for 3 minutes. Next, tap water (water temperature 20 ° C.) having a mass 17 times the mass of the air-dried cotton towel was poured. Next, the fiber treatment agent composition shown in Table 2 corresponding to 1.34% by mass of the mass of the air-dried cotton towel was added and stirred for 3 minutes. Thereafter, the water was discharged, dehydrated for 3 minutes and naturally dried.

(2) Preparation method of softened towel B Washing machine using 24 commercially available cotton towels (white, 34 cm x 86 cm, 68 g / 1 sheet, 100% cotton) using a commercially available laundry detergent (Kao Corp. Attack) [Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0677% by mass, tap water 30L (water temperature 20 ° C.), water temperature 20 ° C., 10 minutes]. Thereafter, the washing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. After stirring for 5 minutes, the rinsing water was discharged and dehydrated for 3 minutes. Next, 30 L of tap water (water temperature 20 ° C.) was poured, and after stirring for 5 minutes, the rinsing water was discharged and dehydrated for 3 minutes. This cycle was repeated 5 times and then air dried at room temperature. The mass of this air-dried cotton towel was measured.

  Next, this cotton towel was washed with a washing machine using a laundry detergent (Kao Corporation Attack) [Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0677% by mass, air-dried cotton towel 17 times the mass of water (water temperature 20 ° C.), water temperature 20 ° C., 5 minutes]. Thereafter, the washing liquid was discharged, and after dehydrating for 3 minutes, tap water (water temperature 20 ° C.) having a mass 17 times the mass of an air-dried cotton towel was poured. After stirring for 5 minutes, the rinse solution was drained and dehydrated for 3 minutes. Next, tap water (water temperature 20 ° C.) having a mass 17 times the mass of the air-dried cotton towel was poured. Next, a composition containing 15% of dicured beef tallow dimethylammonium chloride corresponding to 0.47% by mass of the mass of the air-dried cotton towel was added and stirred for 3 minutes. Thereafter, the water was discharged, dehydrated for 3 minutes and naturally dried.

(3) Texture evaluation The texture when the above-treated cotton towel was folded in half and lightly squeezed with both hands was determined by 10 panelists (10 men in their 30s) according to the following criteria, and the average score was determined. An average score of 0.5 or more was judged as ◎, 0 or more and less than 0.5 as ○, and less than 0 as ×.
-1: Treated towel B is softer than treated towel A 0: Treated towel A and treated towel B were softer +1: Treated towel A is softer than treated towel B

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

Claims (5)

The mixed solution (A) containing the following component (b) and component (c) contains an oil-in-water emulsion emulsified with the following component (a), and the oil-in-water emulsion is component (a): The fiber processing agent composition which is a ratio of (b) component 1-100 mass parts and (c) component 0.005-30 mass parts with respect to 1 mass part.
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 1000/1 Molecular compound (b) component: silicone compound (c) component: a fragrance containing 20% by mass or more of a fragrance component having a log Pow of 2.0 or more 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 1000/1.
-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 8 to 22 carbon atoms which may be substituted with a hydroxy group. ]   The content of the component (a) in the composition is 0.01 to 10% by mass, the content of the component (b) is 3 to 50% by mass, the content of the component (c) is 0.0001 to 15% by mass, The fiber treatment agent composition of Claim 1 or 2 whose content of water ((d) component) is 40-95 mass%.   The fiber treatment agent composition in any one of Claims 1-3 containing the oil-in-water emulsion prepared by adding water and emulsifying a mixed solution (A) with stirring. The fiber treatment agent composition according to any one of claims 1 to 4, wherein the mixed solution (A) further contains at least one selected from the group consisting of (e) a water-soluble solvent and (f) a surfactant.