JP4699159B2 - Textile treatment agent and method for removing wrinkles from textile - Google Patents

Description

  The present invention is capable of effectively removing wrinkles generated when a washed textile product is dried with a dryer or a laundry dryer, which cannot obtain a satisfactory removal effect with the prior art. The present invention relates to an absorbent composition, a fiber product treating agent containing the same, and a method for removing wrinkles from the fiber product.

  In addition to dryers that only have a drying function that has been widely used in the home (tumble dryers), laundry dryers that are equipped with a heater and added a drying function are rapidly becoming popular. Yes. The washing and drying machine has a drying function in the so-called drum-type washing machine that rotates the washing tub to wash clothes and the fully automatic washing machine that generates water flow with the stirring blade (pulsator) at the bottom of the washing tub to wash clothes. Broadly divided into vertical washer-dryers. In all models, the finish of dry clothing is relatively low in wrinkle garments and cotton / synthetic fiber garments, whereas in cotton garments such as T-shirts and underwear, the wrinkles are remarkably wrinkled. There is a strong demand for finishes that can improve the wrinkles of cotton clothing.

  A treating agent and a treating method for textile products using a domestic drier are already known. Patent Documents 1 to 5 disclose fiber product conditioning agents for dryers, which are made of a specific base material impregnated with a softening agent for the purpose of softening the fiber product and preventing static electricity. Patent Documents 6 and 7 disclose a technique for a dryer sheet in which a flexible substrate is impregnated with a composition containing a specific silicone compound. However, these techniques do not suggest any wrinkle removal, and satisfactory wrinkle removal effects cannot be obtained even using the techniques of these publications.

  On the other hand, Patent Documents 8 and 9 disclose a technique for removing wrinkles of a fiber product by heating and drying the fiber product in a rotating tank, but the target fiber product is used as a dry cleaning garment such as a suit. It is limited, and it is premised on spray treatment on the dry clothes after wearing, and there is no suggestion about the improvement of wrinkles that occur when wet clothes are dried with a dryer or washing dryer However, a satisfactory wrinkle removal effect cannot be obtained even using the techniques of these publications.

  Patent Documents 10 and 11 disclose fiber treatment agents using reactive silicone block copolymers and amino-modified polysiloxane-polyoxyalkylene block copolymers. This technology avoids the problems of sliminess and water repellency, which are the characteristics of amino-modified dimethylpolysiloxanes used in products, and imparts flexibility and antistatic properties. Drying wet clothes with a dryer or washing dryer There is no suggestion about the improvement of wrinkles that occur. Further, the treatment concentration is high, and it is necessary to perform the treatment at a high temperature in order to obtain the desired effect.

Patent Document 12 discloses a finish composition that improves the difficulty of removing a textile product from a washing machine at the end of the home washing process of the textile product. This finish composition is a composition obtained by mixing a specific modified silicone and a specific amine compound, a neutralized product of the amine compound and / or a quaternized product of the amine compound and then mixing with an aqueous phase. In addition, these technologies do not suggest any improvement on the wrinkles that occur when wet clothing is dried with a dryer or a washing dryer, and furthermore, even if these technologies are used, a satisfactory wrinkle removal effect can be obtained. I can't get it.
JP-T-9-502369 Japanese National Patent Publication No. 10-512929 JP 7-82669 A Japanese Patent Laid-Open No. 7-18578 JP 52-31200 A JP-A-6-17376 JP 63-42978 A JP 2002-115182 A JP 2003-20561 A JP-A-9-111668 Japanese Patent Laid-Open No. 9-183854 JP 2003-89979 A

  The problem of the present invention is that wrinkles generated when a textile product after washing and dehydration is dried, which cannot be obtained with a satisfactory removal effect with the prior art, especially when dried with a dryer or a washing dryer. It is an object of the present invention to provide a wrinkle remover composition, a textile product treating agent, and a textile product wrinkle removing method that can effectively remove the crease.

The present invention relates to a wrinkle removal composition containing a slip improver that satisfies the following requirement (I).
<Requirement (I)>
For 100 parts by weight of plain cotton fabric, 0.2 part by weight of slip improver, 0.2 parts by weight of polyoxyethylene alkyl ether (alkyl group carbon number: 12, ethylene oxide average added mole number: 13.1), The shear plain hysteresis (2HG5 value) of the cotton plain weave fabric when impregnated with 120 parts by weight of water is 7.7 g / cm or less.

  The present invention also relates to a wrinkle removing composition containing a slip improver having a shear hysteresis (2HG5 value) of 7.0 g / cm or less of the requirement (I).

  The present invention also relates to a wrinkle removing composition containing an organopolysiloxane having an amino-modified organosiloxane chain and a polyoxyalkylene chain represented by the following general formula (1).

[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² represents either R ¹ or A. A is represented by —R ³ —Z (wherein R ³ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Z represents a primary to tertiary amino group-containing group or an ammonium group-containing group). The reactive functional group is shown. a represents an integer of 2 or more, b represents an integer of 1 or more, c represents a number of 4 or more, n represents an integer of 2 to 4, and c (C _n H _2n O) may be the same or different. d represents an integer of 2 or more. Y represents a divalent organic group bonded to an adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene chain via an oxygen atom. The polysiloxane block accounts for 45 to 85% by weight of the total organopolysiloxane. These groups are selected so that the weight average molecular weight of the organopolysiloxane is 8000 or more and 500,000 or less. ]

  The present invention also relates to a wrinkle removing composition containing an organopolysiloxane having an amino group and a polyoxyalkylene group, represented by the following general formula (2).

Wherein, X is -R ^6, -O-R ^6, are -OH, R ⁶ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. R ⁴ independently represents a hydrogen atom, —OH, or a monovalent hydrocarbon having 1 to 6 carbon atoms. R ⁵ represents R ⁴ or either B or C. B and C are —R ⁷ -Q [wherein R ⁷ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Q is a primary to tertiary amino group-containing group or an ammonium group-containing group, or _{-O (C m H 2m O)} i R 8 (m is an integer of 2 to 4, i is a number of 1 to 200, i-number of (C _m H _2m O) is be the same or different R ⁸ represents a monovalent hydrocarbon group or a hydrogen atom)], or —R ⁷ —NR ¹⁰ —R ⁹ —O (C _m H _2m O) _i R ⁸ (R ⁹ represents a direct bond). Or a divalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group in which a part of hydrogen atoms is substituted with a hydroxyl group, and R ¹⁰ represents a hydrogen atom or —R ⁹ —O (C _m H _2m O _i R ⁸ represents a reactive or non-reactive functional group represented by R ⁷ , m, i and R ^{8 as} defined above. B and C may be the same or different, but groups B and C are represented by -R ⁷ -Q, B, when one of Q of C is an amino group-containing group or an ammonium group-containing group, and the other Q is _{-O (C m H 2m O)} i R 8. e, f, and g are integers of 1 or more. These groups are selected such that the organopolysiloxane has a kinematic viscosity at 25 ° C. of 9000 mm ² / s or more. ]

The present invention also relates to a textile treatment agent containing any one of the above wrinkle removal compositions.
Moreover, this invention relates to the wrinkle removal method of the textiles which dries after drying a textiles in the water dilution liquid of the processing agent of the said invention.

  The textile product treating agent containing the composition for removing wrinkles of the present invention can be used by rinsing water in a rinsing step when washing textile products or by diluting with water prepared separately to give the textile products. It is possible to effectively remove wrinkles that are generated when the product is dried, in particular, wrinkles that are generated when the product is dried with a dryer or a washing dryer.

  Wrinkles generated in clothing are considered to be caused by clothing being entangled with each other, causing fibers to break, or a gap between yarns constituting the fibers to be shifted or caught. For example, in the washing process, the clothes are entangled by the mechanical force of the washing machine, and the entanglement that once occurred in the rinsing process cannot be released, and the tangling between the clothes is further enhanced in the dehydration process. There are considerable wrinkles later. However, when hanging clothes afterwards, wrinkles are reduced by spreading one by one, or wrinkles are increased by adding weight including water during hanging, resulting in some reduction in wrinkles. be able to. On the other hand, when clothes are dried with a dryer or washing dryer, the clothes are dried while being entangled in a limited space, so in addition to the wrinkles generated during washing, new wrinkles are generated during drying. As a result, more severe wrinkles occur. It is difficult to effectively remove the wrinkles even when a conventional soft finish is used.

  In order to remove such wrinkles, it is considered necessary to efficiently impart lubricity to the fibers to reduce the friction between yarns / yarns, and to easily return the slippage and catching. The wrinkle remover composition of the present invention contains a slip improver such as modified silicone that exhibits excellent lubricity even for fibers in a wet state so that the fibers can be efficiently lubricated. That is, the effect of reducing the friction between the yarns / yarns is always manifested in a wide range from the beginning to the end of drying, that is, from the state in which the garment is still wet to the state in which drying progresses to the dry state. This is particularly important for efficiently removing wrinkles.

  As a method for estimating the lubricity of the fiber when wet, there is a method of measuring the recoverability to the stress when a shear stress is applied to the fabric. In the present invention, it has been found that the lower the shear hysteresis (2HG5 value) determined by the specific shear measurement, the higher the lubricity of the fiber. In particular, it has been found that a modified silicone having a specific structure exhibits even better lubricity even for wet fibers.

  The shear hysteresis (2HG5 value) of the present invention is a value determined by the following measurement method.

<Measurement method of shear hysteresis>
100 parts by weight of cotton plain weave fabric (for example, cotton plain weave broad cloth (# 60) manufactured by Tanigami Shoten) 0.2 parts by weight of a slip improver such as modified silicone, 0.2 parts by weight of polyoxyalkylene alkyl ether, After impregnating 120 parts by weight of moisture, the cloth was cut into 10 cm × 20 cm while maintaining the wet state, and the cloth was made to have hysteresis hysteresis (2HG5 value: shear shear) using a KES-F system manufactured by Kato Tech Co., Ltd. The hysteresis width at a quantity of 5 degrees was measured. The polyoxyalkylene alkyl ether has an alkyl group having 12 carbon atoms and an average number of moles of ethylene oxide added of 13.1, for example, polyoxyethylene lauryl ether “trade name: Emulgen 120” manufactured by Kao Corporation ( Alkyl group carbon number: 12, average addition mole number of ethylene oxide: 13.1) can be used.

  In the above measurement method, the slip improver, polyoxyalkylene alkyl ether, and moisture are mixed uniformly in advance, and then impregnated while applying mechanical force to the cloth so that a predetermined amount is obtained. Further, the maximum shear shear amount in measurement is ± tan 8 °, the shear shear rate is 0.5 ° / sec, and the tensile tension is 10 gf / cm. The sample length of the clamp part is 5 cm, and the sample width is 20 cm.

  The slip improver according to the present invention has a shear hysteresis (2HG5 value) measured by the method as described above of 7.7 g / cm or less and 7.0 g from the viewpoint of improving the lubricity of the fiber when wet. / Cm or less is preferable.

In the wrinkle removing composition according to the present invention, it is effective that the slip improver has swelling property as one means for improving the lubricity of the fiber when wet. For example, a mica piece is immersed in an aqueous solution of a wrinkle removal agent composition diluted to 0.012% by weight of a slip improver for about 3 minutes, taken out, dried at room temperature and normal pressure, and using an atomic force microscope. After measuring the height (H _D ) of the adsorbed layer on the mica piece, the same sample was gently submerged in water and maintained for 30 minutes, and the height (H _W ) of the adsorbed layer was measured in the same manner. Sometimes, a swelling ratio such that H _W / H _D is 2.5 to 30 is preferable.
When the H _W / H _D is 2.5 or more, the adsorption layer of the slip improver can be appropriately swollen to obtain a sufficient wet friction reducing effect. Further, it is preferable that H _W / H _D is 30 or less because the adsorption layer of the slip improver is not dissolved or easily dispersed in water. H _W / H _D is more preferably 2.5 to 25, still more preferably 3.5 to 20.

In the measurement of the swelling ratio, NanoScope IIIa and Extended Multi Mode AFM manufactured by Digital Instruments are used as an atomic force microscope (AFM). The measurement is performed in a tapping mode, and the shape is measured using a piezo scanner (E-type) that has been previously calibrated with Surface Topography Reference (STR10-180P) manufactured by VLSI. As the cantilever, NP-S manufactured by Veeco Instruments is used, and four cantilevers having a spring constant of 0.38 [N / m] are used among the four cantilevers having different spring constants.
As a substrate for adsorbing the slip improver, mica pieces were substituted as a fiber model, and Indian muscovite was cleaved and used. Immediately after cleaving for about 3 minutes (dilute the wrinkle remover composition so that the slip-improving agent concentration is 0.012% by weight (the dilution solution is sufficiently large relative to the mica pieces) the mica flakes performed for about 30 seconds immersion], for those dried at ambient temperature and pressure taken out to measure the H _D in the atmosphere. Further, the same sample is gently submerged in water using a submerged measurement cell, and the state is maintained for 30 minutes, and then H _W is measured. A line profile analysis is performed on the shape data obtained in the atmosphere and pure water, and the difference in height between the mica substrate and the adsorbed film is measured to calculate the swelling ratio (H _W / H _D ). For each composition, the average value measured five times is taken as the swelling ratio of the wrinkle removal composition.

  A modified silicone is preferable as the slip improver that satisfies the above requirement (I). Examples of the modified silicone include modified silicones having both a polyoxyalkylene group and an amino group-containing group or an ammonium group-containing group. The polyoxyalkylene group and the amino group-containing group or ammonium group-containing group may be contained in the same modifying group or may be composed of different modifying groups. It may be included.

  Examples of the modified silicone compound used in the wrinkle removing composition of the present invention include an organopolysiloxane having an amino-modified organosiloxane chain and a polyoxyalkylene chain represented by the above general formula (1), and the above general formula (2). And an organopolysiloxane having an amino group and a polyoxyalkylene group represented by the formula:

  In the organopolysiloxane of the general formula (1), the polysiloxane block accounts for 45 to 85% by weight of the whole organopolysiloxane, and the weight average molecular weight of the organopolysiloxane is 8,000 to 500,000, preferably 15,000 or more. 400000 or less, more desirably 25000 or more and 350,000 or less.

  Moreover, in the organopolysiloxane of the above general formula (1), it is desirable that the weight average molecular weight of each polysiloxane block is 600 to 5000, and the weight average molecular weight of each polyoxyalkylene block is 500 to 3000.

  In the present invention, the weight average molecular weight is a value measured by a conventional method using gel permeation chromatography and using chloroform as an eluent and polystyrene as a standard substance.

The siloxane block refers to a siloxane having two R ¹ groups represented by — [Si (R ¹ ) ₂ —O] _a — and —Si (R ¹ ) ₂ —O—. The ratio means the ratio of the molecular weight of the siloxane block and the molecular weight of the organopolysiloxane of the general formula (1) expressed in weight%. The above weight percentages are the organopolysiloxane was diluted in methanol -d ₄ solution, a ¹ H-NMR was measured, determined by the peaks of the spectrum.

In addition, the organopolysiloxane of the above general formula (1) has a kinematic viscosity at 25 ° C. of 500 mm ² / s or more, more preferably 10,000 mm ² / s or more, particularly 20000 mm ² / s or more. This viscosity is measured with a B-type viscometer under the condition of 25 ° C.

  The organopolysiloxane of the general formula (1) has an amino equivalent of 500 to 4500 g / mol, more preferably 800 to 2500 g / mol.

In the organopolysiloxane represented by the general formula (2), B, and C is represented by -R ⁷ -Q or ^{-R 7 -NR 10 -R 9 -O (} C m H 2m O) i R 8, A reactive or non-reactive functional group, wherein B and C are groups represented by -R ⁷ -Q, and one of B and C is an amino group-containing group or an ammonium group-containing group, the other Q in the formula is —O (C _m H _2m O) _i R ⁸ , but when one of B and C is —R ⁷ —NR ¹⁰ —R ⁹ —O (C _m H _2m O) _i R ⁸ , The other is not particularly limited.

Organopolysiloxane of the general formula (2), the kinematic viscosity at 25 ° C. and at 9000 mm ² / s or more, preferably 15000 ² / s or more. The weight average molecular weight is preferably 10,000 or more and 500,000 or less, more preferably 15,000 or more and 400,000 or less, and particularly preferably 25,000 or more and 350,000 or less. The methods for measuring these kinematic viscosities and weight average molecular weights are as described above. The organopolysiloxane of the above general formula (2) has an amino equivalent of 500 to 4500 g / mol, more preferably 800 to 2500 g / mol.

  The wrinkle removal composition of the present invention contains 0.5 to 30% by weight, more preferably 2.0 to 20% by weight, and particularly 2.0 to 15% by weight of the slip modifier such as the above-mentioned specific modified silicone. It is desirable for ensuring the blending stability and storage stability of the composition.

  The modified silicone that can be used in the present invention is a known conventional one as described in, for example, JP-A-9-183854, JP-A-6-65056, or JP-A-11-12152. It can manufacture by the combination of these synthesis methods.

  When using the modified silicone represented by the above general formula (1) or (2) as a slipping improving agent, the wrinkle removal composition of the present invention has a formulation such as emulsification / dispersion stability of the modified silicone. It is preferable to add a surfactant as long as the effects of the present invention are not impaired. Suitable surfactants include nonionic surfactants, cationic surfactants, and amphoteric surfactants. Particularly desirable is at least one selected from nonionic surfactants and cationic surfactants.

  Nonionic surfactants include 1) polyoxyalkylene alkyl ethers and polyoxyalkylene alkenyl ethers such as those represented by the following general formula (3), 2) glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters , Fatty acid esters of polyhydric alcohols selected from polyoxyalkylene sorbitol fatty acid esters and sucrose fatty acid esters, and derivatives thereof 3) polyoxyalkylene alkylphenyl ethers, for example, those represented by the following general formula (4) 4) Examples thereof include at least one selected from alkyl polyglycosides, 5) fatty acid esters of monohydric alcohols, 6) polyoxyalkylene alkyl amines, and 7) alkyl alkanol amides.

R ¹⁰ —O— (R ¹¹ O) _h —H (3)

(R ¹⁰ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms. R ¹¹ represents an alkylene group having 2 to 4 carbon atoms, and h represents an average addition mole. Number, 0.5 to 50, preferably 1 to 40, particularly preferably 1 to 20)

(R ¹² represents a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms. R ¹³ is an alkylene group having 2 to 4 carbon atoms, and s is the average number of moles added. 0.5-30, preferably 1-20, particularly preferably 1-10)

  In the above 2), the fatty acid constituting the ester preferably has 8 to 22 carbon atoms. In the above 4), the alkyl group preferably has 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, and the average degree of condensation of the sugar skeleton is preferably 0.3 to 5. In the above 5), the monohydric alcohol preferably has 8 to 22 carbon atoms and more preferably 12 to 18 carbon atoms, and the fatty acid preferably has 8 to 22 carbon atoms and further 12 to 18 carbon atoms. In the above 6), the oxyalkylene group preferably has 2 to 4 carbon atoms, and the alkyl group preferably has 8 to 22 carbon atoms. The above 7) is a compound in which an alkyl group having 8 to 22 carbon atoms and a hydroxyalkyl group having 2 to 4 carbon atoms are interposed via an amide bond, and further an alkyl group having 12 to 18 carbon atoms and a hydroxy group having 2 to 3 carbon atoms. A compound in which an alkyl group is interposed via an amide bond is preferable. As the nonionic surfactant, those selected from the above 1) and 2) are particularly preferable.

  The weight ratio [(X) / (Y)] of the nonionic surfactant (X) to the modified silicone (Y) is preferably 0.1 to 5, more preferably 0.2 to 3, and particularly preferably 0.4 to 2. A nonionic surfactant may be mix | blended by 1 type and may use 2 or more types.

Examples of the cationic surfactant include a mono long chain alkyl quaternary ammonium salt, a di long chain alkyl quaternary ammonium salt, and a tri long chain alkyl quaternary ammonium salt. Examples of the amphoteric surfactant include amine oxide, sulfobetaine, carbobetaine and the like. Examples of the anionic surfactant include alkylbenzene sulfonic acid or a salt thereof, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate ester salt, olefin sulfonate, alkane sulfonate, fatty acid salt, and the like. Since it impairs performance, it must be used with care.
Furthermore, for the purpose of improving the preferred appearance and storage stability, an organic solvent can be blended to such an extent that the performance of the present invention is not impaired.

  As the slip improver of the present invention, among (a) amino-modified silicone and (b) three groups bonded to a nitrogen atom, 1 or 2 is a hydrocarbon group having 8 to 20 carbon atoms, and the remaining is the number of carbon atoms. A tertiary amine which is a hydrocarbon group which may be substituted with 1 to 3 hydroxy groups, a neutralized product thereof or a quaternized product thereof, (a) component / (b) component = 9/1 to 5/5 Those containing at a weight ratio of

Examples of the amino-modified silicone as component (a) include amino-modified silicone compounds described in JP-A-2001-49582, JP-A-2001-192773, JP-A-2002-371474, JP-A-8-325952, JP-A-10-131054, and the like. Can be used. Component (a), kinematic viscosity 25 ° C. (can be determined by the Ostwald-type viscometer), preferably 100~20000mm ² / s, more preferably 200~10000mm ² / s, particularly preferably 500～5000Mm ² / S, amino equivalent (molecular weight per nitrogen atom, amino equivalent = molecular weight / number of N atoms. The molecular weight is a value obtained by gel permeation chromatography using polystyrene as a standard, and the number of nitrogen atoms is The amino-modified silicone compound is preferably 400 to 8000, more preferably 600 to 5000, and particularly preferably 800 to 3000.

  (A) As a suitable specific example of a component, the compound represented by General formula (5) is mentioned.

[Wherein R ^5a represents an alkyl group having 1 to 3 carbon atoms, a hydroxy group, —OR ^5d (where R ^5d is an alkyl group having 1 to 3 carbon atoms) or a hydrogen atom, and R ^5b represents 1 to 3 carbon atoms. An alkyl group, a hydroxy group or a hydrogen atom. E represents a side chain having at least one amino group, and R ^5c represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. j represents a number of 10 to 10,000, k represents a number of 1 to 1,000, and represents a number having a weight average molecular weight of 2,000 to 1,000,000. R ^5a , R ^5b , R ^5c and R ^5d may be the same or different, and a plurality of R ^5b may be the same or different. ]

In the general formula (5), R ^5a is preferably a methyl group or a hydroxy group, R ^5b is preferably a methyl group or a hydroxy group, R ^5c is preferably a methyl group or a hydrogen atom, and R ^5d 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] p -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] q -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)] r -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -NH-cyclo-} C 5 H 11
Here, p, q, and r are numbers from 1 to 30, respectively.

The component (a) of the present invention is, for example, the formula (6)
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ (6)
The hydrolyzate obtained by hydrolyzing the organoalkoxysilane represented by the following formula with excess water and dimethylcyclopolysiloxane are heated to 80 to 110 ° C. using a basic catalyst such as sodium hydroxide. The reaction mixture is allowed to equilibrate and neutralize the basic catalyst with an acid when the reaction mixture reaches a desired viscosity (see JP-A-53-98499).

As the component (a) 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), TSF4708 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 2800), Nippon Unicar Co., Ltd. SS-3551 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 1600), SS- 3552 (viscosity 700 mm ² / s (25 ° C), amino equivalent 7000), FZ-3705 (viscosity 250 mm ² / s (25 ° C), amino equivalent 4000), FZ-319 (viscosity 2000 mm ² / s (25 ° C)), Amino equivalent 4000), SF8451C (viscosity 600 mm) manufactured by Toray Dow Corning Silicone Co., Ltd. ² / s (25 ° C.), amino equivalent 1700), SF8452C (viscosity 700 mm ² / s (25 ° C.), amino equivalent 6400), SF8457C (viscosity 1200 mm ² / s (25 ° C.), amino equivalent 1800), SF8417 (viscosity) 1200 mm ² / s (25 ° C.), amino equivalent 1800), BY16-849 (viscosity 1300 mm ² / s (25 ° C.), amino equivalent 600), BY16-850 (viscosity 1100 mm ² / s (25 ° C.), amino equivalent 1100 ), BY16-892 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 2000), BY16-879B (viscosity 1190 mm ² / s (25 ° C.), amino equivalent 8000), BY16-872 (viscosity 20000 mm ² / s ( 25 ° C.), amino equivalent 1800), KF857, KF85 manufactured by Shin-Etsu Chemical Co., Ltd. , KF859, KF862, KF8001, KF880 , manufactured by Asahi Kasei Wacker Silicone (Ltd.) WR300 (viscosity ^{600mm 2 / s (25 ℃)} , amino eq 3300), WR1100 (viscosity ^{5000mm 2 / s (25 ℃)} , amino equivalent 7000) WR 1600 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 1700), WT 1650 (viscosity 1000 mm ² / s (25 ° C.), amino equivalent 1700), and the like.

  Of the three groups bonded to the nitrogen atom of component (b) of the present invention, one or two are substituted with a hydrocarbon group having 8 to 20 carbon atoms, and the rest are substituted with a hydroxy group having 1 to 3 carbon atoms. Examples of the tertiary amine which is a hydrocarbon group, a neutralized product thereof or a quaternized product thereof may include a tertiary amine represented by the general formula (6), a neutralized product thereof or a quaternized product thereof.

[In the formula, R ^6a is a hydrocarbon group having 8 to 20 carbon atoms, R ^6b is a hydrocarbon group which may be substituted with a hydrocarbon group having 8 to 20 carbon atoms or a hydroxy group having 1 to 3 carbon atoms, R ^6c represents a hydrocarbon group which may be substituted with a hydroxy group having 1 to 3 carbon atoms. ]

In the general formula (6), R ^6a is preferably an alkyl group and / or alkenyl group having 8 to 20 carbon atoms, particularly an alkyl group having 12 to 18 carbon atoms, and R ^6b is an alkyl group having 8 to 20 carbon atoms and An alkenyl group, particularly an alkyl group having 12 to 18 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, particularly a methyl group is preferred. R ^6c is preferably an alkyl group having 1 to 3 carbon atoms, particularly a methyl group. Examples of the neutralized product of the tertiary amine include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and salts of organic acids such as acetic acid, lactic acid, glycolic acid, citric acid, succinic acid and maleic acid. Examples of the quaternized product of the tertiary amine include those quaternized with an alkyl halide having 1 to 4 carbon atoms such as methyl chloride or a dialkyl sulfate having 2 to 6 carbon atoms.

The weight ratio of the component (a) to the component (b) is preferably (a) component / (b) component = 9/1 to 5/5, and 8.5 / 1 in order to obtain a good slip improvement effect. 5 to 6/4 is more preferable.
It is preferable that the component (a) and the component (b) are sufficiently mixed and then mixed with the aqueous phase to obtain a slip improver composition.

  In the textile product treating agent containing the slip improver composition of the present invention, additives (for example, antistatic agents, perfumes, antibacterial agents, bactericides, etc.) that are usually blended in fiber finishes, etc. It can mix | blend to the grade which does not impair.

  The balance of the textile treatment agent of the present invention can be water, and the pH at 20 ° C. is preferably 2 to 9, and more preferably 3 to 8.

  The present invention relates to a method for removing wrinkles from a textile product in which the textile product is immersed in a water-diluted solution of the treatment agent of the present invention and then dried. Drying can be performed by a dryer. That is, after the textile product is preliminarily treated with a water-diluted solution of the treatment agent, the textile product is dried with a dryer or a washing dryer to remove wrinkles of the textile product. The dipping treatment may be performed using a washing basin or a washstand, but it is usually simple and desirable to perform it in a washing rinsing step using a washing machine. The bath ratio during immersing [amount of rinsing water (L) / weight of clothing (kg)] is in the range of about 5 to 20 depending on the type of washing machine used, and the method of the present invention is also carried out in this range. It is desirable. In the wrinkle removal method of the present invention, the concentration of the slip improver such as modified silicone in the water diluted solution (rinsing solution) is preferably 0.001 to 0.1% by weight, more preferably 0.002 to 0.05% by weight. When the concentration of the slip improver is within this range, a sufficient wrinkle removal effect can be obtained, the texture inherent in clothing is not impaired, unnecessary water repellency is not imparted, and also from an economic viewpoint. It is advantageous. By treating the fiber product in a state where the concentration of the slip improver as described above is relatively low, the slip improver can be uniformly applied to the fiber product, and the effects of the present invention are sufficiently exhibited.

  Textile products that are the subject of the present invention include natural fibers such as cellulose fibers and animal hair fibers, regenerated cellulose fibers, semi-synthetic fibers, polyamide fibers, polyester fibers, acrylic fibers and the like, woven fabrics, knitted fabrics, Nonwoven fabrics, laminated fabrics, multilayer woven fabrics, multi-woven fabrics and the like, and processed products thereof are mainly used in general households. Specific examples include clothes such as shirts, suits, slacks, jackets, skirts, blouses, T-shirts, polo shirts, trainers, sheets, curtains, towels, and the like.

  Moreover, drying after immersing a textile product in the water dilution liquid of the processing agent of this invention can be performed by natural drying. That is, the treatment agent of the present invention has an excellent wrinkle removing effect not only in the case of drying a textile product using a dryer or a washing dryer, but also in the case of hanging and drying with a fishing rod or a hanger. The term “hanging and drying” as used herein refers to a normal manner of hanging and drying that is performed in a general home, and includes indoor drying, sun drying, or drying in a bathroom with a drying function.

  The silicone compounds used in Examples and Comparative Examples are shown below, and the physical properties of each silicone compound and the measurement results of shear hysteresis are shown together in Table 1.

Examples 1-5 and Comparative Examples 1-5
Wrinkle removing compositions having the compositions shown in Table 2 were prepared. As a washing and drying machine, a drum washing machine (TW-742EX washing capacity 7 kg, drying capacity 4 kg) manufactured by Toshiba Corporation was used. The clothes described below (total weight 2.5 kg) were put in a washing tub, and 40 g of a wrinkle removing composition was set in advance in an automatic charging port for a softening finish, and washing was performed on a standard course. As the detergent, “Attack” manufactured by Kao Corporation was used, and the wrinkle removing composition set in the automatic charging port was added into the tank for the second time by rinsing. The bath ratio during the rinsing process was about 6. After washing was completed, the drying mode was switched to the drying mode.

  After drying, the clothes were taken out, and the wrinkles of the T-shirt were determined according to the following evaluation criteria using 5 dedicated panelists. The results are shown in Table 2.

<Clothing>
6 underwear (100% cotton), 3 polo shirts (100% cotton), 2 polo shirts (cotton / polyester blend), 5 T-shirts (100% cotton), total weight 2.5kg

"Wrinkle criteria"
5 points: no wrinkles 4 points: almost no wrinkles 3 points: some wrinkles remain 2 points: considerable wrinkles remain 1 point: significant wrinkles remain

Nonionic surfactant: polyoxyethylene lauryl ether (average added mole number of ethylene oxide: 13.1)
PH adjuster: 0.5N-NaOH aqueous solution or 0.5N-HCl aqueous solution

Examples 6 to 10 and Comparative Examples 6 to 9
(Preparation of wrinkle remover composition)
A wrinkle removing composition having the composition shown in Table 3 below was prepared using the silicone compound shown in Table 1. When a silicone compound and a nonionic surfactant (the same as in Example 1) were mixed well in advance, water was added dropwise with stirring. After adding a fragrance | flavor, pH was adjusted to 6.0 using the pH adjuster (the same thing as Example 1 etc.), and the predetermined composition was obtained. All preparations were performed at room temperature.

(Processing method)
Using a fully automatic washing machine (PAM NW-D8CX) manufactured by Hitachi Home and Life Solutions Co., Ltd. 30 g of a wrinkle removing composition was set at the inlet, and washing was performed on a standard course. As the detergent, “Attack” manufactured by Kao Corporation was used, and the wrinkle removing composition set in the automatic charging port was added into the tank for the second time by rinsing. The bath ratio during the rinsing process was about 14. After washing, the clothes were taken out, shaped while tapping, and hung on a hanger and dried indoors (20 ° C., 65% RH).

  After drying, wrinkle determination of the T-shirt was performed according to the following evaluation criteria using 5 dedicated panelists. The results are also shown in Table 3.

<Clothing>
6 underwear (100% cotton), 3 polo shirts (100% cotton), 2 polo shirts (cotton / polyester blend), 5 T-shirts (100% cotton), total weight 2.5kg

"Wrinkle criteria"
5 points: no wrinkles 4 points: almost no wrinkles 3 points: some wrinkles remain 2 points: considerable wrinkles remain 1 point: significant wrinkles remain

Examples 11-19 and Comparative Examples 10-15
A wrinkle removing composition having the composition shown in Table 4 was prepared using each component shown in Table 4. The swelling ratio was measured for this wrinkle remover composition. The swelling ratio (H _W / H _D ) is the height of the adsorption layer when dried (H _D ) and the height of the adsorption layer when wet by the above method using components other than fragrance and water as a slip improver. It was determined by measuring (H _W ). Moreover, the wrinkle removal performance was evaluated by the following method. These results are shown in Table 4.
In addition, about the slip improving agent used in Examples 16-19 and Comparative Examples 12-15, the shear hysteresis was measured by the method shown in the said requirement (I). The results are shown in Table 5.

<Wrinkle removal performance evaluation method>
(1) Hanging and drying drying As a washing machine, a fully automatic washing machine (National NAF70PX5, water volume 48 L) manufactured by Matsushita Electric Industrial Co., Ltd. was used. The clothes described below (total weight: 3.0 kg) were put in a washing tub, and 40 g of a wrinkle removing composition was set in advance in an automatic charging port for a softening finish, and washing was performed on a standard course. As the detergent, “Attack” manufactured by Kao Corporation was used, and the wrinkle removing composition set in the automatic charging port was added into the tank for the second time by rinsing. The bath ratio during the rinsing process was about 16. After washing, the clothes were taken out, shaped while tapping, and hung on a hanger and dried indoors (20 ° C., 65% RH).
Clothing: 10 underwear (100% cotton), 3 polo shirts (100% cotton), 2 polo shirts (polyester blend), 5 T-shirts (100% cotton), total 3.0kg

(2) Drying with a dryer A drum washing machine (TW-742EX washing capacity 7 kg, drying capacity 4 kg) manufactured by Toshiba Corporation was used as a washing dryer. The clothes described below (total weight 2.0 kg) were put in a washing tub, and 27 g of a wrinkle removing composition was set in advance in an automatic charging port for a softening finish, and washing was performed on a standard course. As the detergent, “Attack” manufactured by Kao Corporation was used, and the wrinkle removing composition set in the automatic charging port was added into the tank for the second time by rinsing. The bath ratio during the rinsing process was about 7. After washing was completed, the drying mode was switched to the drying mode.
Clothing: 2 underwear (100% cotton), 2 polo shirts (100% cotton), 2 polo shirts (polyester blend), 4 T-shirts (100% cotton), total 2.0kg

(3) Wrinkle determination After the drying, the clothing was taken out, and the T-shirt was subjected to wrinkle determination according to the following evaluation criteria using 5 dedicated panelists.

"Wrinkle criteria"
5 points: no wrinkles 4 points: almost no wrinkles 3 points: some wrinkles remain 2 points: considerable wrinkles remain 1 point: significant wrinkles remain

* 1 Amino-modified silicone (a-1): KF864 Shin-Etsu Chemical Co., Ltd., viscosity 1700mm ² / s (25 ° C), amino equivalent 3800
* 2 Amino-modified silicone (a-2): TSF4707 manufactured by GE Toshiba Silicone Co., Ltd., viscosity 10000 mm ² / s (25 ° C), amino equivalent 7000
* 3 Amino-modified silicone (a-3): BY16-872, manufactured by Toray Dow Corning Silicone Co., Ltd., viscosity 20000mm ² / s (25 ° C), amino equivalent 1800
* 4 Compound (b-1): Cotamine D86P, manufactured by Kao Corporation, distearyldimethylammonium chloride
* 5 Compound (b-2): Cotamine D2345P, Kao Corporation, dialkyl chloride (C12 to C18) dimethylammonium
* 6 Nonionic surfactant 1: Polyoxyethylene lauryl ether (average added mole number of ethylene oxide: 13.1)
* 7 Nonionic surfactant 2: Polyoxyethylene lauryl ether (average added mole number of ethylene oxide 2.9)

Claims (1)

After immersing the fiber product in an aqueous diluent (slip improving agent concentration: 0.002 to 0.05% by weight) of a fiber product treating agent containing a wrinkle removing agent composition containing the slip improving agent satisfying the following requirement (I) , a wrinkle removal process of fiber product is dried by the washing and drying machine, the slip-improving agent is represented by the general formula (1), organopolysiloxane down with an amino-modified organosiloxane chain and a polyoxyalkylene chain A method for removing wrinkles from textile products.
<Requirement (I)>
For 100 parts by weight of plain cotton fabric, 0.2 part by weight of slip improver, 0.2 parts by weight of polyoxyethylene alkyl ether (alkyl group carbon number: 12, ethylene oxide average added mole number: 13.1), The shear plain hysteresis (2HG5 value) of the cotton plain weave fabric impregnated with 120 parts by weight of water is 7.0 g / cm or less.

[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² represents either R ¹ or A. A is represented by —R ³ —Z (wherein R ³ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Z represents a primary to tertiary amino group-containing group or an ammonium group-containing group). The reactive functional group is shown. a represents an integer of 2 or more, b represents an integer of 1 or more, c represents a number of 4 or more, n represents an integer of 2 to 4, and c (C _n H _2n O) may be the same or different. d represents an integer of 2 or more. Y represents a divalent organic group bonded to an adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene chain via an oxygen atom. The polysiloxane block accounts for 45 to 85% by weight of the total organopolysiloxane. These groups are selected so that the weight average molecular weight of the organopolysiloxane is 8000 or more and 500,000 or less. ]