JP4672385B2 - Textile treatment agent - Google Patents

Description

  The present invention relates to a fiber treatment agent.

Treatment agents for clothing for adsorbing various functional materials to fibers are known. For example, Patent Document 1 discloses a fiber treatment agent containing a substance such as ceramide. Patent Document 2 discloses a softener composition containing sericin. Patent Document 3 discloses a functionalized fiber material containing an ascorbic acid derivative.
JP 2001-146680 A JP 2001-192970 A JP 2002-61073 A

  Although fiber treatment agents for adsorbing various functional materials to fibers are known (described in Patent Documents 1 to 3), a sufficient amount of adsorption still cannot be obtained and the effect of the base can be satisfied. It is necessary to make it adsorb more in order to make it manifest, and there is room for improvement in that respect.

  The subject of this invention is providing the fiber processing agent which promotes the adsorptivity to the fiber of a functional material.

This invention provides the fiber processing agent obtained by emulsifying the following (a) component and (b) component with (c) component.
(A) Functional oil agent whose maximum mass of solute that can be dissolved in 100 g of ion-exchanged water at 20 ° C. is 1% or less (b) Amino-modified silicone compound (c) Monomer unit represented by general formula (1) ( c1) and a monomer unit (c2) represented by the general formula (2), wherein (c1) / (c2) is in a molar ratio of 100/30 to 150/1, Polymer compound in which the ratio of the total monomer units of c1) and (c2) 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), and 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; ^2d is a hydrocarbon group having 8 to 24 carbon atoms, 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 a heterocyclic group having 5 or 6-membered ring structure having at least one amino or amide group in the ring A. 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; ]

  The fiber treatment agent of the present invention can effectively adsorb the functional material to the fiber, can improve the texture of the fiber, and increase the added value of the fiber.

[(A) component]
The component (a) of the present invention is a functional oil having a maximum mass of a solute that can be dissolved in 100 g of water at 20 ° C. of 1% or less. In the present invention, the functional oil agent is not only an agent that can impart flexibility, plumpness, water absorption, etc. to the fiber by being adsorbed to the fiber, but also when this fiber product is modified and worn. Also included are agents that can reduce skin irritation. Moreover, you may implement | achieve the above-mentioned physical property by mixing 2 or more types of functional oil agents. The mass of the solute that can be dissolved in 100 g of water at 20 ° C. as the component (a) of the present invention is more preferably 0.5% or less, and particularly preferably 0.1% or less.

Specific examples of the preferable component (a) include the following components in order to improve texture and increase added value.
(I) C10-18, preferably 12-18, more preferably 14-18 saturated or unsaturated fatty alcohol; specifically decyl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, When using as a fiber treatment agent, mention may be made of linoleic alcohol, isocetyl alcohol, isostearyl alcohol, behenyl alcohol, hexadecyl alcohol, phenylethyl alcohol, cetanol, oleyl alcohol, 2-octyldodecanol, batyl alcohol, 2-hexyldecanol For this, oleyl alcohol, cetanol, and stearyl alcohol are preferred.
(Ii) sterols; for example, cholesterol, cholesteryl isostearate, cholesteryl alkenyl succinate, provitamin D3, campesterol, stegmasteranol, stigmasterol, 5-dihydrocholesterol, α-spinasterol, palisterol, cryonasterol, etc. .
(Iii) Hydrocarbons; for example, hydrocarbons such as solid or liquid paraffin, petrolatum, crystal oil, ceresin, ozokerite, montan wax, squalane, squalene, etc. (iv) vegetable or animal fats or hydrides thereof; Olive oil, avocado oil, evening primrose oil, jojoba oil, camellia oil, macadamia nut oil, mint oil, sunflower oil, rapeseed oil, sesame oil, wheat germ oil, sunflower oil, safflower oil, cottonseed oil, soybean oil, jojoba oil, palm oil, Mention may be made of palm oil, palm kernel oil, beef tallow, lard, fish oil, horse fat, egg yolk oil, carnauba wax and lanolin.
(V) Fatty acid esters having a molecular weight of 300 to 3000 (excluding (iv)); specifically, ester compounds of fatty acids having 10 to 18 carbon atoms and 1 to 6 valent alcohols having 1 to 6 carbon atoms are suitable. It is. Specific preferred examples of the alcohol include monohydric alcohols selected from ethanol, isopropanol, butanol and hexanol, dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and 1,6-hexanediol, glycerin (glycerin In some cases, mono- or diesters), trivalent or higher alcohols such as pentaerythritol, glucose, sorbitol, sorbitan and the like can be mentioned. In the present invention, isopropyl laurate, isopropyl myristate, and pentaerythritol monostearate are particularly suitable.
(Vi) a saturated or unsaturated fatty acid having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, more preferably 14 to 18 carbons; specifically, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid And linoleic acid, and oleic acid or palmitoleic acid is preferred when used as a fiber treating agent.
(Vii) Dimethylpolysiloxane: A compound having a kinematic viscosity of ² to 10 million mm ² / s, preferably 5000 to 1 million mm ² / s is suitable. Specifically Dow Corning Toray Silicone Co., Ltd. ^{SH-200 (10000mm 2 / s} ), SH-200 (100 million in mm ² / s), Shin-Etsu Chemical Co., Ltd. KF-96A (5000mm ² / s), KF-96A (200,000 mm ² / s) is preferable.

  Further, the above substances which are not fluid at 40 ° C. can be used by mixing with liquid paraffin, liquid isoparaffin, low viscosity silicone oil, lower alcohol, lower fatty acid and low molecular weight ester compound.

  Among the components (a) of the present invention, (i), (iii), (v) and (vii) are preferable, (iii) and (vii) are more preferable, and from dimethylpolysiloxane, petrolatum, squalane and paraffin. At least one selected is particularly preferred.

[Component (b)]
The component (b) of the present invention is an amino-modified silicone compound. For example, JP-A-2001-49582, JP-A-2001-192773, JP-A-2002-371474, JP-A-8-325952, JP-A-10-131054, etc. The described amino-modified silicone compounds can be used. As the component (b), a kinematic viscosity at 25 ° C. (which can be determined by an Ostwald viscometer) is preferably 100 to 20000 mm ² / s, more preferably 200 to 10,000 mm ² / s, and particularly preferably 500 to 5000 mm. ² / s, amino equivalent (molecular weight per nitrogen atom, amino equivalent = molecular weight / number of N atoms. Molecular weight is a value obtained by gel permeation chromatography with polystyrene as the standard, and the number of nitrogen atoms. Can be obtained by elemental analysis), but is preferably an amino-modified silicone compound of 400 to 8000, more preferably 600 to 5000, and particularly preferably 800 to 3000.

  (B) As a suitable specific example of a component, the compound represented by General formula (3) is mentioned.

[Wherein R ^3a represents an alkyl group having 1 to 3 carbon atoms, a hydroxy group, —OR ^3d (where R ^3d is an alkyl group having 1 to 3 carbon atoms) or a hydrogen atom, and R ^3b represents 1 to 3 represents an alkyl group, a hydroxy group or a hydrogen atom. E represents a side chain having at least one amino group, and R ^3c represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. p shows the number of 10-10,000, q shows the number of 1-1000, and shows the number from which a weight average molecular weight will be 2,000-1,000,000. R ^3a , R ^3b , R ^3c and R ^3d may be the same or different, and a plurality of R ^3b may be the same or different. ]
In the general formula (3), R ^3a is preferably a methyl group or a hydroxy group, R ^3b is preferably a methyl group or a hydroxy group, R ^3c is preferably a methyl group or a hydrogen atom, and R ^3d is preferably a methyl group. The weight average molecular weight is preferably 5,000 to 100,000, particularly preferably 8,000 to 50,000. Here, the weight average molecular weight can be determined by gel permeation chromatography using polystyrene as a standard. Examples of the side chain E having an amino group include the following.
-C ₃ H ₆ -NH _{2
-C 3 H 6 -NH-C 2} H 4 -NH 2
_{-C 3 H 6 -NH- [C 2} H 4 -NH] r -C 2 H 4 -NH 2
_{-C 3 H 6 -NH (CH 3} )
_{-C 3 H 6 -NH-C 2} H 4 -NH (CH 3)
_{-C 3 H 6 -NH- [C 2} H 4 -NH] s -C 2 H 4 -NH (CH 3)
_{-C 3 H 6 -N (CH 3} ) 2
_{-C 3 H 6 -N (CH 3} ) -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -N (CH 3} ) - [C 2 H 4 -N (CH 3)] t -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -NH-cyclo-} C 5 H 11
Here, r, s, and t are numbers from 1 to 30, respectively.

As the component (b) that can be used in the present invention, TSF4703 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 1600) manufactured by GE Toshiba Silicone Co., Ltd., TSF 4707 (viscosity 10000 mm ² / s (25 ° C.)), Amino equivalent 7000), SS-3551 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 1600), SS-3552 (viscosity 700 mm ² / s (25 ° C.), amino equivalent 7000) manufactured by Nippon Unicar Co., Ltd. DC2-8630 (viscosity 1500mm ² / s (25 ° C), amino equivalent 4300), SF8451C (viscosity 600mm ² / s (25 ° C), amino equivalent 1700), SF8452C (viscosity) manufactured by Toray Dow Corning Silicone Co., Ltd. ^{700mm 2 / s (25 ℃)} , amino eq 6400), SF8457C (viscosity 1200 ^{m 2 / s (25 ℃)} , amino eq 1800), BY16-849 (viscosity ^{1300mm 2 / s (25 ℃)} , amino equivalents 600), BY16-850 (viscosity ^{1100mm 2 / s (25 ℃)} , amino equivalent of 1100 ), BY16-892 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 2000), KF857, KF858, KF859, KF862, KF864 manufactured by Shin-Etsu Chemical Co., Ltd., WR300 (viscosity manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) 600 mm ² / s (25 ° C.), amino equivalent 3300), WR1100 (viscosity 5000 mm ² / s (25 ° C.), amino equivalent 7000), WR 1600 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 1700) and the like. be able to.

[Component (c)]
The component (c) of the present invention contains the monomer unit (c1) represented by the general formula (1) and the monomer unit (c2) represented by the general formula (2), and (c1) / (c2 ) Is a polymer compound having a molar ratio of 100/30 to 150/1, and a ratio of the total monomer units of (c1) and (c2) to all monomer units in the molecule is 50 to 100 mol%.

  The polymer compound (c) 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. A represents the above meaning, and R ^1d , R ^1e , R ^1g , R ^1h and R ¹ⁱ in A 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, and R ^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 of component (c), in the general formula (2), the structural unit in which a is 1 is preferable for the purpose of obtaining the effects of the present invention, and has an affinity for the main chain of the polymer compound and component (a). It is presumed that the stability of the emulsified particles is improved by providing a spacer between the hydrophobic 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 of component (c) having the monomer unit is a radical polymerization of the monomer (c1 ′) derived from the monomer unit (c1) and the monomer (c2 ′) derived from the monomer unit (c2). It can be obtained by copolymerization by a known method such as The monomer unit (c2) is a monomer unit (c2 ″) represented by C (R ^2a ) ((R ^2b ) = C (R ^2c ) (Z ¹ ), which is a single unit derived from the monomer unit (c1). It can also be obtained by reacting R ^2d -Z ² with a polymer compound previously copolymerized with the monomer (c1 ′), wherein Z ¹ and Z ² react to form —B— (D) _a. It is a reactive group forming ^-R2d .

  Specific examples of the monomer (c1 ′) derived from the monomer unit (c1) include (meth) acrylic acid (or an alkali metal salt or alkaline earth metal salt thereof), (anhydrous) maleic acid (or an alkali metal thereof). Salt, alkaline earth metal salt), α-hydroxyacrylic acid (or its alkali metal salt, alkaline earth metal salt), dialkyl (meth) acrylate (C1-3) amide, dialkanol (meth) acrylate (C2-C3) amide, (meth) acrylic acid monoalkanol (C2-C3) amide, vinyl acetate (vinyl acetate is saponified after polymerization and converted to a vinyl alcohol skeleton), N- (meth) Acryloyloxyalkyl (C1-3) -N, N-dialkyl (C1-3) amine, N- (meth) acryloyloxyalkyl (C1-3) -N, -Dialkanol (carbon number 1 to 3) amine, N- (meth) acryloyloxyalkyl (carbon number 1 to 3) -N, N, N-dialkyl (carbon number 1 to 3) ammonium salt (chlorine salt as a salt) , Methyl sulfate ester salt, ethyl sulfate ester salt are preferred), N- (meth) acryloylaminoalkyl (C1-3) -N, N-dialkyl (C1-3) amine, N- (meth) acryloyl Aminoalkyl (C1-C3) -N, N-dialkanol (C1-C3) amine, N- (meth) acryloylaminoalkyl (C1-C3) -N, N, N-dialkyl (carbon Formulas 1-3) Ammonium salt (chlorine salt, methyl sulfate ester salt, ethyl sulfate ester salt is preferable as the salt), N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 3-vinyl piperidine, N-vinyl imidazole, N-vinyl-2-caprolactam and the like can be mentioned.

  Examples of the monomer (c2 ′) derived from the monomer unit (c2) 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 copolymerization of the monomer (c1 ′) and vinyl acetate, OH of the vinyl alcohol unit obtained by saponification, the formula (4)

(In the formula, R ^2d and d have the above-mentioned meanings.)
It is also possible to obtain a monomer unit (c2) by reacting the glycidyl ether compound represented by the formula (1) and the average added mole number of the monomer (c1 ′) and the oxyethylene group is 1 to 300, preferably 1 to 100. More preferably, after copolymerizing 1 to 50 polyoxyethylene vinyl ether, the formula (5)

(In the formula, R ^2d has the above-mentioned meaning.)
It is also possible to obtain a monomer unit (c2) by reacting a compound represented by the formula: Furthermore, the monomer (c1 ′), 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 (c2).

  The polymer compound of component (c) is a total of monomer units (c1) and (c2) in the molecule, preferably 50 to 100 mol%, more preferably 55 to 100 mol%, particularly preferably 60 to 100 mol. It is also possible to copolymerize the monomer (c1 ′) and the monomer (c2 ′) or other monomer copolymerizable with the monomer (c2 ″). Other copolymerizable monomers include ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, Mention may be made of compounds such as 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene and α-methylstyrene.

  The weight average molecular weight of the polymer compound (c) 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.

[Fiber treatment agent]
The fiber treatment agent of the present invention is obtained by emulsifying the component (a) and the component (b) with the component (c), and in particular, the component (a), the component (b) and the component (c) are dispersed in water. The form is preferred. 0.1-50 mass% is preferable, as for content of (a) component in the fiber processing agent of this invention, 1-40 mass% is more preferable, and 2-30 mass% is especially preferable. (B) 0.1-30 mass% is preferable, as for content of a component, 0.5-25 mass% is more preferable, and 0.5-20 mass% is especially preferable. Furthermore, the mass ratio of the component (a) to the component (b) is preferably (a) / (b) = 1/10 to 10/1, from the viewpoint of obtaining good adsorptivity of the component (a), and 1/8 ~ 8/1 is more preferable, and 1/5 to 5/1 is particularly preferable. In addition, the mass ratio between the component (c) and the total amount of the components (a) and (b) is (c) / [(a) + ( b)] = 1/150 to 30/100 is preferable, 1/100 to 20/100 is more preferable, and 1/80 to 10/100 is particularly preferable.

  The pH of the fiber treatment agent of the present invention is preferably 2.0 to 9.0, more preferably 2.0 to 8.0, and particularly preferably 3.0 to 7.5, from the viewpoint of storage stability. As a method for adjusting to such a pH, it is possible to use ordinary acids such as sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, and succinic acid, and alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. it can.

  The fiber treatment agent of the present invention contains a surfactant (hereinafter referred to as component (d)) to the extent that the effect of the present invention is not impaired from the viewpoint of dispersing, solubilizing or emulsifying component (a) and storage stability. Can be used together.

  Examples of the surfactant that can be used in the present invention include alkylbenzene sulfonates having 8 to 15 carbon atoms in the alkyl group, alkyl sulfate esters having 8 to 36 carbon atoms in the alkyl group, and average addition moles of oxyethylene groups. 1-4, polyoxyethylene alkyl ether sulfate ester having 8 to 36 carbon atoms in alkyl group, alkyl ether carboxylate having alkyl group having 12 to 22 carbon atoms, alkyl ether having alkyl group having 12 to 22 carbon atoms Anionic surfactant selected from phosphates; polyoxyethylene (and / or polyoxypropylene) alkyl ethers and alkyls having an average addition mole number of oxyalkylene groups of 4 to 20 and alkyl groups of 8 to 18 carbon atoms An alkylpolyglucoside having 8 to 16 carbon atoms and an average degree of condensation of 1 to 5; A nonionic surfactant selected from 6 fatty acid sorbitan esters; a quaternary ammonium type cationic surfactant having one or two alkyl groups having 12 to 22 carbon atoms which may be separated by an ester group or an amide group Examples include agents or amine salt type surfactants; sulfobetaine type or carbobetaine type amphoteric surfactants having an alkyl group having 10 to 18 carbon atoms. Among these surfactants, nonionic surfactants and cationic surfactants are preferable from the viewpoint of storage stability. Particularly, the nonionic surfactants represented by the general formula (d1), the general formula (d2-1) ) Or a compound selected from cationic surfactants represented by the general formula (d2-2).

R ¹⁰ -G-[(R ¹¹ O) _u -H] _v (d1)
[Wherein, R ¹⁰ is an alkyl group or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R ¹¹ is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. U is a number of 2 to 60, preferably 5 to 40, particularly preferably 20 to 40. G is —O— or —CON—. When G is —O—, v is 1, and when G is —CON—, v is 2. ]

[Wherein, R ¹² and R ¹⁴ each independently represents an alkyl group or alkenyl group having 10 to 22 carbon atoms, preferably 14 to 20 carbon atoms, and K and L each independently represent —COO—, —CONR ¹⁸ — , -OCO- or -NR ¹⁸ is CO-. R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a hydrogen atom. R ¹³ and R ¹⁵ are each independently an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and R ¹⁶ is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or R ¹² -K. -R ¹³ - is. R ¹⁷ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. x and y are each independently a number of 0 or 1, preferably a number of 1. Z ⁻ is an inorganic or organic anion, preferably a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, or a fatty acid ion having 1 to 12 carbon atoms. ]
The content of the component (d) in the fiber treatment agent of the present invention is preferably 0.01 to 50% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass. In particular, when the component (d) contains a cationic surfactant, the content of the cationic surfactant in the fiber treatment agent of the present invention is preferably less than 15% by mass, and more preferably 5% by mass or less.

  The fiber treatment agent of the present invention has the purpose of improving storage stability, the purpose of stably dissolving, dispersing or solubilizing the component (a) in the fiber treatment agent, and the component (a) of the present invention to the object. In order to further increase the adsorptivity, it is preferable to use a water-soluble organic solvent (hereinafter referred to as component (e)). Specifically, preferred organic solvents are ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, glycerin, and 1,3-butanediol, and particularly preferred are glycerin, ethylene glycol, propylene glycol, and 1,3-butanediol. . Such an organic solvent is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, and particularly preferably 5 to 20% by mass in the fiber treatment agent of the present invention.

  In the fiber treatment agent of the present invention, from the viewpoint of storage stability, an ester compound of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol, and these alkylene oxide adducts are added to the fiber treatment agent in an amount of 0. 1 to 10% by mass, particularly 0.5 to 5% by mass can be blended. As the ester compound, triglyceride, diglyceride, monoglyceride, and mono, di, triester and sorbitan ester of pentaerythritol are preferable. Moreover, when adding an alkylene oxide to these compounds, ethylene oxide is suitable and the average addition mole number is 10-200, Preferably it is 20-150.

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

  In the fiber treatment agent of the present invention, a fragrance usually blended with the fiber treatment agent (particularly preferably a combination of the fragrance components shown in components (c) and (d) described in JP-A-8-11387). Alternatively, a component such as a pigment may be blended.

  The fiber treatment agent of the present invention is, for example, a method in which the fiber treatment agent of the present invention is added at the time of rinsing after washing the target garment, and after dehydrating / drying, the target garment is immersed in the fiber treatment agent of the present invention, A method of performing dehydration / drying, a method of filling the fiber treatment agent of the present invention in a container equipped with a spraying device, spraying directly on the target clothing, and then drying or ironing, a method of performing the fiber treatment agent of the present invention on a nonwoven fabric The article carried on a flexible absorbent such as can be processed into clothing by a method in which the article is put together with the target clothing in a rotary heating and drying apparatus and subjected to heat treatment. The amount of treatment on the clothing is such that the component (a) is 0.0005 to 10 mass%, preferably 0.005 to 5 mass%, more preferably 0.05 to 3 mass%, particularly preferably 0, based on the clothing. 0.05 to 2% by mass, most preferably 0.1 to 1% by mass.

  The compounding components used in the examples are summarized below.

<Compounding ingredients>
-(A) component (a-1-1): squalane (a-1-2): liquid isoparaffin (a-1-3): liquid paraffin (a-1-4): petrolatum
(A-2-1): KF-96A (Shin-Etsu Chemical Co., Ltd. dimethylpolysiloxane, viscosity 200,000 mm ² / s)
(A-2-2): SH-200 (dimethylpolysiloxane manufactured by Toray Dow Corning Silicone Co., Ltd., viscosity 1 million mm ² / s)
(B) Component (b-1): TSF-4707 (GE Toshiba Silicone Co., Ltd. amino-modified silicone, viscosity 10000 mm ² / s, amino equivalent 7000)
(B-2): SF-8457C (Toray Dow Corning Silicone Co., Ltd. amino-modified silicone, viscosity 1200 mm ² / s, amino equivalent 1800)
(B-3): BY16-849 (Amino modified silicone manufactured by Toray Dow Corning Silicone Co., Ltd., viscosity 1300 mm ² / s, amino equivalent 600)
(B-4): KF-864 (Amino-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 1700 mm ² / s, amino equivalent 4300)
(B-5): DC2-8630 (Amino modified silicone manufactured by Toray Dow Corning Silicone Co., Ltd., viscosity 1500 mm ² / s, amino equivalent 4300)
(C) Component (c-1): Vinyl pyrrolidone, dimethylaminopropyl methacrylate, and quaternary ammonium salt copolymer of dimethylaminopropyl methacrylate with lauryl chloride (Styrise W-20, manufactured by ASP Japan Co., Ltd.)
(C-2): Polymer compound (c-3) produced in Synthesis Example 1 below: Acrylic acid / alkyl methacrylate copolymer (PEMUREN TR-2, manufactured by Nikko Chemicals Co., Ltd.)
(C-4): Acrylic acid / alkyl acrylate / methacrylic acid / alkyl methacrylate copolymer (Aculin 22, manufactured by Rohm and Haas Co., Ltd.)
-Component (c ') (Comparative polymer compound)
(C′-1): sodium polyacrylate (manufactured by Nippon Shokubai Co., Ltd., Aquaric DL-384, weight average molecular weight: 8000)
(D) Component (d1-1): Nonionic surfactant obtained by adding an average of 12 moles of ethylene oxide per mole of alcohol to lauryl alcohol (d2-2-1): N-stearoylaminopropyl-N-stearoyloxy Ethyl-N, N-dimethylammonium chloride (d2-2-2): N-stearoylaminopropyl-N-2-hydroxyethyl-N, N-dimethylammonium chloride (e) Component (e-1): Glycerin (F) Component (f): Water Synthetic Example 1: Synthetic Example of Polymer Compound (c-2) N, N-dimethylacrylamide 94.2 g, ALE-900 (manufactured by NOF Corporation, 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 a polymer compound (c-2) represented by the formula (6) was obtained. As a result of measuring the introduction rate [m2 / (m1 + m2)] of the obtained (c-2) lauroxypolyethylene glycol monoacrylate by NMR, it was 0.054. Moreover, the weight average molecular weight was 65000.

Examples 1-7 and Comparative Examples 1-7
Using the components (a) to (f) shown in Tables 1 and 2, fiber treating agents having the compositions shown in Tables 1 and 2 were prepared by the method described below. The obtained fiber treating agent was processed to clothing by the following method, and the adsorptivity and flexibility were evaluated. The results are shown in Tables 1 and 2.

<Method for preparing fiber treatment agent>
The components (a), (b) and (c) or (c ′) of Table 1 and Table 2, and (d) and (e) components were mixed as necessary and stirred at 65 ° C. for 1 hour. Then, it is cooled to 50 ° C. Next, the component (f) is added dropwise with stirring. After completion of the dropwise addition, the mixture was stirred for 1 hour to adjust pH, and then cooled to room temperature to obtain a fiber treatment agent containing an oil-in-water emulsion.

<Adsorbability evaluation method>
2 g of each fiber treatment agent is added to 2250 ml of 4 ° hard water at 20 ° C. and stirred for 1 minute (using a mini washing machine). Thereafter, about 16 g × 8 cotton knitted fabrics (about 150 g in total) are added and treated for 5 minutes. After completion of the treatment, dehydration (3 minutes) is carried out and dried overnight (air drying). After drying, 1 g is cut from the treated cloth, 5 mL of hexane and an internal standard are added, and then treated with a bath sonicator for 15 minutes. Quantification is performed with a capillary GC using the extract (hexane).

Column: DB-1HT 15m
Conditions: 100 ° C. → 10 ° C./min→340° C. → 340 ° C. hold 36 min
<Flexibility evaluation method>
(1) Preparation of softening towel A 24 cotton towels (white, 34 cm x 86 cm, 68 g / 1 sheet, 100% cotton) were washed in a washing machine using a commercial laundry detergent (Kao Corporation Attack). Washed (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 detergent for clothes (Kao Corp. Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0677% by mass, mass of air-dried cotton towel Of water (water temperature 20 ° C.), water temperature 20 ° C., 5 minutes). Thereafter, the washing liquid was discharged, dehydrated for 3 minutes, and tap water (water temperature 20 ° C.) having a mass 17 times the mass of the 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 agents shown in Tables 1 and 2 corresponding to 0.47% by mass of the mass of the air-dried cotton towel were added and stirred for 3 minutes. Thereafter, water was discharged, dehydrated for 3 minutes, and air-dried to obtain a soft towel A.

(2) Preparation of Soft Treated Towel B Fiber treatment containing 15% of di-cured beef tallow dimethylammonium chloride corresponding to 0.47% by mass of air-dried cotton towel instead of the fiber treatment agent shown in Tables 1 and 2 A softened towel B was obtained in the same manner as the softened towel A except that the agent was used.

(3) Texture evaluation The above-treated cotton towels A and B are folded in half, and the texture when lightly grasped with both hands is determined by 10 panelists (10 men in their 30s) according to the following criteria, and the average score is determined. Asked. 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 (1)

The fiber processing agent obtained by emulsifying the following (a) component and (b) component with (c) component.
(A) At least one functional oil selected from dimethylpolysiloxane, petrolatum, squalane and paraffin (b) amino-modified silicone compound (c) monomer unit (c1) represented by general formula (1) and general formula ( 2) containing the monomer unit (c2) represented by (c1) / (c2) in a molar ratio of 100/30 to 150/1, and (c1) and (c2) with respect to all monomer units in the molecule The polymer compound in which the ratio of the total monomer units 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), and 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; ^2d is a hydrocarbon group having 8 to 24 carbon atoms, 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 a heterocyclic group having 5 or 6-membered ring structure having at least one amino or amide group in the ring A. 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; ]